JP2006268024A - Method for replenishing development replenisher in automatic developing device for photosensitive lithographic printing plate and automatic developing device therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for replenishing a development replenisher in an automatic developing device for a photosensitive lithographic printing plate that can minimize variation in liquid developer sensitivity with change of conditions for development processing while making the constitution of a development section of the automatic developing device simple and low-cost, and an automatic developing device for a photosensitive lithographic printing plate. <P>SOLUTION: The electric conductivity of the liquid developer is measured in each predetermined fixed period, a development replenisher is replenished every fixed time as a time lapse replenisher in an amount based upon a set value of a time lapse replenishment rate, the development replenisher is replenished every processing of a fixed area of a photosensitive lithographic printing plate as a processing replenisher in an amount based upon a set value of a processing replenishment rate, the calculated value of the electric conductivity is calculated from the amount of the time lapse replenisher and the amount of processing replenisher. When a replenishment system is an electric conductivity system, the set value of the time lapse replenishment rate and the set value of the processing replenishment rate are increased or decreased according to the result of a comparison of the calculated value of the electric conductivity with the measured value of the electric conductivity of the liquid developer. When a replenishment system is not an electric conductivity system, the set value of the time lapse replenishment rate and the set value of the processing replenishment rate are not increased nor decreased. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a developing replenisher replenishing method for a photosensitive lithographic printing plate automatic developing apparatus and a photosensitive lithographic printing plate automatic developing apparatus, and more particularly to a technique for minimizing fluctuations in developer sensitivity to changes in development processing conditions.

  In general, in an automatic developing device for photosensitive lithographic printing plates, as a method for managing the sensitivity of the developer, the lithographic printing plate to be processed is replenished with time with a developer replenisher in a developer tank in which the developer is stored. A developing replenisher solution aging and processing replenishment method (hereinafter referred to as “area aging reference replenishment method”) is employed in which the plate area is measured and an amount of development replenisher solution is replenished in accordance with the measured value.

  However, such an area chronological reference replenishment method requires a highly accurate planographic printing plate area measuring device in the development processing section of the automatic developing device, resulting in a complicated structure and high cost. . In addition, it is difficult to determine whether the lithographic printing plate has only one side or both sides (hereinafter referred to as “single side / both sides”) and to determine the type of plate (plates with different photosensitive layer coating amounts). For this reason, if the replenishment amount of the required development replenisher changes due to changes in the plate area, single side / both sides, and plate type of the lithographic printing plate, it becomes difficult to properly replenish the development replenishment amount. there were.

  Therefore, conventionally, as described in, for example, Patent Document 1, as a method for replenishing a developer replenisher in an automatic developing device for a photosensitive lithographic printing plate, the conductivity of the developer is measured and the measured value is obtained in advance by an experiment. Compared with the conductivity value indicating the optimum sensitivity (hereinafter referred to as “appropriate conductivity value”), a replenishment method for replenishing the developer replenisher when the measured value falls below the proper conductivity value (hereinafter referred to as “conductivity”). Called the "degree standard replenishment method"). In such a conductivity-based replenishment method, an appropriate amount of development replenisher can be replenished even if the plate area, single side / both sides, and plate type of the lithographic printing plate to be processed changes. The sensitivity of can be kept appropriate.

  However, in general, there is an empirical fact that a proper conductivity value is different between a developer that is fatigued only by carbon dioxide gas over time and a developer that is fatigued only by plate processing (silicate-based processing agent / time-dependent fatigue (carbon dioxide gas). (Fatigue) -Replenishment recovery: 65 mS / cm, Treatment fatigue-Replenishment recovery: 55 mS / cm, Non-silicate processing agent / Aging fatigue-Replenishment recovery: 56 mS / cm, Treatment fatigue-Replenishment recovery: 39 mS / cm) . Therefore, in the above-mentioned conductivity reference replenishment method, when the processing frequency, for example, the processing amount per day is different from the expected amount, the ratio between the actual replenishment amount and the processing replenishment amount also differs from the expected value. The appropriate conductivity value of the entire developer in the developer tank calculated from the conductivity changes, and there is a discrepancy with the appropriate conductivity value set in advance, making it impossible to maintain the developer sensitivity properly. Problems arise.

  On the other hand, in Patent Document 2 and Patent Document 3 improved from Patent Document 2, the replenishment time interval is measured, the replenishment amount required over time is obtained, and the replenishment amount per time is calculated from this replenishment amount. By subtracting the replenishment amount as the processing replenishment amount, the processing replenishment amount and the temporal replenishment amount are obtained, respectively, and the developer conductivity is calculated with the conductivity value calculated from the ratio of the obtained processing replenishment amount and the temporal replenishment amount. Proposes an automatic development device to manage. According to this method, even if the plate area, one side / both sides, and the plate type of the lithographic printing plate to be processed are changed, an appropriate developer conductivity value can be obtained by estimating the ratio between the processing replenishment amount and the replenishment amount with time. Can be determined. However, in these methods, the difference in the required amount of replenishment over time resulting from the difference in developer fatigue due to carbon dioxide gas between the operation and stop of the automatic developing device (difference in developer temperature, presence or absence of liquid circulation, etc.) Cannot be detected, and an accurate ratio between the replenishment amount and the replenishment amount with time cannot be obtained from the replenishment time interval over which the automatic developing apparatus is stopped.

Therefore, in Patent Document 4, a method for calculating the conductivity reference value using different arithmetic expressions at the time of starting the automatic developing device for replenishing a replenisher required when the automatic developing device is stopped and when the automatic developing device is in operation. is suggesting.
Japanese Patent No. 2516022 (Japanese Patent Laid-Open No. 64-21451) JP-A-9-96910 JP-A-2004-219442 JP 2004-212681 A

  However, in the above-described method of managing the developer conductivity with the conductivity value calculated from the ratio of the processing replenishment amount calculated from the replenishment time interval and the replenishment amount with time, when the fatigue conditions with time differ, There is a problem that the ratio of the replenishment amount with time cannot be obtained. The case where the fatigue conditions with time are different is, for example, when the carbon dioxide concentration in the surrounding atmosphere changes, or when the wind speed in the surrounding atmosphere changes, etc. It is known that it changes depending on the number of workers, and the latter changes depending on the position of the air outlet of the air conditioner and the air volume. In other words, in the above replenishment method, the amount of replenishment over time per unit time and the amount of replenishment over time per actual unit time determined in advance by experiments according to the increase or decrease in the number of workers in the room or the state of the air conditioner. There is a concern that the correct replenishment amount cannot be obtained from the replenishment time interval and an incorrect target conductivity value is calculated.

  In the case of electrode-type conductivity sensors, it is known that depending on the combination of developer and plate material, dirt may adhere to the electrode surface and cause malfunctions. In the degree replenishment method, there is a risk that the developer activity may not be managed at all due to an abnormality in the measured value of the conductivity sensor due to adhesion of electrodes and the like.

  In view of such circumstances, the present invention is a photosensitive lithographic printing plate automatic development capable of minimizing fluctuations in developer sensitivity to changes in development processing conditions while having a simple and inexpensive development unit of an automatic development apparatus. It is an object of the present invention to provide a developing replenisher replenishing method for an apparatus and a photosensitive lithographic printing plate automatic developing apparatus.

The object of the present invention has been achieved by the following constitutions (1) to (4).
(1) Development of an exposed photosensitive lithographic printing plate with a developer containing an electrolyte, and automatic development of a photosensitive lithographic printing plate that replenishes the developer replenisher and keeps the developer activity constant. A method for replenishing a developing replenisher of an apparatus,
The developer conductivity is measured at predetermined intervals, and an amount of development replenisher based on a predetermined replenishment amount set value is replenished as a time-dependent replenisher every fixed time. Replenishing the amount of development replenisher based on a predetermined processing replenishment amount as a processing replenisher, and calculating the conductivity calculation value from the amount of the replenisher over time and the amount of the processing replenisher,
When the predetermined replenishment method set value is a value indicating the conductivity method, based on the result of comparing the conductivity calculation value and the measured value of the developer conductivity, the replenishment amount set value with time Increase or decrease the processing replenishment amount set value,
In the photosensitive lithographic printing plate automatic developing device, the replenishment method setting value does not increase or decrease the replenishment amount setting value with time and the processing replenishment amount setting value when the replenishment method setting value is not a value indicating the conductivity method. Development replenisher replenishment method.

(2) Development of an exposed photosensitive lithographic printing plate with a developer containing an electrolyte, and automatic development of a photosensitive lithographic printing plate that replenishes the developer replenisher and keeps the developer activity constant. A method for replenishing a developing replenisher of an apparatus,
The developer conductivity value is measured every predetermined period, and the predetermined replenishment amount set value is integrated into the replenishment amount integrated value every predetermined time, and predetermined for each plate processing of a certain area. The processing replenishment amount set value is added to the processing replenishment amount integrated value, the replenisher replacement rate that is the ratio of the replenishment amount in the developer in the developing tank is calculated, and the replenishment over time that is the ratio of the replenisher over time in the developing tank After calculating the ratio, if the total amount of the replenishment amount integrated value over time and the processing replenishment amount integrated value exceeds a predetermined replenishment amount minimum value,
When the predetermined replenishment method setting value is a value indicating the conductivity method, the following (A-1), (A-2), (A-3), (A-4), (A-5), (A-6) is executed, and when the replenishment method set value is not a value indicating the conductivity method, the following (B-1) and (B-2) are executed. A developing replenisher replenishing method for a printing plate automatic developing apparatus.
(A-1) Measure the elapsed time from the previous replenishment time to the present time, calculate the first conductivity calculation value from the elapsed time and the replenisher replacement rate,
(A-2) changing the replenishment amount setting value with time and the processing replenishment amount setting value according to the result of comparing the first conductivity calculation value and the measured developer conductivity value,
(A-3) calculating a second conductivity calculation value using the replenisher replacement rate and the replenishment ratio with time,
(A-4) changing the replenishment amount setting value with time and the processing replenishment amount setting value according to a result of comparing the second conductivity calculation value and the measured developer conductivity value,
(A-5) Replenish the developer in the developing tank with a replenisher of the total amount of the replenishment amount integrated over time and the processing replenishment amount integrated value;
(A-6) The integrated replenishment amount with time and the processing replenishment amount integrated value are initialized.
(B-1) replenishing the developer in the developing tank with a replenisher of a total amount of the replenishment amount integrated value over time and the processing replenishment amount integrated value;
(B-2) The integrated replenishment amount with time and the integrated replenishment amount with processing are initialized.

(3) A conductivity value in which the activity of the developer is within an appropriate range is calculated as a target conductivity value, and a predetermined replenishment method setting is a value indicating the conductivity method immediately after the operation of the automatic developing device is started. In this case, execute (C-1), (C-2), (C-3), (C-4) below,
(2) The replenishing solution is replenished to the developer according to the time during which the automatic developing device has been stopped when the replenishing method set value is not a value indicating the conductivity method. Development replenisher replenishment method of the photosensitive lithographic printing plate automatic developing apparatus.
(C-1) Measure the conductivity of the developer at fixed intervals.
(C-2) When the measured developer conductivity value is lower than the target conductivity value, a predetermined amount of developer replenisher is replenished to the developer,
(C-3) Update the target conductivity value with the replenishment,
(C-4) Repeat (C-1), (C-2), and (C-3) until the developer conductivity value exceeds the target conductivity.
(4) A photosensitive lithographic printing plate automatic developing apparatus that develops a large number of exposed photosensitive lithographic printing plates with a developer containing an electrolyte and maintains constant developer activity,
A development processing unit for developing the photosensitive lithographic printing plate with a developer;
Conductivity measuring means for measuring the conductivity of the developer;
Developer replenishing means for replenishing the developer with a developer replenisher;
A photosensitive lithographic printing plate automatic developing device comprising: replenishing the developer with the developer replenisher based on the developer replenisher replenishing method according to (2) or (3).

  When developing a large number of exposed photosensitive lithographic printing plates with a developer composed of an aqueous solution containing an electrolyte, the time elapsed according to the current environmental and processing conditions using the measured developer conductivity. By calculating the replenishment amount and the processing replenishment amount, and performing replenishment based on this to maintain the developer sensitivity stable, the processing frequency (the processing replenishment amount and the replenishment amount with time) is achieved despite the simple and inexpensive device configuration. If the environmental carbon dioxide concentration changes or when different types of photosensitive materials are processed, the values are automatically brought close to the corresponding values. Therefore, automatic development processing with high sensitivity stability can be realized. In addition, even when the conductivity sensor breaks down, it is possible to switch to an alternative replenishment method, so that it is possible to continue processing the plate material.

  In the present invention, the “developing replenisher” refers to a processing liquid that is replenished to keep development performance constant. In general, as this replenisher, there are those prepared by diluting the replenisher stock solution with a diluent (eg, water) and those using the replenisher stock solution as it is without dilution. “Liquid” means a solution prepared by diluting a replenisher stock solution with a diluent. Further, as a replenishment method, there are a method of replenishing the developer with a replenisher prepared by diluting in advance, and a method of directly replenishing the developer with a replenisher stock solution and a diluted solution separately.

  In the present invention, known means such as an AC conductivity meter, an AC bridge meter, or other conductivity meter can be used as the conductivity sensor for measuring the conductivity value of the developer. The measurement current value and oscillation frequency of the measuring device vary depending on the developer composition, etc., but the current value is low to some extent in order to prevent electrolysis of the water-soluble developer. It is preferably several hundred mA to several μA. Further, the frequency is preferably several hundred Hz to several hundred kHz from the relationship with the electrostatic capacitance component in the developer.

  The conductivity value of the developer containing the electrolyte depends on the temperature of the aqueous solution, and the value decreases as the liquid temperature increases. Therefore, it is more preferable to measure the conductivity value with a measuring instrument equipped with a temperature sensor and a temperature compensation circuit. In the control device that controls replenishment, it is also possible to compensate for the temperature by converting the actually measured liquid resistance value and liquid temperature into a conductivity value at a predetermined temperature. The sensor installation position of the AC conductivity meter, AC bridge meter, or other conductivity meter may be a place where the AC conductivity value of the developer can be measured by being immersed in the developer at the time of measurement. The developer circulation system, particularly in the developing tank or the circulation pipe is a preferable position. Moreover, as a detection part, the well-known measurement cell which used platinum, stainless steel, etc. for the electrode can be used.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of a developing replenisher replenishing method for a photosensitive lithographic printing plate automatic developing apparatus and a photosensitive lithographic printing plate automatic developing apparatus according to the present invention will be described below.
First, an alkaline developer used in the automatic developing apparatus of the present invention will be described. The alkaline developer of the present invention can be used as a developer to be charged at the start of development (referred to as a development starter) or a development replenisher. Hereinafter, unless otherwise specified, the development starter and the development replenisher are collectively referred to as a developer.
The developer of the present invention has an alkaline aqueous solution as a basic composition, and can be appropriately selected from conventionally known alkaline aqueous solutions.
Examples of the alkaline aqueous solution include a developer composed of an alkali silicate or non-reducing sugar and a base, and those having a pH of 12.5 to 14.0 are particularly preferable.
The alkali silicate exhibits alkalinity when dissolved in water, and examples thereof include alkali metal silicates such as sodium silicate, potassium silicate and lithium silicate, and ammonium silicate.
The alkali silicate may be used alone or in combination of two or more.

The alkali aqueous solution can be easily developed by adjusting the mixing ratio and concentration of silicon oxide SiO ₂ and alkali oxide M ₂ O (M represents an alkali metal or ammonium group), which is a silicate component. Can be adjusted to.
Among the alkali aqueous solutions, those having a mixing ratio (SiO ₂ / M ₂ O: molar ratio) of the silicon oxide SiO ₂ and the alkali oxide M ₂ O of 0.5 to 3.0 are preferably in this range. In addition, a general-purpose aluminum plate is rarely etched as a support for a lithographic printing plate, and developability is good. SiO ₂ / M ₂ O (molar ratio) is more preferably 1.0 to 2.0.

  The concentration of the alkali silicate in the developer is preferably 1 to 10% by mass, and 3 to 8% by mass with respect to the mass of the aqueous alkali solution, from the viewpoint of good developability and processing capability and convenience of waste liquid treatment. More preferably, 4 to 7% by mass is most preferable.

In a developer composed of a non-reducing sugar and a base, the non-reducing sugar means a sugar that does not have a reducing property because it does not have a free aldehyde group or a ketone group. Glycosides in which saccharide reducing groups and non-saccharides are combined, and sugar alcohols reduced by hydrogenation of saccharides. Any of these can be preferably used in the present invention.
Examples of trehalose-type oligosaccharides include saccharose and trehalose, and examples of the glycoside include alkyl glycosides, phenol glycosides, and mustard oil glycosides.
Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-digit, D, L-talit, dulcit, allozulcit, meso-inosit and the like. . Furthermore, maltitol obtained by hydrogenation of a disaccharide, a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide, and the like can also be suitably exemplified.

Among the above, as the non-reducing sugar, sugar alcohol and saccharose are preferable, and among them, D-sorbite, meso-inosit, saccharose, and reduced starch syrup are more preferable because they have a buffering action in an appropriate pH range.
These non-reducing sugars may be used singly or in combination of two or more. The proportion of the non-reducing sugar in the developer is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass.

In the alkali silicate or non-reducing sugar, an alkali agent as a base can be appropriately selected from conventionally known compounds and combined.
Examples of the alkali agent include sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, carbonic acid. Inorganic alkaline agents such as sodium, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, potassium citrate, tripotassium citrate, sodium citrate, etc. Is mentioned.

Furthermore, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethylene An organic alkali agent such as imine, ethylenediamine, pyridine and the like can also be suitably exemplified.
These alkaline agents may be used alone or in combination of two or more.
Of these, sodium hydroxide and potassium hydroxide are preferred. The reason is that the pH can be adjusted in a wide pH range by adjusting the amount added to the non-reducing sugar. Further, trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are preferable because they have a buffering action.

The developer of the present invention contains at least one selected from the group consisting of carboxyalkylthiosuccinic anhydride, carboxyalkylthiosuccinic acid and salts thereof.
Examples of at least one selected from the group consisting of the carboxyalkylthiosuccinic anhydride, carboxyalkylthiosuccinic acid and salts thereof include compounds represented by the following general formula (I) or (II). In the developer of the present invention, these compounds can be used alone or in combination of two or more.

(In formula (I), R ¹ represents an alkylene group having 1 to 30 carbon atoms, and M ¹ represents a hydrogen atom, a metal atom, or ammonium.)

(In formula (II), R ² represents an alkylene group having 1 to 30 carbon atoms, and M ² , M ³ and M ⁴ each independently represents a hydrogen atom, a metal atom or ammonium.)

In the carboxyalkylthiosuccinic anhydride represented by the above formula (I) or a salt thereof, the carboxyalkylthiosuccinic acid represented by the above formula (II) or a salt thereof, R ¹ and R ² each have 1 to 30 carbon atoms. An alkylene group, which may be linear or branched. Specific examples of the alkylene group include ethylene group, propylene group, butylene group, pentylene group, hexylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene. Group, octadecylene group, nonadecylene group, eicosylene group, heicosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, octacosylene group, nonacosylene group, triaconylene group and the like. Among these, an alkylene group having 1 to 18 carbon atoms is preferable.

In the above formula (I) and the above formula (II), the metal atoms represented by M ¹ , M ² , M ³ and M ⁴ are monovalent metal atoms, specifically lithium, sodium, potassium, etc. Examples thereof include monovalent metal atoms which are alkali metals, calcium, magnesium, zinc, aluminum, iron, cobalt, nickel, copper, tin and the like. Of these, lithium, sodium, potassium, calcium, and magnesium are preferable. Here, for a metal atom having a valence of 2 or more as a metal atom, a virtual metal atom obtained by dividing the metal atom by its valence is a metal atom corresponding to a monovalent, for example, a divalent metal such as calcium or magnesium. In some cases, it is expressed as Ca _1/2 , Mg _1/2 or the like, and in the case of a trivalent metal such as aluminum, it is expressed as Al _1/3 . Actually, in the compound represented by the general formula (I), in the case of a divalent metal atom, one of them has a structure of bridging two molecules, and in the case of a trivalent metal, one of them has three molecules. It becomes the structure which bridge | crosslinks. On the other hand, in the compound represented by the general formula (II), one divalent metal atom corresponds to two of M ² , M ³ and M ⁴ . The divalent metal atom may correspond to two of M ² , M ³ and M ⁴ in one molecule of the compound represented by the general formula (II), and is represented by the general formula (II). It corresponds to 2 out of 2 molecules of M ² , M ³ and M ⁴ of the compound, and may have a structure in which 2 molecules are cross-linked.
Further, the trivalent metal atom corresponds to 3 of 1 to 3 molecules of M ² , M ³ and M ⁴ of the compound represented by the general formula (II).

In the above formula (I) and the above formula (II), ammonium represented by M ¹ , M ² , M ³ and M ⁴ includes NH ₄ ⁺ , primary ammonium, secondary ammonium and tertiary ammonium. In primary ammonium, secondary ammonium and tertiary ammonium, the substituent may be an aliphatic group having 1 to 24 carbon atoms and an aromatic group, and the aliphatic group and aromatic group have a substituent. For example, it may be substituted with a hydroxyl group or the like. In secondary ammonium and tertiary ammonium, each di- and tri-substituent may be the same or different, and may be bonded to each other to form a ring.
Examples of organic amines from which the above ammonium salts are derived include aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, Examples include alkanolamines such as triisopropanolamine, aromatic amines such as aniline, and heterocyclic amines such as morpholine, pyridine, pyrrolidine, and piperidine. Of these, morpholine and alkanolamine are particularly preferred.

  The compound represented by the general formula (I) or (II) used in the present invention can be produced by a conventional method, for example, by the method disclosed in JP-A-8-337789. For example, a carboxyalkylthio succinic anhydride or a carboxyalkylthio succinic anhydride represented by the general formula (I) is obtained by adding mercaptocarboxylic acid or a salt thereof to maleic anhydride. In addition, the compound represented by the general formula (I) thus obtained is hydrolyzed and neutralized with an appropriate basic compound as it is to obtain a salt. Can be obtained.

  In the developer of the present invention, the content of at least one selected from the group consisting of carboxyalkylthiosuccinic anhydride, carboxyalkylthiosuccinic acid and salts thereof is suitably 0.001 to 10.0% by mass, preferably It is 0.01-1.0 mass%, More preferably, it is 0.05-0.5 mass%.

As described above, as the alkaline developer, a developer containing an alkali silicate or non-reducing sugar and a base is used, and Li ⁺ , Na ⁺ , K ⁺ , and NH ₄ ⁺ are conventionally used as the cationic component, In a system containing a large amount of cations having a small ionic radius, the penetrability into the image recording layer is high and the developability is excellent. Therefore, there is a certain limit to increasing the alkali concentration, and in order to completely process the image recording layer (residual film) so as not to remain in the non-image area without causing defects in the image area, it is delicate. It was required to set a proper liquid condition.
However, by using a cation having a large ionic radius as the cation component, the penetrability of the developer into the image recording layer can be suppressed, and the image density can be reduced without reducing the alkali concentration, that is, the developability. The dissolution inhibiting effect of the part can also be improved.
As the cation component, in addition to the alkali metal cation and ammonium ion, other cations can be used.

The usage mode of the developer of the present invention is not particularly limited.
In recent years, automatic development apparatuses for printing plates have been widely used in the plate making and printing industries in order to rationalize and standardize plate making operations. The developer of the present invention can be used for development processing by an automatic development apparatus.
Such an automatic developing device generally comprises a developing unit and a post-processing unit, and comprises a printing plate conveying device, each processing tank and a spray device, and the exposed printing plate is pumped up while being conveyed horizontally. Each processing solution is sprayed from a spray nozzle and developed. In addition, recently, a method is also known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid. In such automatic processing, each processing solution can be processed while being replenished with a replenisher according to the processing amount, operating time, and the like.

  In this case, a large amount of image forming material can be processed without changing the developing solution in the developing tank for a long time by adding an aqueous solution having a higher alkali strength than the developing starting solution to the developing solution as a developing replenisher. Also in the plate making method of the present invention, it is a preferable aspect to adopt this replenishment method.

  Various surfactants, organic solvents, and the like can be added to the developer as necessary for the purpose of promoting and suppressing developability, dispersing development residue, and improving ink affinity of the printing plate image area.

The surfactant can be selected from nonionic, anionic, cationic or amphoteric surfactants.
Examples of nonionic surfactants include polyethylene glycols such as polyethylene glycol and polyethylene glycol polypropylene glycol block copolymers, polyethylene glycol alkyl ethers such as polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol oleyl ether, and polyethylene glycol behenyl ether. Polyethylene glycol polypropylene glycol cetyl ether, polyethylene glycol polypropylene glycol decyl tetradecyl ether and other polyethylene glycol polypropylene glycol alkyl ethers, polyethylene glycol octyl phenyl ether, polyethylene glycol nonyl phenyl ether and other polyesters Polyethylene glycol fatty acid esters such as lenglycol alkylphenyl ethers, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol stearate, polyethylene glycol distearate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate Glyceryl monomyristate, glyceryl monostearate, glyceryl monoisostearate, glyceryl distearate, glyceryl monooleate, glyceryl dioleate and the like, and polyethylene oxide adducts thereof, sorbitan monopalmitate, mono Sorbitan stearate, sorbitan tristearate, mono Sorbitan fatty acid esters such as sorbitan oleate and sorbitan trioleate, and polyethylene oxide adducts thereof, sorbite monosorbate, sorbite tetrastearate, sorbite hexastearate, sorbite tetraoleate, and the like Examples thereof include polyethylene oxide adducts and polyethylene oxide adducts of castor oil.

  Examples of the anionic surfactant include fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid ester salts, α-olefin sulfonic acid salts, linear alkyl benzene sulfonic acid salts, branched alkyl benzene sulfonic acid. Acid salts, alkylnaphthalene sulfonates, alkylphenoxy polyoxyethylenepropyl sulfonates, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, Petroleum sulfonates, sulfated beef tallow oil, fatty acid alkyl ester sulfates, alkyl sulfate esters, polyoxyethylene alkyl ether sulfates, fatty acid compounds Glyceryl sulfate ester salt, polyoxyethylene alkyl phenyl ether sulfate ester salt, polyoxyethylene styryl phenyl ether sulfate ester salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate ester salt, polyoxyethylene alkyl phenyl ether phosphate ester Preferable examples include salts, partially saponified products of styrene / maleic anhydride copolymer, partially saponified products of olefin / maleic anhydride copolymer, and naphthalene sulfonate formalin condensates.

Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts such as tetrabutylammonium bromide, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.
Examples of amphoteric surfactants include carboxybetaines, alkylaminocarboxylic acids, sulfobetaines, aminosulfuric esters, imidazolines, and the like.
The surfactant concentration in the developer is suitably 0.001 to 10% by mass, more preferably 0.005 to 1% by mass, and most preferably 0.01 to 0.5% by mass.

The following additives can be added to the developer for the purpose of further improving the development performance.
For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, chelating agents such as EDTA and NTA described in JP-A-58-190952, JP-A-59-121336 [Co (NH ₃ ) ₆ ] Cl ₃ , CoCl ₂ .6H ₂ O and other complexes described in JP-A-50-51324, sodium alkylnaphthalene sulfonate, n-tetradecyl-N, N-dihydroxy Anionic or amphoteric surfactants such as ethylbetaine, nonionic surfactants such as tetramethyldecynediol described in US Pat. No. 4,374,920, p described in JP-A-55-95946 -Cationic polymers such as methyl chloride quaternary compound of dimethylaminomethyl polystyrene, JP 56-142528 Amphoteric polymer electrolytes such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A No. 57-195951, reducing inorganic salts such as sodium sulfite described in JP-A-57-192951, Inorganic lithium compounds such as lithium chloride described in Japanese Patent No. 59444, organometallic surfactants containing organic Si, Ti, etc. described in Japanese Patent Laid-Open No. 59-75255, and organic compounds described in Japanese Patent Laid-Open No. 59-84241 Examples thereof include boron compounds and quaternary ammonium salts such as tetraalkylammonium oxides described in EP101010.

In addition, benzyl alcohol or the like is preferable as the organic solvent included in the developer. Moreover, addition of polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof is also preferable.
Furthermore, if necessary, an inorganic salt-based reducing agent such as hydroquinone, resorcin, sulfurous acid or sodium or potassium hydrogen sulfite, an organic carboxylic acid, an antifoaming agent, and a hard water softening agent may be added.

The alkaline developer of the present invention can be used for development processing of various photosensitive lithographic printing plates.
Accordingly, the present invention is directed to a method for making a lithographic printing plate comprising developing a photosensitive lithographic printing plate with the above alkaline developer after exposure.
Examples of the photosensitive lithographic printing plate to which the alkaline developer of the present invention can be applied include various photosensitive lithographic printing plates in which an image recording layer such as a photosensitive layer and a heat-sensitive layer is provided on a support. For example, as such a photosensitive lithographic printing plate, a conventional positive type, a conventional negative type, a photopolymer type, a thermal positive type, a thermal negative type, and the like are preferably exemplified. The term "conventional" as used herein refers to a conventional lithographic printing plate precursor that performs imagewise exposure through a transparent positive image or a transparent negative image.

Hereinafter, these various image recording layers will be described.
<Conventional positive type>
A preferable example of a conventional positive photosensitive resin composition is a composition containing an o-quinonediazide compound and an alkali-soluble polymer compound. Examples of o-quinonediazide compounds include esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and phenol-formaldehyde resin or cresol-formaldehyde resin, and US Pat. No. 3,635,709. There are esters of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride and pyrogallol acetone resin as described. Examples of the alkali-soluble polymer compound include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde co-condensation resin, polyhydroxystyrene, N- (4-hydroxyphenyl) methacrylamide copolymer, Examples thereof include carboxy group-containing polymers described in Japanese Patent No. 36184. Also, acrylic resins containing phenolic hydroxy groups as described in JP-A-51-34711, acrylic resins having sulfonamide groups as described in JP-A-2-866, and urethane Various alkali-soluble polymer compounds such as resins can also be used. Further, the photosensitive resin composition includes compounds such as sensitivity modifiers, printing agents, dyes and the like disclosed in JP-A-7-92660 [0024] to [0027] and those disclosed in the same publication [0031]. It is preferable to add a surfactant for improving the coatability.

<Conventional negative type>
Examples of conventional negative photosensitive resin compositions include those containing a diazo resin and an alkali-soluble or swellable polymer compound (binder). Examples of the diazo resin include a condensate of an aromatic diazonium salt and an active carbonyl group-containing compound such as formaldehyde. Further, for example, a condensate of p-diazophenylamines and formaldehyde and hexafluorophosphate or An organic solvent-soluble diazo resin inorganic salt that is a reaction product with tetrafluoroborate is exemplified. In particular, a high molecular weight diazo compound containing 20 mol% or more of a hexamer described in JP-A-59-78340 is preferable. Suitable binders include copolymers containing acrylic acid, methacrylic acid, crotonic acid or maleic acid as essential components, for example, 2-hydroxyethyl (meta) as described in JP-A-50-118802. ) Acrylate, (meth) acrylonitrile, multi-component copolymers of monomers such as (meth) acrylic acid, alkyl acrylate, (meth) acrylonitrile, and unsaturated as described in JP-A-56-4144 Mention may be made of multi-component copolymers composed of carboxylic acids. Furthermore, a plasticizer for imparting flexibility and abrasion resistance to the photosensitive resin composition as disclosed in JP-A-7-281425 [0014] to [0015]. It is preferable to add a compound such as a development accelerator and a surfactant for improving the coating property. As a lower layer of the above-mentioned conventional type positive type or negative type photosensitive layer, a polymer compound having a component having an acid group and a component having an onium group described in JP-A-2000-105462 is used. It is preferable to provide an intermediate layer to be contained.

<Photopolymer type>
(Photosensitive layer)
A photopolymer type photopolymerizable photosensitive composition (hereinafter referred to as “photopolymerizable composition”) is an addition-polymerizable ethylenically unsaturated bond-containing compound (hereinafter simply referred to as “ethylenically unsaturated bond-containing compound”). And a photopolymerization initiator and a polymer binder as essential components, and if necessary, various compounds such as a colorant, a plasticizer, a thermal polymerization inhibitor and the like.
The ethylenically unsaturated bond-containing compound contained in the photopolymerizable composition is such that, when the photopolymerizable composition is irradiated with actinic rays, it undergoes addition polymerization by the action of the photopolymerization initiator, crosslinks and cures. It is a compound having an ethylenically unsaturated bond. The ethylenically unsaturated bond-containing compound can be arbitrarily selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, such as monomers, prepolymers (ie, dimers). Trimers and oligomers), mixtures thereof, and copolymers thereof. Examples of monomers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids and aliphatic polyhydric compounds. And amides with a polyvalent amine compound. Urethane addition polymerizable compounds are also suitable.
As the initiator contained in the photopolymerizable composition, various photopolymerization initiators or a combination system (photoinitiation system) of two or more photopolymerization initiators are appropriately selected and used depending on the wavelength of the light source used. For example, an initiation system shown in JP 2001-22079 A [0021] to [0023] is preferable. The polymer binder contained in the photopolymerizable composition not only functions as a film-forming agent for the photopolymerizable composition, but also needs to dissolve the photosensitive layer in an alkali developer. An organic high molecular weight polymer that is swellable is used. As the polymer, those shown in the publications [0036] to [0063] are useful. In addition, it is also preferable to add the additive (for example, surfactant for improving applicability | paintability) shown by the same gazette [0079]-[0088] to a photopolymerizable composition.
Further, it is preferable to provide an oxygen-blocking protective layer on the photosensitive layer in order to prevent the oxygen polymerization inhibiting action. Examples of the polymer contained in the oxygen barrier protective layer include polyvinyl alcohol and its copolymer. Furthermore, it is also preferable to provide an intermediate layer or an adhesive layer as shown in JP-A-2001-228608 [0124] to [0165] as the lower layer of the photopolymer type photosensitive layer.

<Thermal positive type>
(Thermosensitive layer)
The thermal positive type heat-sensitive layer contains an alkali-soluble polymer compound and a photothermal conversion substance. This alkali-soluble polymer compound includes a homopolymer containing an acidic group in the polymer, a copolymer thereof, and a mixture thereof. In particular, an acidic group such as the following (1) or (2) is included. It is preferable from the viewpoint of solubility in an alkaline developer: (1) a phenolic hydroxy group (—Ar—OH), (2) a sulfonamide group (—SO ₂ NH—R). In particular, it is preferable to have a phenolic hydroxy group from the viewpoint of excellent image formability upon exposure with an infrared laser or the like, for example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m− / p−. Preferable examples include mixed cresol formaldehyde resin, phenol / cresol (any of m-, p- and m- / p-mixed) mixed formaldehyde resin, etc .; pyrogallol acetone resin. In more detail, the polymers shown in [0023] to [0042] of JP-A No. 2001-305722 are preferably used. The photothermal conversion substance converts exposure energy into heat and can efficiently cancel the interaction of the exposed area of the heat sensitive layer. From the viewpoint of recording sensitivity, a pigment or dye having a light absorption region in the infrared region with a wavelength of 700 to 1200 nm is preferable. As a dye. Specifically, azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes (for example, A dye such as a nickel thiolate complex) can be used. Among these, cyanine dyes are preferable, and examples include cyanine dyes represented by general formula (I) in JP-A No. 2001-305722. In the composition of the thermal positive type, it is preferable to add a sensitivity modifier, a printing agent, a compound such as a dye similar to those described for the conventional positive type, and a surfactant for improving the coating property. Specifically, the compounds shown in [0053] to [0059] of JP-A No. 2001-305722 are preferable.
The thermal positive type heat-sensitive layer may be a single layer or may be provided as a two-layer structure as described in JP-A-11-218914.
An undercoat layer is preferably provided between the thermal positive type heat-sensitive layer and the support. Examples of components contained in the undercoat layer include various organic compounds shown in JP-A-2001-305722, [0068].

<Thermal negative type>
(Thermosensitive layer)
The thermal negative-type heat-sensitive layer is a negative-type heat-sensitive layer in which the infrared laser irradiation part is cured to form an image part.
As one of such thermal negative type heat-sensitive layers, a polymerization type layer is preferably exemplified. The polymerization layer comprises (A) an infrared absorber, (B) a radical generator (radical polymerization initiator), a curing reaction caused by the generated radical (C) a radical polymerizable compound, and (D) a binder. Containing polymer.
In the polymerization layer, the infrared rays absorbed by the infrared absorber are converted into heat, and the generated heat decomposes radical polymerization initiators such as onium salts to generate radicals. The radically polymerizable compound is selected from compounds having a terminal ethylenically unsaturated bond, and a polymerization reaction is caused in a chain by the generated radicals and is cured. Examples of the infrared absorber (A) include the above-described photothermal conversion substance contained in the above-described thermal positive type heat-sensitive layer. In particular, as a specific example of the cyanine dye, paragraph number of JP-A No. 2001-133969 [0017] to [0019] may be mentioned. (B) Examples of the radical generator include onium salts. Specific examples of onium salts that can be suitably used are described in paragraphs [0030] to [0033] of JP-A No. 2001-133969. Things can be mentioned. (C) The radically polymerizable compound is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. (D) It is preferable to use a linear organic polymer as the binder polymer, and a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected. Of these, a (meth) acrylic resin having a benzyl group or an allyl group and a carboxy group in the side chain is particularly preferable because of its excellent balance of film strength, sensitivity, and developability. With respect to (C) the radical polymerizable compound and (D) the binder polymer, those described in detail in the publications [0036] to [0060] can be used. As other additives, it is also preferable to add an additive (for example, a surfactant for improving coatability) shown in the publications [0061] to [0068].

  In addition to the polymerization type, an acid-crosslinking type layer is preferably used as one of the thermal negative type heat-sensitive layers. The acid cross-linking layer comprises (E) a compound that generates an acid by light or heat (hereinafter referred to as “acid generator”) and (F) a compound that cross-links by the generated acid (hereinafter referred to as “cross-linking agent”). And (G) an alkali-soluble polymer compound that can react with a crosslinking agent in the presence of an acid. In order to efficiently use the energy of the infrared laser, (A) an infrared absorber is blended in the acid crosslinking layer. Examples of the acid generator (E) include compounds capable of generating an acid upon thermal decomposition, such as a photoinitiator for photopolymerization, a photochromic agent for dyes, and an acid generator used for a microresist. . (F) The crosslinking agent includes (i) an aromatic compound substituted with a hydroxymethyl group or an alkoxymethyl group, (ii) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group, Or (iii) an epoxy compound is mentioned. (G) Examples of the alkali-soluble polymer compound include novolak resins and polymers having a hydroxyaryl group in the side chain.

<Back coat layer>
In order to prevent the image recording layer from being scratched when it is overlaid on the back surface of the photosensitive lithographic printing plate obtained by providing various image recording layers, a coating layer made of an organic polymer compound. (Referred to as “back coat layer”).
<Exposure>
The photosensitive lithographic printing plate is subjected to image exposure by various processing methods corresponding to the image recording layer. Examples of the active light source used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, and a chemical lamp. Examples of the laser beam include a helium-neon laser (He-Ne laser), an argon laser, a krypton laser, a helium-cadmium laser, a KrF excimer laser, a semiconductor laser, a YAG laser, and a YAG-SHG laser.

The alkaline developer of the present invention is particularly preferably used for plate making from an infrared-sensitive lithographic printing plate. Therefore, here, the photosensitive layer (hereinafter also referred to as a heat-sensitive layer) having a photosensitive layer on the support is exposed to an infrared-sensitive lithographic printing plate containing an infrared-absorbing dye and an alkali-soluble resin. The lithographic printing plate making method including development with an alkaline developer described in detail in 1) is touched.
The infrared photosensitive lithographic printing plate will be described in detail below. First, the components of the heat-sensitive layer serving as the image recording layer will be described.

[Infrared absorbing dye]
The infrared absorbing dye used in the heat sensitive layer is not particularly limited as long as it absorbs infrared rays and generates heat, and various dyes known as infrared absorbing dyes can be used.
As the infrared absorbing dye, commercially available dyes and known dyes described in the literature (for example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include azo dyes, metal complex azo dyes, pyrazolone azo dyes, quinoneimine dyes, methine dyes, and cyanine dyes. In the present invention, among these dyes, those that absorb infrared light or near-infrared light are particularly preferable because they are suitable for use in lasers that emit infrared light or near-infrared light.
Examples of dyes that absorb such infrared light or near infrared light include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, and JP-A-60-78787. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, etc., JP-A-58-112793, Naphthoquinone dyes described in JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-59240, JP-A-60-63744, etc. Examples thereof include squarylium dyes described in JP-A-58-112792, and cyanine dyes described in British Patent 434,875.

Further, a near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used as the dye, and a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 58-220143, 59-41363, 59-84248 Nos. 59-84249, 59-146063, 59-146061, pyranlium compounds, cyanine dyes described in JP-A-59-216146, US Pat. No. 4,283,475 Pentamethine thiopyrylium salts described in No. 5 and pyrylium compounds disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 But, as commercially available products, Eporin Co. Epolight
III-178, Eplight III-130, Eplight III-125 and the like are particularly preferably used.
Infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 are particularly preferred as infrared absorbing dyes used in the heat sensitive layer. The dye exhibits a very strong interaction with the alkalized soluble resin, and is excellent in the unexposed area alkaline development resistance of the heat-sensitive layer.

The amount of the infrared absorbing dye added to the heat-sensitive layer is suitably 3 to 50% by weight, preferably 5 to 40% by weight, more preferably 8 to 35% by weight from the viewpoint of sensitivity and layer durability with respect to the heat-sensitive layer mass. %.
Specific examples of the infrared absorbing dye are shown below, but the present invention is not limited thereto.

[Alkali-soluble resin]
The alkali-soluble resin used in the heat-sensitive layer is a water-insoluble and alkali-water-soluble resin (hereinafter, appropriately referred to as an alkali-soluble polymer), which contains an acidic group in the main chain and / or side chain in the polymer. Homopolymers, copolymers thereof, or mixtures thereof. Therefore, the heat-sensitive layer of the photosensitive lithographic printing plate has a property of dissolving when contacted with an alkaline developer.
The alkali-soluble polymer used in the heat-sensitive layer is not particularly limited as long as it is a conventionally known polymer. However, any one of (1) a phenolic hydroxyl group, (2) a sulfonamide group, and (3) an active imide group may be used. A polymer compound having a group in the molecule is preferred. For example, although the following are illustrated, it is not limited to these.

(1) Examples of the polymer compound having a phenolic hydroxyl group include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p Any of-or m- / p-mixing) may be used. Examples thereof include novolak resins such as mixed formaldehyde resins and pyrogallol acetone resins. In addition to this, a polymer compound having a phenolic hydroxyl group in the side chain is preferably used as the polymer compound having a phenolic hydroxyl group. As a polymer compound having a phenolic hydroxyl group in the side chain, a polymerizable monomer comprising a low molecular compound having at least one unsaturated bond polymerizable with the phenolic hydroxyl group is homopolymerized, or other polymerizable property is added to the monomer. Examples thereof include a polymer compound obtained by copolymerizing monomers.

  Examples of the polymerizable monomer having a phenolic hydroxyl group include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene having a phenolic hydroxyl group. Specifically, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N -(3-Hydroxyphenyl) methacrylamide, N- (4-Hydroxyphenyl) methacrylamide, o-Hydroxyphenyl acrylate, m-Hydroxyphenyl acrylate, p-Hydroxyphenyl acrylate, o-Hydroxyphenyl methacrylate , M-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (2-hydroxyphenyl) ethyl acrylate, 2- (3-hydroxyphenyl) ethyl Acrylate, 2- 4-hydroxyphenyl) ethyl acrylate, 2- (2-hydroxyphenyl) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate can be suitably used 2- (4-hydroxyphenyl) ethyl methacrylate. Such resins having a phenolic hydroxyl group may be used in combination of two or more. Furthermore, as described in US Pat. No. 4,123,279, phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, These copolymers may be used in combination.

(2) Examples of the alkali-soluble polymer compound having a sulfonamide group include a polymer compound obtained by homopolymerizing a polymerizable monomer having a sulfonamide group or copolymerizing the monomer with another polymerizable monomer. . The polymerizable monomer having a sulfonamide group includes at least one sulfonamide group —NH—SO ₂ — in which at least one hydrogen atom is bonded on a nitrogen atom and one polymerizable unsaturated bond in one molecule. And a polymerizable monomer comprising a low molecular weight compound. Among these, a low molecular compound having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group is preferable.

(3) The alkali-soluble polymer compound having an active imide group preferably has an active imide group in the molecule, and the polymer compound has an unsaturated bond polymerizable with an active imide group in one molecule. Examples thereof include a polymer compound obtained by homopolymerizing a polymerizable monomer composed of one or more low-molecular compounds or by copolymerizing the polymerizable monomer with another polymerizable monomer.
As such a compound, specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be preferably used.

  Furthermore, as the alkali-soluble polymer compound, a polymer compound obtained by polymerizing two or more of the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, and the polymerizable monomer having an active imide group is used. Alternatively, it is preferable to use a polymer compound obtained by copolymerizing these two or more polymerizable monomers with another polymerizable monomer. When a polymerizable monomer having a phenolic hydroxyl machine is copolymerized with a polymerizable monomer having a sulfonamide group and / or a polymerizable monomer having an active imide group, the compounding polymerization ratio (mass ratio) of these components is It is preferably in the range of 50:50 to 5:95, particularly preferably in the range of 40:60 to 10:90.

  When the alkali-soluble polymer is a copolymer of a polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group and another polymerizable monomer The monomer that imparts alkali solubility is preferably contained in an amount of 10 mol% or more, more preferably 20 mol% or more. When the copolymerization component is less than 10 mol%, alkali solubility tends to be insufficient, and the development latitude improvement effect may not be sufficiently achieved.

Examples of the monomer component to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group include the compounds listed in the following (m1) to (m12). However, the present invention is not limited to these.
(M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
(M2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, and glycidyl acrylate.
(M3) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, and glycidyl methacrylate.
(M4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.

(M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(M6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(M7) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene.
(M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.
(M10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(M12) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

The alkali-soluble polymer compound preferably has a phenolic hydroxyl group in terms of excellent image-forming properties in exposure with an infrared laser or the like, such as phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, Preferred examples include novolak resins and pyrogallol acetone resins such as m- / p-mixed cresol formaldehyde resin and phenol / cresol (which may be m-, p-, or m- / p-mixed) mixed formaldehyde resin.
Further, as an alkali-soluble polymer compound having a phenolic hydroxyl group, as described in US Pat. No. 4,123,279, carbon such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin is used. Examples include condensation polymers of phenol and formaldehyde having an alkyl group of 3 to 8 as a substituent.
As a copolymerization method of the alkali-soluble polymer compound, a conventionally known graft copolymerization, block copolymerization, random copolymerization method or the like can be used.

In the present invention, when the alkali-soluble polymer is a homopolymer or copolymer of a polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group, the weight average Those having a molecular weight of 2,000 or more and a number average molecular weight of 500 or more are preferred. More preferably, the weight average molecular weight is 5,000 to 300,000, the number average molecular weight is 800 to 250,000, and the dispersity (weight average molecular weight / number average molecular weight) is 1.1 to 10. .
In the present invention, when the alkali-soluble polymer is a resin such as phenol formaldehyde resin or cresol aldehyde resin, the weight average molecular weight is 500 to 20.000, and the number average molecular weight is 200 to 10,000. preferable.
These alkali-soluble polymer compounds may be used alone or in combination of two or more. From the viewpoint of both the sensitivity and durability of the heat-sensitive layer, the heat-sensitive layer has a total solid content of 30 to 99% by mass, preferably It is used in an amount of 40 to 95% by mass, particularly preferably 50 to 90% by mass.

The heat-sensitive layer may also contain an alkali-soluble polymer compound having a carboxyl group (hereinafter sometimes referred to as “component (B1)”).
The polymer compound (B1) may be any alkali-soluble polymer compound having a carboxyl group, but polymer compounds (b1-1) and (b1-2) defined below are preferred.
(B1-1) An alkali-soluble polymer compound having a polymerizable monomer unit represented by the following general formula (i) (hereinafter also referred to as polymer compound (b1-1))

(In the formula, Xm represents a single bond or a divalent linking group, Y represents hydrogen or a carboxyl group, and Z represents hydrogen, an alkyl group or a carboxyl group.)
As the monomer constituting the polymerizable monomer unit represented by the general formula (i), there is a polymerizable monomer having at least one carboxyl group and one polymerizable unsaturated group in the molecule.
Specific examples of such polymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and itaconic anhydride.

Examples of the monomer to be copolymerized with the polymerizable monomer having a carboxyl group include, but are not limited to, the following (1) to (11).
(1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl Alkyl acrylates such as acrylates;
(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl Alkyl methacrylate such as methacrylate.

(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide.
(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene. (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.

  Moreover, the monomer of the following general formula (ii) is also preferably used.

In the formula, X represents O, S, or N—R ¹² . R ^{10 to} R ¹² each independently represents a hydrogen atom or an alkyl group. m, n, and o each independently represent an integer of 2 to 5, and C _m H _2m , C _n H _2n , and C _o H _2o may each be a straight chain or a branched structure. p, q, and r each independently represent an integer of 0 to 3,000, and p + q + r ≧ 2.

The alkyl group in R ¹⁰ to R ^12, preferably one having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, n- propyl group, an isopropyl group. p, q, and r preferably represent an integer of 0 to 500, and more preferably represent an integer of 0 to 100.
Although the example of the monomer corresponding to the repeating unit represented by the said general formula (ii) is given below, it is not this limitation.

The repeating unit represented by the general formula (ii) is a commercially available hydroxypoly (oxyalkylene) material such as a trade name Pluronic (Pluronic (manufactured by Asahi Denka Kogyo Co., Ltd.), Adeka Polyether (Asahi Denka Kogyo Co., Ltd.) ), Carbowax (Carbowax (Glyco Product)), Triton (Toriton (Rohm and Haas (Rohm and Haas)), and PE (Daiichi Kogyo Seiyaku Co., Ltd.) Can be produced by reacting the product with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride in a known manner.
Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.

  As a commercially available monomer, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer AE-90, Blemmer AE-200, Blemmer as a hydroxyl-terminated polyalkylene glycol mono (meth) acrylate manufactured by NOF Corporation. AE-400, Blemmer PP-1000, Blemmer PP-500, Blemmer PP-800, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer AP-800, Blemmer 50 PEP-300, Blemmer 70PEP-350B, Blemmer AEP series, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-800, Blemmer AET series, Blemmer 30PPT-800, Blemmer 5 PPT-800, Blemmer 70PPT-800, Blemmer APT series, Brenmer 10PPB-500B, and the like Brenmer 10APB-500B. Similarly, Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer as alkyl-terminated polyalkylene glycol mono (meth) acrylates manufactured by NOF Corporation. 50POEP-800B, Blemmer 50AOEP-800B, Blemmer PLE-200, Blemmer ALE-200, Blemmer ALE-800, Blemmer PSE-400, Blemmer PSE-1300, Blemmer ASE series, Blemmer PKEP series, Blemmer AKEP series, Blemmer AE-300 , Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANE -500, BLEMMER 70ANEP-550, etc., and Kyoeisha Chemical Co., Ltd. light ester MC, light ester 130MA, light ester 041MA, light acrylate BO-A, light acrylate EC-A, light acrylate MTG-A, light acrylate 130A, light Examples thereof include acrylate DPM-A, light acrylate P-200A, light acrylate NP-4EA, and light acrylate NP-8EA.

The minimum constitutional unit having a polymerizable monomer component having at least one carboxyl group and at least one polymerizable unsaturated group in the polymer compound (b1-1) is not necessarily limited to one kind, and is the same. It is also possible to use a copolymer obtained by copolymerizing two or more kinds of minimum structural units having the above acidic group or two or more kinds of minimum structural units having different acidic groups.
As the copolymerization method, conventionally known graft copolymerization, block copolymerization, random copolymerization, and the like can be used.

(B1-2) A basic skeleton is a reaction product of a diol compound represented by the following general formula (iii), (iv) or (v) having a carboxyl group and a diisocyanate compound represented by the following general formula (viii) And an alkali-soluble polymer compound having a carboxyl group (hereinafter, also referred to as polymer compound (b1-2)).

R ¹³ is a hydrogen atom, a substituent (for example, alkyl, aryl, alkoxy, ester, urethane, amide, ureido, halogeno are preferable), alkyl, alkenyl, aralkyl, aryl, alkoxy, aryloxy Preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
R ¹⁴ , R ¹⁵ and R ¹⁶ may have the same or different single bond and substituent (for example, alkyl, alkenyl, aralkyl, aryl, alkoxy and halogeno groups are preferred). Or a divalent aliphatic or aromatic hydrocarbon. Preferably an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms is shown.
If necessary, R ¹⁴ , R ¹⁵ , R ¹⁶ have other functional groups that do not react with isocyanate groups, such as ester groups, urethane groups, amide groups, ureido groups, and carbon-carbon unsaturated bonds. Also good. In addition, you may comprise a ring by 2 or 3 of R < ¹³ >, R <^14> , R <^15> , R < ¹⁶ >.
Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and preferably an aromatic group having 6 to 15 carbon atoms.

OCN-R ¹⁸ -NCO (viii)
In the formula, R ¹⁸ represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent (eg, alkyl, alkenyl, aralkyl, aryl, alkoxy and halogeno groups are preferable). If necessary, R ¹⁸ may have another functional group that does not react with an isocyanate group, such as an ester, urethane, amide, ureido group, or carbon-carbon unsaturated bond.

Specific examples of the diol compound having a carboxyl group represented by the general formula (iii), (iv) or (v) include those shown below.
3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, Bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide Etc.

  The alkali-soluble polymer compound having a carboxyl group (b1-2) is preferably a reaction product in which a diol represented by the following general formula (vi) or (vii) is combined.

In the formula, R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 2 or more. Examples of the alkyl group having 1 to 8 carbon atoms in R ^17, a methyl group, an ethyl group, i- propyl, n- butyl group, etc. i- butyl group.
Specific examples of the diol represented by the general formula (vi) or (vii) are shown below, but the present invention is not limited thereto.

Specific examples of (vi) HO — (— CH ₂ CH ₂ O—) ₃ —H
HO — (— CH ₂ CH ₂ O—) ₄ —H
HO — (— CH ₂ CH ₂ O—) ₅ —H
HO — (— CH ₂ CH ₂ O—) ₆ —H
HO — (— CH ₂ CH ₂ O—) ₇ —H
HO — (— CH ₂ CH ₂ O—) ₈ —H
HO — (— CH ₂ CH ₂ O—) ₁₀ —H
HO — (— CH ₂ CH ₂ O—) ₁₂ —H
Polyethylene glycol (average molecular weight 1000)
Polyethylene glycol (average molecular weight 2000)
Polyethylene glycol (average molecular weight 4000)
HO — (— CH ₂ CH (CH ₃ ) O—) ₃ —H
HO — (— CH ₂ CH (CH ₃ ) O—) ₄ —H
HO — (— CH ₂ CH (CH ₃ ) O—) ₆ —H
Polypropylene glycol (average molecular weight 1000)
Polypropylene glycol (average molecular weight 2000)
Polypropylene glycol (average molecular weight 4000)

Specific examples of (vii) HO — (— CH ₂ CH ₂ CH ₂ O—) ₃ —H
HO — (— CH ₂ CH ₂ CH ₂ O—) ₄ —H
HO — (— CH ₂ CH ₂ CH ₂ O—) ₈ —H
HO — (— CH ₂ CH ₂ CH (CH ₃ ) O—) ₁₂ —H

Specific examples of the diisocyanate compound represented by the general formula (viii) include those shown below.
That is, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, Aromatic diisocyanate compounds such as 1,5-naphthalene diisocyanate and 3,3′-dimethylbiphenyl-4,4′-diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate Compound, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) -diisocyanate, 1 An aliphatic diisocyanate compound such as 1,3- (isocyanatomethyl) cyclohexane; a diisocyanate compound which is a reaction product of a diol and diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate, and the like. Can be mentioned.

  The molar ratio of the diisocyanate and the diol compound used for the synthesis of the polymer compound (b1-2) is preferably 0.8: 1 to 1.2-1, and when an isocyanate group remains at the polymer terminal, alcohols or By treating with amines or the like, it is finally synthesized in a form in which no isocyanate group remains.

As the component (B1), one type may be used alone from the above polymer compounds (b1-1) and (b1-2), or two or more types may be used in combination.
The content of the repeating unit having a carboxyl group contained in the component (B1) is 2 mol% or more based on the total amount of each monomer of the component (B1), preferably 2 to 70 mol%. Yes, more preferably in the range of 5 to 60 mol%.
The preferred weight average molecular weight of the component (B1) is preferably 3000 to 300,000, more preferably 6,000 to 100,000.

  Furthermore, the preferable addition amount of (B1) component is the range of 0.005-80 mass% with respect to the total solid content mass of a heat sensitive layer, Preferably it is the range of 0.01-50 mass%, More preferably Is in the range of 1-20% by weight.

〔Additive〕
In forming the heat-sensitive layer, in addition to the above components, various additives can be added as necessary as long as the effects of the present invention are not impaired.
-Solubility inhibiting compound-
The photosensitive lithographic printing plate can contain various inhibitors in the heat-sensitive layer for the purpose of enhancing the inhibition (solubility inhibition).
Although it does not specifically limit as this inhibitor, A quaternary ammonium salt, a polyethyleneglycol type compound, etc. are mentioned.

Although it does not specifically limit as a quaternary ammonium salt, A tetraalkyl ammonium salt, a trialkyl aryl ammonium salt, a dialkyl diaryl ammonium salt, an alkyl triaryl ammonium salt, a tetraaryl ammonium salt, a cyclic ammonium salt, and a bicyclic ammonium salt are mentioned. .
Specifically, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, tetraoctylammonium bromide, tetralaurylammonium bromide, tetraphenylammonium bromide, tetranaphthylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide , Tetrastearyl ammonium bromide, lauryl trimethyl ammonium bromide, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium bromide, lauryl triethyl ammonium bromide, phenyl trimethyl ammonium bromide, 3-trifluoromethylphenyl trimethyl ammonium bromide, benzyl trimethyl ammonium bromide De, dibenzyl dimethyl ammonium bromide, distearyl dimethyl ammonium bromide, tristearyl methyl ammonium bromide, benzyl triethyl ammonium bromide, hydroxyphenyl trimethyl ammonium bromide, N- methyl pyridinium bromide, and the like. In particular, quaternary ammonium salts described in Japanese Patent Application Nos. 2001-226297, 2001-370059, and 2001-398047 are preferable.

  The addition amount of the quaternary ammonium salt is 0.1 to 50% by mass in terms of solid content with respect to the total solid content of the image recording layer in that it does not adversely affect the sufficient solubility inhibiting effect and film forming property of the binder. It is preferable that there is more preferably 1 to 30% by mass.

  Although it does not specifically limit as a polyethyleneglycol type compound, The thing of the following structure is mentioned.

^{R 1 - {- O- (R} 3 -O-) m-R 2} n
(R ¹ is a polyhydric alcohol residue or polyhydric phenol residue, R ² is a hydrogen atom, an alkyl group, alkenyl group, alkynyl group, alkyloyl group, aryl optionally having a substituent having 1 to 25 carbon atoms A group or an aryloyl group, R ³ represents an alkylene residue which may have a substituent, m is an average of 10 or more, and n is an integer of 1 to 4.

  Examples of polyethylene glycol compounds having the above structure include polyethylene glycols, polypropylene glycols, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol aryl ethers, polypropylene glycol aryl ethers, polyethylene glycol alkyl aryl ethers. , Polypropylene glycol alkyl aryl ethers, polyethylene glycol glycerin esters, polypropylene glycol glycerin esters, polyethylene sorbitol esters, polypropylene glycol sorbitol esters, polyethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, polyethylene glycolated ethylene Diamines, polypropylene glycolated ethylenediamines, polyethylene glycolated diethylenetriamine, and polypropylene glycol diethylenetriamines.

  Specific examples thereof include polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 10000, polyethylene glycol 20000, polyethylene glycol 50000, polyethylene glycol 100000, polyethylene glycol 200000, polyethylene glycol 500000, polypropylene glycol 1500, polypropylene glycol. 3000, polypropylene glycol 4000, polyethylene glycol methyl ether, polyethylene glycol ethyl ether, polyethylene glycol phenyl ether, polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol diphenyl ether , Polyethylene glycol lauryl ether, polyethylene glycol dilauryl ether, polyethylene glycol nonyl ether, polyethylene glycol cetyl ether, polyethylene glycol stearyl ether, polyethylene glycol distearyl ether, polyethylene glycol behenyl ether, polyethylene glycol dibehenyl ether, polypropylene glycol methyl ether, polypropylene Glycol ethyl ether, polypropylene glycol phenyl ether, polypropylene glycol dimethyl ether, polypropylene glycol diethyl ether, polypropylene glycol diphenyl ether, polypropylene glycol lauryl ether, polypropylene glycol dilauryl ether, Ripropylene glycol nonyl ether, polyethylene glycol acetyl ester, polyethylene glycol diacetyl ester, polyethylene glycol benzoic acid ester, polyethylene glycol lauryl ester, polyethylene glycol dilauryl ester, polyethylene glycol nonyl acid ester, polyethylene glycol cetyl acid ester, polyethylene glycol stearoyl ester, Polyethylene glycol distearoyl ester, polyethylene glycol behenate ester, polyethylene glycol dibehenate ester, polypropylene glycol acetyl ester, polypropylene glycol diacetyl ester, polypropylene glycol benzoate ester, polypropylene glycol dibenzoate ester, Polypropylene glycol laurate, polypropylene glycol dilaurate, polypropylene glycol nonyl ester, polyethylene glycol glycerol ether, polypropylene glycol glycerol ether, polyethylene glycol sorbitol ether, polypropylene glycol sorbitol ether, polyethylene glycolated ethylenediamine, polypropylene glycolated ethylenediamine, polyethylene Examples include glycolated diethylenetriamine, polypropylene glycolated diethylenetriamine, and polyethylene glycolated pentamethylenehexamine.

  The addition amount of the polyethylene glycol compound is preferably 0.1 to 50% by mass in terms of solid content with respect to the total solid content of the image recording layer, from the viewpoint of sufficient solubility inhibiting effect and image forming property. More preferably, it is -30 mass%.

Further, when the above-described measures for improving the inhibition (solubility inhibition) are performed, the sensitivity is lowered. In this case, it is effective to add a lactone compound. This lactone compound is considered to be that when the developer penetrates into the exposed area, the developer and the lactone compound react to generate a new carboxylic acid compound, contributing to dissolution of the exposed area and improving sensitivity.
Although it does not specifically limit as a lactone compound, The compound represented by the following general formula (LI) and general formula (L-II) is mentioned.

In General Formula (LI) and General Formula (L-II), X ¹ , X ² , X ³ and X ⁴ are ring constituent atoms or atomic groups, which may be the same or different and are independent of each other. And may have a substituent, and at least one of X ¹ , X ² and X ^{3 in} the general formula (LI) and X ¹ , X ² , X ³ and X in the general formula (L-II) ^At least one of ⁴ has an electron-withdrawing substituent or a substituent substituted with an electron-withdrawing group.
The constituent atoms or atomic groups of the ring represented by X ¹ , X ² , X ³ and X ⁴ are nonmetallic atoms having two single bonds for forming a ring or atomic groups containing the nonmetallic atoms.
A preferred nonmetallic atom or nonmetallic atomic group is an atom or atomic group selected from a methylene group, a sulfinyl group, a carbonyl group, a thiocarbonyl group, a sulfonyl group, a sulfur atom, an oxygen atom, and a selenium atom, and more preferably, It is an atomic group selected from a methylene group, a carbonyl group and a sulfonyl group.

At least one of X ¹ , X ² and X ^{3 in} the general formula (LI) or at least one of X ¹ , X ² , X ³ and X ^{4 in} the general formula (L-II) is an electron withdrawing group Have In this specification, the electron-withdrawing substituent refers to a group in which Hammett's substituent constant σp takes a positive value. For Hammett's substituent constants, see Journal of Medicinal Chemistry, 1973, Vol. 16, no. 11, 1207-1216 etc. can be referred to. Examples of electron-withdrawing groups in which Hammett's substituent constant σp takes a positive valence include halogen atoms (fluorine atoms (σp value: 0.06), chlorine atoms (σp value: 0.23), bromine atoms (σp value). : 0.23), iodine atom (σp value: 0.18)), trihaloalkyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.33), trifluoromethyl (σp) Value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0. 72)), aliphatic / aryl or heterocyclic acyl groups (for example, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), alkynyl groups (for example, C≡CH (σp value: 0)) .23)), Aliphatic Ali Or a heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.44)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value: 0.57), sulfoxide groups, heterocyclic groups, oxo groups, phosphoryl groups and the like.

Preferred electron withdrawing groups include amide groups, azo groups, nitro groups, fluoroalkyl groups having 1 to 5 carbon atoms, nitrile groups, alkoxycarbonyl groups having 1 to 5 carbon atoms, acyl groups having 1 to 5 carbon atoms, and carbon numbers. An alkylsulfonyl group having 1 to 9 carbon atoms, an arylsulfonyl group having 6 to 9 carbon atoms, an alkylsulfinyl group having 1 to 9 carbon atoms, an arylsulfinyl group having 6 to 9 carbon atoms, an arylcarbonyl group having 6 to 9 carbon atoms, and thiocarbonyl A group selected from a group, a fluorine-containing alkyl group having 1 to 9 carbon atoms, a fluorine-containing aryl group having 6 to 9 carbon atoms, a fluorine-containing allyl group having 3 to 9 carbon atoms, an oxo group, and a halogen element.
More preferably, a nitro group, a fluoroalkyl group having 1 to 5 carbon atoms, a nitrile group, an alkoxycarbonyl group having 1 to 5 carbon atoms, an acyl group having 1 to 5 carbon atoms, an arylsulfonyl group having 6 to 9 carbon atoms, carbon It is a group selected from an arylcarbonyl group of formulas 9 to 9, an oxo group and a halogen element.
Specific examples of the compounds represented by formula (LI) and formula (L-II) are shown below, but the present invention is not limited to these compounds.

The addition amount of the compounds represented by the general formula (LI) and the general formula (L-II) is based on the total solid content of the image recording layer in order to exhibit sufficient effects and good image forming properties. The solid content is preferably 0.1 to 50% by mass, and more preferably 1 to 30% by mass. In addition, since this compound reacts with a developing solution, it is desirable to contact a developing solution selectively.
These lactone compounds may be used alone or in combination. Two or more compounds of the general formula (LI) or two or more compounds of the general formula (L-II) may be used in combination at an arbitrary ratio within the above range.

  In addition, a substance that is thermally decomposable, such as an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, and an aromatic sulfonic acid ester compound, and that substantially reduces the solubility of the alkaline water-soluble polymer compound without being decomposed. Use in combination is preferable in terms of improving the dissolution inhibition of the image area in the developer. Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts.

Preferred examples of the onium salt used in the present invention include S.P. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in JP-A-5-158230, U.S. Pat. Nos. 4,069,055, 4,069,056, and JP-A-3-140140. Ammonium salts described in the specification of C. Necker et al, Macromolecules, 17, 2468 (1984), C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055 and 4,069,056; V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Pat. Nos. 339,049, 410,201, JP-A-2-150848, JP-A-2-296514, . V. Crivello et al, Polymer J. et al. 17, 73 (1985), J. Am. V. Crivello et al, J.A. Org. Chem. 43, 3055 (1978); R. Watt et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al, Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al, Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. 17, 2877 (1979), European Patent Nos. 370,693, 233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377 and 3,902,114. Nos. 410, 201, 339, 049, 4, 760, 013, 4, 734, 444, 2, 833, 827, German Patent No. 2,904, 626, Sulfonium salts described in JP-A-3,604,580 and JP-A-3,604,581; V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478, Tokyo, Oct (1988).
Of the onium salts, diazonium salts are particularly preferred. Particularly suitable diazonium salts include those described in JP-A-5-158230.

  The counter ion of the onium salt includes tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfone Examples include acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, and paratoluenesulfonic acid. Of these, particularly preferred are alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid.

  Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide assists the solubility of the sensitive material system by both the effect of losing the inhibition of dissolution of the binder by thermal decomposition and the change of o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include J. The compounds described by Korser, “Light-Sensitive Systems”, (John Wiley & Sons. Inc.), pp. 339-352 can be used, but in particular, they react with various aromatic polyhydroxy compounds or aromatic amino compounds. The o-quinonediazide sulfonic acid ester or sulfonic acid amide is preferred. Further, benzoquinone (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and pyrogallol-acetone resin as described in JP-B-43-28403 Esters of benzoquinone- (1,2-diazide sulfonic acid chloride or naphthoquinone- (1,2) -diazide-5 described in US Pat. Nos. 3,046,120 and 3,188,210. Esters of sulfonic acid chloride and phenol-formaldehyde resin are also preferably used.

  Further, an ester of naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazido-4-sulfonic acid chloride and pyrogallol-acetone resin Similarly, the esters are also preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96575, JP-A-49-38701, JP-A-48-13354, Japanese Patent Publication Nos. 41-11222, 45-9610, 49-17478, U.S. Pat. Nos. 2,797,213, 3,454,400, 3,544,323, 3,573,917, 3,674,495, 3,785,825, British Patents 1,227,602, 1,251,345, 1,267, No. 005, No. 1,329,888, No. 1,330,932, German Patent No. 854,890, and the like.

  The addition amount of the o-quinonediazide compound is preferably in the range of 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 30% by mass with respect to the total solid content of the image recording layer. These compounds can be used alone, but may be used as a mixture of several kinds. Moreover, you may include the alkali-soluble resin by which at least one part of Unexamined-Japanese-Patent No. 11-288089 was esterified.

  Further, for the purpose of enhancing the dissolution inhibiting property on the surface of the image recording layer and enhancing the resistance to scratches on the surface, it is possible to improve the resistance against scratches on the surface as described in JP-A No. 2000-187318. It is preferable to use a polymer having a polymerization component of a (meth) acrylate monomer having 2 or 3 fluoroalkyl groups. As addition amount, the ratio for which it occupies in a layer material is 0.1-10 mass%, More preferably, it is 0.5-5 mass%.

-Development accelerator-
For the purpose of further improving sensitivity, acid anhydrides, phenols and organic acids can be used in combination.
As the acid anhydrides, cyclic acid anhydrides are preferable. Specific examples of the cyclic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride described in US Pat. No. 4,115,128. Acid, 3,6-endooxy-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of the non-cyclic acid anhydride include acetic anhydride.
The phenols include bisphenol A, 2,2′-bishydroxysulfone, p-nitrophenol, p-ethoxyphenol, 2,4,4′-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4- Examples include hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane. .

Furthermore, examples of organic acids include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphate esters, and carboxylic acids described in JP-A-60-88942 and JP-A-2-96755. Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, Examples include adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like. .
The proportion of the acid anhydride, phenols and organic acids in the image recording layer is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 10%. % By mass.

-Surfactant-
In the heat-sensitive layer, as described in JP-A-62-251740 and JP-A-3-208514, in order to improve the coating properties and to expand the stability of processing with respect to development conditions. Nonionic surfactants, amphoteric surfactants as described in JP-A-59-121044, JP-A-4-13149, siloxane compounds as described in EP950517, A fluorine-containing monomer copolymer as described in JP-A No. 62-170950, JP-A No. 11-288093, and Japanese Patent Application No. 2001-247351 can be added.
Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like. Specific examples of amphoteric activators include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Type (for example, trade name “Amorgen K” manufactured by Daiichi Kogyo Co., Ltd.).
The siloxane compound is preferably a block copolymer of dimethylsiloxane and polyalkylene oxide. Specific examples include DBE-224, DBE-621, DBE-712, DBP-732, DBP-534, manufactured by Chisso Corporation. And polyalkylene oxide-modified silicones such as Tego Glide 100 manufactured by Tego, Germany. The proportion of the nonionic surfactant and amphoteric surfactant in the image recording layer is preferably 0.01 to 15% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.05 to 0%. 0.5% by mass.

-Bakeout agent / colorant-
In the printing plate material, a printing-out agent for obtaining a visible image immediately after heating by exposure or a dye or pigment as an image coloring agent can be added.
Typical examples of the printing-out agent include a combination of a compound that releases an acid by heating by exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halides and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, 36223, 54-74728, 60-3626, 61-143748, 61-151644 and 63-58440, and trihalomethyl compounds and salt-forming organic dyes Can be mentioned. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear printout images.

As the image colorant, other dyes can be used in addition to the aforementioned salt-forming organic dyes. Examples of suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (oriental chemical industry) Co., Ltd.), Victoria Pure Blue, Crystal Violet Lactone, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000), Methylene Blue (CI52015), etc. it can. The dyes described in JP-A-62-293247 are particularly preferred.
These dyes can be added to the printing plate material in a proportion of 0.01 to 10% by mass, preferably 0.1 to 3% by mass, based on the total solid content of the image recording layer.

-Plasticizer-
Furthermore, a plasticizer is added to the printing plate material as necessary to impart flexibility of the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid These oligomers and polymers are used.

-Wax agent-
In the image recording layer of the photosensitive lithographic printing plate, for the purpose of imparting scratch resistance, a compound that lowers the static friction coefficient of the surface can be added. Specifically, esters of long chain alkyl carboxylic acids as used in US Pat. No. 6,117,913, Japanese Patent Application No. 2001-261627, Japanese Patent Application No. 2002-032904, Japanese Patent Application No. 2002-165854 And the like. The amount of addition in the material forming the layer is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

A photosensitive lithographic printing plate can be produced by dissolving a photosensitive layer (heat-sensitive layer) composition of a plate material usually containing the above-described components in a solvent and coating the solution on a suitable support.
[Coating solvent]
Solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy Ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene, water, etc. However, the present invention is not limited to this. These solvents are used alone or in combination.
When selecting the coating solvent, the coating solvent for the upper recording layer is used for the upper recording layer and the lower recording layer in order to prevent compatibility at the interface between the layers when they are provided adjacent to each other. Is preferably selected so as not to substantially dissolve the lower recording layer. The concentration of the above components (total solid content including additives) in the solvent is preferably 1 to 50% by mass.
When using an acid anhydride, the water in the coating solution is preferably 0.5% or less.

[Amount of application]
The coating amount (solid content) of the heat-sensitive composition varies depending on the use, but it is appropriate to provide a coating amount of 0.3 to 3.0 g / m ² from the viewpoint of film properties and printing durability. . Preferably it is 0.5-2.5 g / m < ² >, More preferably, it is 0.8-1.6 g / m < ² >.

[Multilayer structure]
The photosensitive lithographic printing plate to which the present invention is applied has an image recording layer containing the above-mentioned components provided on a support, and these image recording layers have a multilayer structure of at least two layers. (For convenience, the case of two layers consisting of an upper layer and a lower layer will be described below).
In this case, the alkali-soluble resin that constitutes the upper layer and the lower layer can be the alkali-soluble resin described above, but the upper layer has a lower solubility in alkali than the lower layer. Is preferred.
The infrared absorbing dye may be an infrared absorbing dye different in each layer, or an infrared absorbing dye composed of a plurality of compounds may be used in each layer. The amount to be contained is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, and particularly preferably 0.1% to 50% by mass, based on the total solid content of the layer to be added, as described above, when used in any layer. It can add in the ratio of 0.1-30 mass%. When adding to a several layer, it is preferable to add so that the total of addition amount may become the said range.

In the state of being thermally decomposable and not thermally decomposable, the substance that substantially lowers the solubility of the alkali-soluble resin may be partially decomposed over time. Although it is effective to contain it in the lower layer, it may be any layer or both layers. The amount to be contained is as described above. When adding to a several layer, it is preferable to add so that the total of addition amount may become the said range.
In the case of a multilayer structure, the lactone compound is effective to be contained in the upper layer, but it may be any layer or both layers.

[Support]
Examples of the hydrophilic support used in the photosensitive lithographic printing plate include a dimensionally stable plate having necessary strength and durability. For example, paper, plastic (for example, polyethylene, polypropylene, Paper laminated with polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene) Terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper laminated with a metal as described above, or vapor-deposited paper, or plastic film.

  As the support, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate that has good dimensional stability and is relatively inexpensive is particularly preferable. A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by mass.

  A particularly suitable aluminum is pure aluminum, but completely pure aluminum is difficult to manufacture in terms of refining technology, and may contain slightly foreign elements. Thus, the composition of the aluminum plate is not specified, and an aluminum plate made of a publicly known material can be used as appropriate. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution for removing rolling oil on the surface is performed as desired. The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.
The roughened aluminum plate is subjected to an alkali etching treatment and neutralization treatment as necessary, and then subjected to an anodization treatment to enhance the water retention and wear resistance of the surface as desired. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used, and thus cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / dm ^2. A voltage of 1 to 100 V and an electrolysis time of 10 seconds to 5 minutes are suitable. The amount of the anodized film is preferably 1.0 g / m ² or more in terms of printing durability. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. Examples of the hydrophilic treatment include alkali metal silicates as disclosed in US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. (For example, sodium silicate aqueous solution) method. In this method, the support is immersed in an aqueous sodium silicate solution or electrolytically treated. In addition, it is disclosed in potassium fluoride zirconate disclosed in Japanese Patent Publication No. 36-22063 and U.S. Pat. Nos. 3,276,868, 4,153,461, and 4,689,272. A method of treating with polyvinyl phosphonic acid is used.

In the photosensitive lithographic printing plate, at least the above-described image recording layer is provided on a support, and an undercoat layer can be provided between the support and the image recording layer as necessary.
Various organic compounds are used as an undercoat layer component. For example, phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, 2-aminoethylphosphonic acid, and optionally substituted phenylphosphonic acid Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, optionally substituted phenylphosphoric acid, naphthylphosphonic acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid, glycerophosphinic acid and other organic phosphinic acids, glycine and β-alanine amino acids, and triethanolamine hydrochloric acid Has a hydroxy group such as salt -Alanine, and hydrochlorides of amines that may be used in combination of two or more.

  Furthermore, an undercoat layer containing at least one compound selected from the group of organic polymer compounds having a structural unit represented by the following formula is also preferred.

R ¹¹ represents a hydrogen atom, a halogen atom or an alkyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, —OR ^14. , -COOR ¹⁵ , -CONHR ¹⁶ , -COR ¹⁷ or -CN, or R ¹² and R ¹³ may be bonded to form a ring, and each of R ^{14 to} R ¹⁷ independently represents an alkyl group or Represents an aryl group, X represents a hydrogen atom, a metal atom, NR ¹⁸ R ¹⁹ R ²⁰ R ²¹ , and R ^{18 to} R ²¹ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl. Represents a group, or R ¹⁸ and R ¹⁹ may combine to form a ring, and m represents an integer of 1 to 3.

This undercoat layer can be provided by the following method. That is, a method in which water or an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent thereof is dissolved and applied on an aluminum plate and dried, and water, methanol, ethanol, methyl ethyl ketone, etc. In this method, an aluminum plate is immersed in a solution in which the above organic compound is dissolved in the above organic solvent or a mixed solvent thereof to adsorb the above compound, and then washed and dried with water or the like to provide an undercoat layer. In the former method, a solution having a concentration of 0.005 to 10% by mass of the organic compound can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by mass, preferably 0.05 to 5% by mass, the immersion temperature is 20 to 90 ° C., preferably 25 to 50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this can be adjusted to a pH range of 1 to 12 with a basic substance such as ammonia, triethylamine or potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
The coating amount of the undercoat layer is suitably ² to 200 mg / m ² , preferably 5 to 100 mg / m ² in order to obtain sufficient printing durability.

The photosensitive lithographic printing plate prepared as described above is exposed imagewise, and then developed with the alkaline developer described in detail above.
Examples of the active light source used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used. Examples of the laser beam include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, and KrF excimer laser. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser or a semiconductor laser is particularly preferable.

  If the lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming has an unnecessary image area, the unnecessary image area is erased. . Such erasing is preferably performed by applying an erasing solution as described in, for example, Japanese Patent Publication No. 2-13293 to an unnecessary image portion, leaving it for a predetermined time, and then washing with water. A method of developing after irradiating an unnecessary image portion with an actinic ray guided by an optical fiber as described in JP-A-59-174842 can also be used.

The lithographic printing plate obtained as described above can be subjected to a printing process after applying a desensitized gum if desired. However, if it is desired to obtain a lithographic printing plate with higher printing durability, Processing is performed. In the case of burning a lithographic printing plate, the preparation as described in JP-B-61-2518, JP-A-55-28062, JP-A-1-31859, and JP-A-61-159655 is performed before burning. It is preferable to treat with a surface liquid.
As the method, a method of applying the lithographic printing plate with a sponge or absorbent cotton soaked with the surface-adjusting liquid, or immersing the printing plate in a vat filled with the surface-adjusting liquid, or applying an automatic coater Application by, for example, is applied. Further, it is more preferable to make the coating amount uniform with a squeegee or a squeegee roller after coating.

In general, the amount of surface-adjusting solution applied is suitably from 0.03 to 0.8 g / m ² (dry weight). The lithographic printing plate coated with the surface-adjusting solution is dried if necessary, and then heated to a high temperature with a burning processor (for example, burning processor “BP-1300” sold by Fuji Photo Film Co., Ltd.). . The heating temperature and time in this case are preferably in the range of 180 to 300 ° C. and in the range of 1 to 20 minutes, although depending on the type of components forming the image.
The lithographic printing plate that has been subjected to burning treatment can be subjected to conventional treatments such as water washing and gumming as needed, but a surface-conditioning solution containing a water-soluble polymer compound is used. If so, so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such treatment is applied to an offset printing machine and used for printing a large number of sheets.

Next, the automatic developing apparatus according to the present invention will be described.
FIG. 1 is a configuration diagram of a first embodiment of an automatic developing apparatus for carrying out a developing replenisher replenishing method according to the present invention. As shown in FIG. 1, the automatic developing device 2 includes a developing unit 6 for developing a photosensitive lithographic printing plate (hereinafter referred to as “PS plate”) 4 and a development adhered to the PS plate 4 after development. A post-processing unit 8 for washing out the liquid and applying the gum solution and a drying unit 10 for drying the PS plate after application of the gum solution are provided.

  In the case of processing a PS plate that needs to be heated before the development processing, a preheating unit (not shown in FIG. 1) can be provided. The preheating unit is installed upstream of the developing unit 6 in the transport direction, and has a function of maintaining the specified PS plate surface temperature for a specified time while transporting the PS plate. The PS plate inserted in the preheating unit is automatically conveyed to the next process while being heated. Furthermore, it is possible to provide a pre-water washing section (not shown in FIG. 1). The pre-washing unit is installed on the upstream side in the transport direction of the developing unit 6 and on the downstream side in the transport direction of the pre-heating unit, and has a function of cleaning and cooling the surface of the PS plate with washing water while transporting the PS plate. The PS plate inserted in the pre-water washing unit is automatically conveyed to the developing unit 6 which is the next process.

  An insertion port 14 is formed in the side plate 12 of the automatic developing device 2, and the PS plate 4 inserted from the insertion port 14 is conveyed to the developing unit 6 by the conveyance roller 16. The insertion port 14 is provided with a rubber blade 18, and the insertion port 14 is closed by the rubber blade 18 when the PS plate 4 is not inserted.

  In the developing tank 20 of the developing unit 6, a conveyance roller 22, a brush roller 24, and a squeeze roller 26 are sequentially provided from the upstream side in the conveyance direction, and a backup roller 28 is provided at an appropriate position therebetween. The PS plate 4 is developed by being immersed in the developer while being conveyed by the conveying roller 22.

  The post-processing unit 8 connected to the developing unit 6 includes a water washing unit 8a and a finisher unit 8b. The washing unit 8 a is provided with rollers 30 a ′ and 30 a that convey the PS plate 4 and an injection member 34 a that sprays the washing solution in the washing tanks 32 a and 32 a onto the PS plate 4. And the flush water supply pump 78a which supplies flush water to the flush tank 32a is provided. Each of the finisher sections 8b is provided with a roller 30b for conveying the PS plate 4 and an injection member 34b for spraying the finisher liquid in the finisher tanks 32b and 32b to the PS plate 4, and supplying gum liquid to the finisher tank 32b. A liquid supply pump 77 and a gum liquid diluent supply pump 78b for supplying the gum liquid diluent are provided. Then, the PS plate 4 after the development processing is washed with water by spraying the washing liquid by the ejection member 34a while being conveyed by the conveyance roller 30a. Further, the PS plate 4 is applied by spraying the finisher liquid by the ejection member 34b while being conveyed by the conveyance roller 30b.

  At this time, the washing tank 32a is replenished with the dilution liquid 57 in the replenishment dilution liquid storage tank 53 by the washing water supply pump 78a, and the finisher tank 32b is replenished with the gum liquid in the gum liquid tank 56 by the pump 77. The dilution liquid 57 in the replenishment dilution liquid storage tank 53 is replenished by the gum liquid dilution liquid supply pump 78b. Here, the replenishment ratio of the gum solution and the diluent is, for example, 1: 1. Along with the replenishment, the washing liquid overflowed from the washing tank 32a and the gum waste liquid overflowed from the finisher tank 32b are collected in the waste liquid tank 54 in the same manner as the development waste liquid.

  Further, it is also effective to provide the washing unit 8a with a washing brush roller (not shown in FIG. 1). The washing brush roller is installed on the upper surface or upper and lower surfaces of the PS plate 4 between the spray member 34a and the PS plate 4, and rubs and rinses the surface of the PS plate 4 being conveyed while rotating.

  On the other hand, a structure in which the water washing portion 8a is the first finisher portion 8a and the finisher portion 8b is the second finisher portion 8b is also effective. The first finisher portion 8a and the second finisher portion 8b are provided with transport rollers 30a and 30b for transporting the PS plate 4, and injection members 34a and 34b for spraying the gum solution in the finisher tanks 32a and 32b to the PS plate 4, The PS plate 4 after the development processing is applied by spraying a gum solution by the spray members 34a and 34b while being transported by the transport rollers 30a and 30b. At this time, the gum solution in the finisher tank 32b of the second finisher section 8b on the downstream side is supplied by overflowing into the finisher tank 32a of the first finisher section 8a on the upstream side. Instead of this, it may be similarly supplied by a pump or the like. In this case, the flush water supply pump 78a is not used.

  At this time, the gum liquid in the gum liquid tank 56 is replenished to the second finisher tank 32 b by the pump 77 and the dilution liquid 57 in the replenishment dilution liquid storage tank 53 is replenished by the replenishment dilution liquid supply pump 78. Here, the replenishment ratio of the gum solution and the diluent is, for example, 1: 1. With this replenishment, the gum waste liquid overflowed from the first finisher tank 32a is collected in the waste liquid tank 54 in the same manner as the development waste liquid.

  The drying unit 10 connected to the finisher unit 8 is provided with a guide roller 36 and a pair of skewer rollers 38 in order from the upstream side in the transport direction. The drying unit 10 is provided with drying means such as hot air supply means and heat generation means (not shown). The drying unit 10 is provided with a discharge port 40, and the PS plate 4 dried by the drying means is discharged from the discharge port 40. In addition, a shutter 44 is provided in a path between the drying unit 10 and the finisher unit 8, and the path 46 is closed by the shutter 44 when the PS plate 4 does not pass through the path 46.

  The developing tank 20 is provided with a box-shaped shielding lid 60 integrally with the tank wall. The bottom wall of the shielding lid 60 is continuously curved in an arc shape so as not to come into contact with the upper outer peripheral surfaces of the transport roller 22, the brush roller 24, and the backup roller 28, and does not interfere with the roller or the like. Since the shielding lid 60 is box-shaped, an airtight space is defined in the upper part of the developing tank 20, and the amount of air in the developing unit 6 is reduced as much as possible. Further, since the shielding lid 60 is provided, the contact area between the developer and air is reduced as much as possible.

  In the automatic developing apparatus 2 having the above-described configuration, the rubber blade 62 is provided at an appropriate place, and the developing unit 6 to the finisher unit 8b are substantially airtight with respect to the external atmosphere, so that outside air does not flow in. ing. Further, a space between the developing unit 6 and the water washing unit 8a is substantially airtight by the rubber blade 62 so that air in the water washing unit 8a does not flow into the developing unit 6. Therefore, the developing unit 6 has a hermetically sealed structure in which air flows in slightly when the PS plate 4 passes, but is substantially airtight and hardly receives air.

  Next, the developing unit 6 will be described in detail. A developing solution circulation pipe 80 is connected to the developing tank 20. In the circulation pipe 80, a developer circulation pump 71, a conductivity sensor 73, and a filter (not shown) are provided. The developer circulation pump 71 sucks the developer in the developer tank 20 from the suction hole at the bottom of the developer tank 20 into the circulation pipe 80 and circulates in the circulation pipe 80, and again into the developer tank 20. Discharge. The filter filters the developer flowing in the circulation pipe 80. The electrical conductivity sensor 73 as electrical conductivity measuring means measures the electrical conductivity of the developer flowing in the circulation pipe 80.

  In addition, the developing unit 6 includes replenishment pipes 90 and 91, a replenishment stock solution storage tank 55 connected to the replenishment pipe 90, and a replenishment stock solution interposed in the replenishment pipe 90. A pump 74, a replenishment diluent storage tank 53 connected to the replenishment pipe 91, and a replenishment diluent supply pump 76 interposed in the replenishment pipe 91 are provided, and these function as developer replenishing means. Further, the developing waste liquid overflowed from the developing tank 20 is collected in the waste liquid tank 54.

  More specifically, a pair of development replenisher replenishment pipes 90 and 91 obtained by diluting the development replenishment stock solution 58 with the replenishment diluent 57 is provided in the vicinity of the developing tank 20. The other end (lower end in FIG. 1) of the replenishment piping 90 for the development replenishing stock solution 58 is connected to the replenishing stock solution storage tank 55, and a replenishing stock solution supply pump 74 is provided in the piping. The replenishment stock solution supply pump 74 supplies the development replenishment stock solution 58 from the replenishment stock solution storage tank 55 to the developing tank 20. The replenishment pipe 91 for the replenishment diluent 57 has the other end (lower end in FIG. 1) connected to the replenishment diluent storage tank 53, and a replenishment diluent supply pump 76 is provided in the pipe. The replenishment diluent supply pump 76 supplies the replenishment diluent (water) 57 from the replenishment diluent storage tank 53 to the developing tank 20. That is, the replenishment pipe 91, the replenishment diluent supply pump 76, and the replenishment diluent storage tank 53 constitute a dilution water replenishment device.

  The replenishment stock solution supply pump 74 and the replenishment dilution solution supply pump 76 are provided with a control ROM 51a or a control RAM 51b as a condition storage means and a time measurement unit 52 based on signals from the conductivity sensor 73 and the time measurement unit 52. It is controlled by a device (control means) 50. Further, the control device 50 drives the transport roller 22, the brush roller 24, the squeeze roller 26, and the like at appropriate timing based on the signal from the plate detection sensor 27, and transports the PS plate.

  Further, the control device 50 uses the time measuring unit 52 to measure the elapsed time from the previous time of replenishment integration time, the elapsed time from the previous conductivity measurement time, and the elapsed time since the previous replenishment. The area of the plate is calculated on the basis of the signal from, and the conductivity of the developer is measured by the conductivity sensor 73. Then, if necessary using the values, the control device 50 supplies the developer replenisher (development replenisher stock 58 + replenisher diluent 57) at a replenishment amount / replenisher dilution rate determined in advance, and the replenishment stock solution storage tank 55. And supplied from the replenishment diluent storage tank 53 to the developing tank 20.

  Next, control by the control device 50 will be described. 2 to 12 are examples of flowcharts showing a control method by the control device 50. In the basic control method (first control method) of the present invention shown in FIG. 2, the development is roughly based on the replenishment amount set value with time and the replenishment amount set value for processing determined in advance. By calculating the amount of replenishment over time and the amount of processing replenishment necessary to keep the liquid activity constant, and comparing the calculated conductivity value obtained from these values with the developer conductivity value measured at a predetermined time interval. After increasing / decreasing and correcting the time-dependent replenishment amount set value / process replenishment amount set value, the necessary time-dependent / replenishment liquid amount is replenished. By doing this, even if the processing conditions such as the plate type, plate size and processing frequency, and environmental conditions such as environmental carbon dioxide concentration and humidity change, replenishment based on the appropriate replenishment amount with time and processing replenishment amount is performed. It becomes possible.

First, the first control process shown in FIG. 2 will be described.
In step 1 (hereinafter abbreviated as S1), the replenishment liquid amount with time calculated from the replenishment amount with time and the elapsed time is replenished if a predetermined time interval has elapsed. Next, in S2, if a plate for each predetermined fixed area has been processed, the amount of processing replenisher calculated from the processing replenishment amount setting value and the processing area is replenished.
Next, in S3, if the value of the replenishment method set value: R is 1 indicating the conductivity reference replenishment method, the process proceeds to S4. If the value indicating the conductivity reference replenishment method is not 1, the process proceeds to S10. The replenishment method set value: R is set to the conductivity reference replenishment method in normal operation. However, if the conductivity sensor 73 fails, the conductivity reference replenishment method does not function normally. Change to a value other than 1 in some cases.
The value of the replenishment method setting value: R may be changed automatically or manually. Replenishment method setting value: When the value of R is automatically changed, for example, the output value of the conductivity sensor 73 is compared with a predetermined range, and if it exceeds this range, the conductivity sensor 73 has failed. The value is automatically changed to a value other than 1 for the replenishment method setting value: R. The determination of the occurrence of a failure is not limited to this, and may be another method such as, for example, visual inspection of the probe portion of the conductivity sensor 73.
On the other hand, when the value of the replenishment method setting value: R is automatically changed, for example, the photosensitive layer of the image portion is excessively developed and melted and thinned on the processed plate. When a phenomenon such as an image portion that originally forms a small dot image has been developed and dissolved, or a photosensitive layer of a non-image portion is left undissolved, is observed by visual observation, the conductivity sensor 73 fails. Therefore, it is assumed that the conductivity reference replenishment method has failed, and the value of the replenishment method setting value: R is manually changed to a value other than 1.

  Therefore, in S3, the process is divided into a case where the conductivity sensor 73 is operating normally and a case where other failure occurs, and different processes are performed. When the former is in normal operation, it is operated by the conductivity reference supplement method, and in the other cases, it is operated by the area aging method without using the conductivity measurement value. This makes it possible to continue operation with a developer replenishment method that does not depend on conductivity when the conductivity sensor 73 fails, etc., while calling the operator for maintenance without completely stopping the device. Can continue to operate.

In S4, it is determined whether the elapsed time from the time of start-up or the previous measurement of the developer conductivity has reached a predetermined time. If it has reached, the process proceeds to S5.
In S5, the conductivity of the developer is measured. Next, in S6, an electric conductivity calculation value is calculated from the replenished temporal replenisher amount / process replenisher amount.
In S7, the calculated conductivity value is compared with the measured conductivity value, and if the measured conductivity value is large, the process proceeds to S8, and if the measured conductivity value is small, the process proceeds to S9.
In S8, both the process replenishment set value and the time-dependent replenishment set value are decreased by a predetermined amount. On the other hand, in S9, both the process replenishment set value and the time-dependent replenishment set value are increased by a predetermined amount.
In S10, the state of the operation switch of the automatic developing apparatus is checked. If the operation switch is turned on, the process returns to S1, and if the operation switch is turned off, the process is terminated by stopping the apparatus.

Next, the second control process will be described with reference to FIGS.
In S11, the time-dependent replenishment integrated value: I _VC and the process replenishment integrated value: I _VB , which are variables used during the control, are initialized, that is, 0 is substituted. Further, it is determined whether or not the automatic developing apparatus is activated for the first time. If the automatic developing apparatus is activated for the first time, the replenisher replacement rate: X and the replenishment ratio with time: F, which are variables used during the control, are initialized. That is, 0 is substituted for X and C ₅ is substituted for F.

In S12, the elapsed time from the time of integrating the startup or previous time lapse replenishment amount, a predetermined time: determining whether reached T _K, to S13 if elapsed, the process proceeds to S14 when not reached . In S13, the elapsed time: required by _{T K} time lapse replenishment amount with time replenishment amount set value: calculated from _{V C,} is integrated in the _{I VC.} For example, the calculation is performed as follows.
_{I VC + V C × T K} → I VC (9)

In S14, it is determined whether the processing area at the time of activation or the previous processing replenishment amount has been accumulated has reached a predetermined processing area: S, and if it is processed, the process proceeds to S15, and if not, the process proceeds to S16. . In S15, the processing area: processing replenishment rate processing replenishment amount set value required by S: calculated from _{V B,} is integrated into _{I VB.} For example, the calculation is performed as follows.
I _VB + V _B × S → I _VB (10)

Next, in S16, the time elapsed from the time or the time of measuring the last electric conductivity of developer starts, predetermined time: it is determined whether or not reached T _D, to step S17 if the elapsed when not reached Proceed to S33.
Step S17 electric conductivity of the developer is measured, the value assigned to a variable: d _M. In the next S18, the elapsed time from the time of performing the last replenishment to measure T _P. Further, in the next S19, a conductivity calculation value 1: d _T1 is calculated from a predetermined arithmetic expression such as a replenisher replacement rate: X and a time-dependent replenishment ratio: F. As an arithmetic expression at this time, for example, the following expression is appropriate.
d _T1 = (1−X) × D _M + X × [(1−F) × D _B + F × D _C ] (11)
(D _M , D _C , and D _B are constants obtained experimentally in advance)

In the next S20, an electric conductivity calculation value 2: d _T2 is calculated from d _T1 , T _P , (I _VC + I _VB ) and a predetermined arithmetic expression. As an arithmetic expression at this time, for example, the following expression is appropriate.
_{d T2 = [V T × d} T1 + V C × T P × D C + (I VC + I VB -V C × T P) × D B] ÷ (V T + I VC + I VB) (12)
(VT: Capacity of developing tank of automatic developing device)
Further, in the next S21, an electric conductivity calculation value 3: d _T3 is calculated from d _T1 , (IV _C + I _VB ), F and a predetermined calculation formula. As an arithmetic expression at this time, for example, the following expression is appropriate.
d _T3 = [V _T × d _T1 + (I _VC + I _VB ) × F × D _C + (I _VC + I _VB ) × (1−F) × D _B ] ÷ (V _T + I _VC + I _VB ) (13)

In the next S22, the replenishment amount integrated amount: (I _VC + I _VB ) is compared with a predetermined replenishment amount per time: V _L, and if (I _VC + I _VB ) is large, the process proceeds to S23. Advances to S33.

  In S23, if the value of the replenishment method setting value: R is 1 indicating the conductivity reference replenishment method, the process proceeds to S24. If the value indicating the conductivity reference replenishment method is not 1, the process proceeds to S31.

In S24, the electric conductivity of developer: _{d M} and electric conductivity calculated value _2: compares the _{d T2,} when _{d M} is small to S25, otherwise proceed to S26.
Time lapse replenishment amount in S25 setpoint: _{V C} to a predetermined constant: _{C 1} is added, subtracted _{C 1} from the _{V C} S26. On the other hand, the processing replenishment amount set value in S25: _V predetermined constant _{B: C 2} was added, subtracted _{C 2} from S26 in _{V B.}
In the next S27, the electric conductivity of developer: _{d M} and electric conductivity calculated value _3: compare _{d T3,} when _{d M} is small to S28, otherwise proceed to S29.
A predetermined constant to S28 in _{V C: C 3} was added, subtracted _{C 3} from the _{V C} S29. On the other hand, a predetermined constant from S28 in _{V B:} subtracting _{C 4,} added _{C 4} to S29 in _{V B.}

In the next S30, the values of X and F are updated with the (I _VC + I _VB ) value. It is appropriate to update the value as follows, for example.
(V _T × X + I _VC + I _VB ) ÷ (V _T + I _VC + I _VB ) → X (14)
(V _T × X × F + I _VC ) ÷ (V _T × X + I _VC + I _VB ) → F (15)

In S31, the developer is replenished with an amount of replenisher of (I _VC + I _VB ). In the next S32, I _VC and I _VB are initialized, that is, 0 is substituted for each.

  In S33, the state of the operation switch of the automatic developer is investigated. If the operation switch is turned on, the process returns to S12, and if the operation switch is turned off, the process is terminated by stopping the apparatus.

As described above, the control processing of this embodiment can be summarized as follows.
In this control process, the developer conductivity value is measured at predetermined intervals, and the predetermined replenishment amount set value is integrated into the replenishment amount integrated value every predetermined time, and the plate processing of a constant area is performed. The processing replenishment amount set value predetermined for each time is added to the processing replenishment amount integrated value, a replenisher replacement rate that is a ratio of the replenishment amount in the developer in the developing tank is calculated, and After calculating the replenishment ratio with time, which is a ratio, when the total amount of the replenishment amount integrated value with time and the processing replenishment amount integrated value exceeds a predetermined replenishment amount minimum value, the predetermined replenishment method setting value is the conductivity If the value indicates a method, execute the following (A-1), (A-2), (A-3), (A-4), (A-5), (A-6) When the replenishment method set value is not a value indicating the conductivity method, the following (B-1) and (B-2) are executed. Note that the execution order of each step may be appropriately changed. (A-1) The elapsed time from the last replenishment time to the present time is measured, and the first conductivity calculation value is calculated from the elapsed time and the replenisher replacement rate.
(A-2) The time-dependent replenishment amount setting value and the processing replenishment amount setting value are changed based on a result of comparing the first conductivity calculation value and the measured developer conductivity value.
(A-3) The second conductivity calculation value is calculated using the replenisher replacement rate and the time-dependent replenishment ratio.
(A-4) The replenishment amount setting value with time and the processing replenishment amount setting value are changed according to a result of comparing the second conductivity calculation value and the measured developer conductivity value.
(A-5) A replenisher of a total amount of the replenishment amount integrated value with time and the processing replenishment amount integrated value is replenished to the developer in the developing tank.
(A-6) The integrated replenishment amount with time and the processing replenishment amount integrated value are initialized.
(B-1) A replenisher of a total amount of the replenishment amount integrated value with time and the processing replenishment amount integrated value is replenished to the developer in the developing tank.
(B-2) The integrated replenishment amount with time and the integrated replenishment amount with processing are initialized.

Next, the third control process will be described with reference to FIGS. The third control process is obtained by adding a dedicated control process for starting the automatic developing device to the second control process shown in FIGS. 3 and 4.
In S41, the replenishment integrated value over time: I _VC and the process replenishment integrated value: I _VB which are variables used during the control are initialized, that is, 0 is substituted. Further, it is determined whether or not the automatic developing apparatus is activated for the first time. If the automatic developing apparatus is activated for the first time, the replenisher replacement rate: X and the replenishment ratio with time: F, which are variables used during the control, are initialized. That is, 0 is substituted for X and C ₅ is substituted for F.

  Next, in S42, if the replenishment method setting value: R is 1 indicating the conductivity reference replenishment method, the process proceeds to S43. If the value indicating the conductivity reference replenishment method is not 1, the process proceeds to S50.

Next, in S43, the time elapsed from the time or the time of measuring the last electric conductivity of developer starts, predetermined time: it is determined whether or not reached T _D, in S44 if the elapsed when not reached Proceed to S49.
Step S44 electric conductivity of the developer is measured, the value assigned to a variable: d _M. Further, in the next S45, a conductivity calculation value 1: d _T1 is calculated from a predetermined arithmetic expression such as a replenisher replacement rate: X and a time-dependent replenishment ratio: F. As an arithmetic expression at this time, for example, the following expression is appropriate.
d _T1 = (1−X) × D _M + X × [(1−F) × D _B + F × D _C ] (14)
_{(D M, D B, D} C are constants experimentally determined in advance)

In the next S46, compares the _{d M} and _{d T1,} the process proceeds to S47 The smaller the _{d M,} the process proceeds to S51 otherwise.
In S47, a replenisher of _VL amount is replenished to the developer. In the next S48, the values of X and F are updated with the value of _VL . It is appropriate to update the value as follows, for example.
(V _T × X + V _L ) ÷ (V _T + V _L ) → X (15)
_{(V T × X × F +} V L) ÷ (V T × X + V L) → F (16)

  In S49, the state of the operation switch of the automatic developer is investigated. If the operation switch is turned on, the process returns to S42, and if the operation switch is turned off, the process is terminated by stopping the apparatus.

In S50, the amount of replenisher calculated from the time when the automatic developing device has been stopped: T _OFF is replenished to the developer in the developing tank. In this case, it is appropriate to calculate the amount of replenisher: _VHC as follows.
V _HC = V _COFF × T _OFF (17)
(V _COFF is an experimental value obtained in advance)

  Only when the control proceeds to S51, the photosensitive material can be developed. Therefore, for example, a message that processing is possible at this time is displayed.

  Since the steps of S51 to S71 are the same as S12 to S32 in the control processing shown in FIGS. 3 and 4, the description thereof is omitted here, but the target conductivity value is updated with the replenishment, Conductivity measurement and developer replenishment are repeated until the developer conductivity value exceeds the target conductivity.

  In S72, the state of the operation switch of the automatic developer is checked. If the operation switch is turned on, the process returns to S51. If the operation switch is turned off, the process is terminated by stopping the apparatus.

As described above, the control processing of this embodiment can be summarized as follows.
In this control process, a conductivity value in which the activity of the developer is within an appropriate range is calculated as a target conductivity value, and a predetermined replenishment method setting indicates the conductivity method immediately after the operation of the automatic developing device is started. In the case of a value, execute the following (C-1), (C-2), (C-3), (C-4), and the replenishment method set value is not a value indicating the conductivity method In this case, the developer replenisher is replenished to the developer according to the time during which the automatic developing device has been stopped. Note that the execution order of each step may be appropriately changed.
(C-1) Measure the conductivity of the developer at fixed intervals.
(C-2) When the measured developer conductivity value is lower than the target conductivity value, a predetermined amount of developer replenisher is replenished to the developer,
(C-3) Update the target conductivity value with the replenishment,
(C-4) Repeat (C-1), (C-2), and (C-3) until the developer conductivity value exceeds the target conductivity.

  According to the above control of the automatic developing device, the replenishment amount with time and the processing replenishment amount are automatically corrected by utilizing the value of the developer conductivity. In other words, even with changes in the type, size, and processing frequency of photosensitive materials, changes in ambient carbon dioxide concentration, and wind speed in the surrounding atmosphere, it is possible to always set appropriate aging and processing replenishment amounts with stable and constant sensitivity. Development processing can be performed. Therefore, it is possible to minimize the variation of the developer sensitivity with respect to the change in the development processing conditions while making the developing unit of the automatic developing device simple and inexpensive. In addition, even when the conductivity sensor breaks down, it is possible to switch to an alternative replenishment method, so that it is possible to continue processing the plate material.

  Next, a second embodiment of the present invention will be described. FIG. 8 is a block diagram of an automatic developing apparatus according to the second embodiment of the present invention. As shown in FIG. 8, in the automatic developing apparatus 100 of the present embodiment, the internal processing unit is covered with an outer panel 114. Inside the outer panel 114, a developing tank 118 for developing the PS plate 112, a developing section 122 having an overflow pipe 120 for collecting the developer overflowed from the developing tank 118, and the PS plate 112 were attached. A water washing part 124 for washing the developer with water and a finisher part 126 for applying a gum solution to the PS plate 112 after washing with water and desensitizing it are disposed. The flushing section 124 is provided with a flushing tank 128, and the finisher section 126 is provided with a gum solution tank 130.

  The outer panel 114 is provided with a slit-like insertion port 202 and a discharge port 204, respectively. A reentry insertion port (sub-insertion port) 250 for inserting the PS plate 112 is provided between the developing unit 122 and the water washing unit 124 on the upper surface of the outer panel 114. The sub-insertion opening 250 serves as an insertion opening for the PS plate 112 for performing processing excluding development processing.

  A blade 252 is disposed in the sub insertion port 250. The blade 252 is in contact with the outer panel 114 whose tip is used as a guide support surface of the sub insertion port 250, and the base is fixed to the back side of the outer panel 114 via a bracket 254. For this reason, the sub insertion port 250 is closed by the blade 252.

  The drying unit (not shown) is configured to blow hot air on both sides of the PS plate 112 while the PS plate 112 fed from the finisher unit 126 is conveyed by a large number of rollers (not shown). Yes.

  A pair of conveying rollers 132 is disposed on the side of the developing unit 122 where the PS plate 112 is inserted into the developing tank 118, and the PS plate 112 is inserted between the pair of conveying rollers 132 from the insertion port 202. It is like that.

  A rubber blade 206 is attached in the vicinity of the downstream side of the conveying roller 132. The tip of the blade 206 is in contact with the side wall of the developing tank 118 of the developing unit 122, and the base is attached to the outer panel 114 via a bracket 256. The bracket 256 includes a fixed portion 256A and a slide portion 256B attached to the fixed portion with a thumbscrew 258, and the blade 206 is fixed to the slide portion 256B. For this reason, the blade 206 is configured such that the tip end portion can be separated from the side wall of the developing tank 118 by loosening the thumbscrew 258 and sliding the slide portion 256B relative to the fixed portion 256A.

  In addition, a plate detection sensor 208 capable of measuring the presence / absence of the PS plate 12 and the plate area of the conveyed plate is attached in the vicinity of the insertion port 202.

  The developing tank 118 has a substantially inverted mountain shape with the upper part opened and the bottom center part protruding downward. A pump 260 is provided in the developing tank 118, and the developer in the developing tank 118 is sucked out by the pump 260 and ejected from spray pipes 144 and 272 described later. Thereby, the developer stored in the developing tank 118 is circulated. During this circulation, it passes through a conductivity sensor 262 that measures the conductivity of the developer. The developing tank 118 is supplied with a replenishing stock solution from a development replenishing stock solution tank 266 via a replenishing stock solution supply pump 264. As will be described later, the developing tank 118 is supplied with dilution water from a washing tank 128 via a pump 286.

  The pump 264 and the pump 286 are controlled by a control device 50 including a control ROM 51a or a control RAM 51b, which is a condition storage unit, and a time measurement unit 52 based on signals from the conductivity sensor 262 and the time measurement unit 52. In addition, since the effect of the control apparatus 50 is the same as that of 1st Embodiment, the description is abbreviate | omitted.

  In the developing tank 118, a guide plate 268 is disposed on the upstream side, and a number of guide rollers 134 and a rotating brush roller 270 are disposed on the downstream side. The guide roller 134 and the rotating brush roller 270 are rotatably spanned between a pair of side plates of the developing tank 118.

  A guide roller 136 having a relatively large diameter is provided above the guide plate 268, a rotating brush roller 138 and a guide roller 140 are provided above the guide roller 134, and a rotating brush roller 270 is provided below the guide roller 140, respectively. Arranged. In addition, a pair of squeezing rollers 142 having a function of squeezing the surface of the PS plate 112 are disposed in the center of the developing tank 118.

  The overflow pipe 120 is disposed on the most downstream side of the developing tank 118. When the liquid level of the developer exceeds a predetermined level, the developer is guided to the waste liquid tank 284 and discarded.

  A liquid level lid 150 is disposed on the surface of the developer in the developing tank 118. The liquid level cover 150 has a portion corresponding to the rotating brush roller 138 and the guide roller 140 adjacent thereto protruding in a substantially arc shape, and is in close contact with the developer surface in order to minimize the contact between the developer surface and air, Both ends of the liquid surface lid 150 in the transport direction of the PS plate 112 are attached to a side plate (not shown) so as to move up and down according to the increase / decrease of the developer.

  The tip of the blade 274 is in contact with the downstream end of the liquid level lid 150 in the transport direction. The blade 274 is fixed to the outer panel 114 via a bracket 276. The blade 274 partitions the liquid level of the developer exposed from the downstream end in the transport direction of the liquid level cover 150 from the upper side of the liquid level cover 150, and the blade 206 (the developing tank 118 of the developing tank 118) in the vicinity of the insertion port 202. The state in contact with the side wall) completely separates the upper portion of the liquid level cover 150 from the outside air, and can suppress evaporation of the developer.

  A pair of rollers 154 that sandwich and transport the PS plate 112 and squeeze the developer from the surface of the PS plate 112 are disposed on the most downstream side in the transport direction of the developing tank 118.

  On the other hand, the automatic developing apparatus 100 is provided with a water washing tank 128 of a water washing unit 124 on the downstream side of the developing unit 122. Two pairs of transport rollers 152 and 153 are disposed above the water washing tank 128.

The rinsing water 128 stores rinsing water after washing away the developer from the PS plate 112 sent out from the developing tank 118. A spray pipe 156 is provided on the upstream side of the transport roller 153 and on the upper side of the transport path, and a plurality of discharge ports communicating with the inside are provided on the outer periphery of the spray pipe 156. From the spray pipe 156, the washing water pumped up from the washing water tank 278 by the pump 280 is dropped onto the roller on the upper side of the conveying roller 153, and the conveying roller 153 rotates, so that the washing water quickly flows onto the surface of the PS plate 112. The surface of the PS plate 112 is washed with water.

  The lower part of the lower roller of the transport rollers 152 and 153 is accommodated in the tray 162. Washing water is stored in the tray 162 and is pumped up by the lower roller to clean the back surface of the PS plate 112 and to prevent the upper transport rollers 152 and 153 from drying.

  Further, the washing water diffused in the width direction on the surface of the PS plate 112 falls from the both ends in the width direction of the PS plate 112 to the receiving tray 162 below, and the back surface of the PS plate 112 is washed away by the washing water pumped up from the receiving plate 162. It is configured to be processed. The flush water overflowing from the tray 162 is guided to the flush tank 128. The flush tank 128 is provided with an overflow pipe 282, which is discarded into a waste liquid tank 284 when a predetermined liquid level is exceeded.

  The washing tank 128 and the developing tank 118 are communicated with each other via a pump 286, and the washing water in the washing tank 128 is guided to the developing tank 118 by driving the pump 286, and the replenishing stock solution is supplied to the developing tank 118. It can be used as a diluting solution when supplying.

  A pair of transport rollers 178 are provided above the gum solution tank 130 of the finisher portion 126. The PS plate 112 sent out by the transport roller 153 is guided to the transport roller 178.

  In addition, spray pipes 182 and 288 are arranged on the upstream side of the conveyance roller 178 in the vertical direction of the conveyance path. From the spray pipes 182 and 288, the gum solution pumped up from the gum solution tank 290 by the pump 292 is discharged and supplied to the front and back surfaces of the PS plate 112.

  The conveyance roller 178 nips and conveys the PS plate 112 and squeezes the gum solution supplied by the spray pipe 182 to desensitize the surface of the PS plate 112. The gum solution squeezed from the surface of the PS plate 112 is collected in the gum solution tank 130. The gum solution in the gum solution tank 130 is circulated by a pump 294. The gum solution tank 130 is provided with an overflow pipe 296 so that when the gum solution exceeds a predetermined liquid level, it is guided to the waste solution tank 284 and discarded.

  Further, the lower part of the lower conveyance roller 178 is immersed in the gum liquid stored in the gum liquid tank 130, and the lower conveyance roller 178 is connected to the gum liquid tank 130 from the gum liquid tank 130 on the back side of the PS plate 112. The coating process is performed by pumping up. As a result, the conveying roller 178 takes out the gum solution to perform the desensitization process on the back surface of the PS plate 112 and suppresses the drying of the upper conveying roller 178 so that the components of the processing liquid do not deposit on the surface of the conveying roller 178. It has become.

  The PS plate 112 that has been processed by the finisher unit 126 passes through the discharge port 204 of the casing 200 and is sent to a drying unit (not shown).

  Here, the discharge port 204 is provided with a lid 210 as a partition plate. The lid 210 is fixed to the shaft 212. The shaft 212 can be rotated by driving means (not shown) (for example, a solenoid). The rotation of the shaft 212 is performed based on the detection of the PS plate 112 by the plate detection sensor 208 provided in the vicinity of the insertion port 202. In other words, the lid 210 is substantially horizontal (after the detection of the discharge port 204) while the plate detection sensor 208 is detecting the PS plate 112 and after it is no longer detected (after the rear end is detected) until a predetermined time elapses. It is held in an open state, and the others are vertical (the discharge port 204 is closed).

  The operation of this embodiment will be described below. First, processing tanks such as the developing tank 118, the water washing tank 128, and the gum solution tank 130 are covered with a casing 200 such as an outer panel 114 serving as an upper lid and the main body 108. Further, when the PS plate 112 is not developed by the automatic developing device 100, the insertion port 202 is closed because the blade 206 is in contact with the side wall of the developing tank 118. On the other hand, since the discharge plate 204 does not detect the PS plate 112 by the plate detection sensor 208, the lid 210 is in a vertical state, and the discharge port 204 is also closed. Further, the sub insertion port 250 is also closed by the blade 252, and the liquid level cover 150 of the developing unit 122 is also closed by the blades 206 and 122. For this reason, the developing solution in the developing tank 118, the washing water in the washing unit 124, and the gum solution in the finisher unit 126 are not exposed to the outside air, and there is almost no carbon dioxide fatigue. For this reason, since it is possible to suppress a decrease in developing ability due to deterioration over time, for example, the replenishing amount of the replenishing stock solution in the developing unit 122 can be drastically reduced. In particular, since the surface of the developer in the developing tank 118 is covered with the liquid level lid 150, the effect of preventing contact between the developer and the outside air is great.

  In order to minimize the contact between the developing solution and the outside air, it is preferable to shorten the opening time of the lid 210 as much as possible. Therefore, a structure in which the PS plate 112 is open only while it passes and is closed during the other time is preferable.

  Since the control by the control device 50 is the same as the contents of the flowchart of the replenishing method of the developing replenisher in FIGS. 2 to 7 described in the first embodiment, the description thereof is omitted here.

  Next, in the case where the development replenisher replenishment method and the conventional developer replenisher replenishment method in the above embodiment were applied, the variation range of the developer sensitivity was obtained by experiments. Production of developer A, B, C, D, replenisher A, B, C, D, photosensitive material A, B, C, D, E used in Examples 1-10 and Comparative Examples 1-20 below Describes the method.

[Developer A]
A developer DP-7 manufactured by Fuji Photo Film Co., Ltd. was diluted 1/9 and used.
[Developer B]
A developer DT-2 manufactured by Fuji Photo Film Co., Ltd. was diluted 1/9 and used.
[Developer C]
The following components were dissolved in water, and a developer was prepared so as to have the following pH with KOH.
Surfactant (see [Chemical Formula 15]) 5% by mass
2,4,7,9-Tetramethyl-5-decyne-4,7-diol 0.1% by mass
Ethylenediaminetetraacetic acid 4Na salt 0.2% by mass
Potassium carbonate 0.2% by mass
pH [25 ° C] 12.0

[Developer D]
The following components were dissolved in water, and a developer was prepared so as to have the following pH with KOH.
Compound (Y) of general formula (I) 5.0 g
Ethylenediaminetetraacetic acid 4Na salt 0.1 g
Additive 1 (P) 1.0 g
Additive 2 (Q) 1.0 g
pH [25 ° C] 12.0

Y:

P:

Q:

[Replenisher A]
A developer replenisher DP-7RW manufactured by Fuji Photo Film Co., Ltd. was used.
[Replenisher B]
A developer replenisher DT-2R manufactured by Fuji Photo Film Co., Ltd. was used.
[Replenisher C]
The following components were dissolved in water, and a developer was prepared so as to have the following pH with KOH.
Surfactant (see [Chemical Formula 19]) 5% by mass
2,4,7,9-tetramethyl-5-decyne-4,7-diol
0.1% by mass
Ethylenediaminetetraacetic acid 4Na salt 0.2% by mass
Potassium carbonate 0.2% by mass
pH [25 ° C] 13.0

[Replenisher D]
The following components were dissolved in water, and a developer was prepared so as to have the following pH with KOH.
Compound (Y) of general formula (I) 5.0 g
Ethylenediaminetetraacetic acid 4Na salt 0.1 g
Additive 1 (P) 1.0 g
Additive 2 (Q) 1.0 g
pH [25 ° C] 13.0

Y:

P:

Q:

[Photosensitive material A]
It created based on Example 1 of Unexamined-Japanese-Patent No. 2000-231188 specification. The resulting photosensitive plate was subjected to image exposure for 1 minute using a printer FT26V2UPNS (light source: 2 kW metal halide lamp) manufactured by Nuark, USA.
[Photosensitive material B]
It created based on Example 1 of Unexamined-Japanese-Patent No. 7-295212. The obtained photosensitive plate was subjected to 50 count image exposure with a printer FT26V2UPNS (light source: 2 kW metal halide lamp) manufactured by Nuark, USA.
[Photosensitive material C]
A 0.3 mm thick aluminum plate (material 1050) was washed with trichlorethylene and degreased, and then a nylon brush and a 400 mesh pumice-water suspension were used to make the surface grainy and washed thoroughly with water. After washing, this aluminum plate was etched by immersing it in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds, washed with water, further immersed in a 20% nitric acid aqueous solution for 20 seconds, and washed again with water. The etching amount of the grained surface at this time was about 3 g / m ² . Next, the aluminum plate was provided with an anodized film of 3 g / m ² with a direct current of 15 A / dm ² using 7% sulfuric acid as an electrolyte, washed with water and dried. This was treated with a 2.5% aqueous solution of sodium silicate at 30 ° C. for 10 seconds, the following undercoat layer coating solution was applied, and dried at 80 ° C. for 15 seconds to obtain a support. The dry coating amount of the undercoat layer after drying was 15 mg / m ² .

<Coating liquid for undercoat layer>
The following copolymer P (molecular weight 28000) 0.3 g
Methanol 100g
1g of water
Copolymer P

<Synthesis of specific copolymer>
Synthesis example (specific copolymer 1)
A 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel is charged with 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile and cooled in an ice-water bath. The mixture was stirred while. To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped with a dropping funnel over about 1 hour. After completion of the dropwise addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes. To this reaction mixture, 51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was added to 1 liter of water with stirring, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to take out a precipitate, which was slurried with 500 ml of water, and then the slurry was filtered, and the resulting solid was dried to give white N- (p-aminosulfonylphenyl) methacrylamide. A solid was obtained (yield 46.9 g).
Next, 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide (0.0192 mol) and 2.94 g of ethyl methacrylate (0.0258) were added to a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel. Mol), 0.80 g (0.015 mol) of acrylonitrile and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while being heated to 65 ° C. with a hot water bath. To this mixture, 0.15 g of “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining at 65 ° C. A further mixture of 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide, 2.94 g of ethyl methacrylate, 0.80 g of acrylonitrile, N, N-dimethylacetamide and 0.15 g of “V-65” was added to this reaction mixture. It dropped by the dropping funnel over 2 hours. After completion of the dropwise addition, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol is added to the mixture, the mixture is cooled, and the resulting mixture is poured into 2 liters of water while stirring the water. After stirring the mixture for 30 minutes, the precipitate is removed by filtration and dried. Gave 15 g of a white solid. It was 53,000 when the weight average molecular weight (polystyrene standard) of this specific copolymer was measured by the gel permeation chromatography.

The following image recording layer coating solution was applied onto the obtained support so that the dry coating amount was 1.8 g / m ² to obtain a positive-type infrared-sensitive lithographic printing plate.
<Coating liquid for image recording layer>
0.4 g of the above specific copolymer
0.6 g of m, p-cresol novolak
(M / p ratio = 6/4, weight average molecular weight 8000, containing 0.5% of unreacted cresol)
Cyanine dye A 0.1g
Phthalic anhydride 0.05g
0.002 g of p-toluenesulfonic acid
Ethyl violet 0.02g
(Counterion: 6-hydroxy-β-naphthalenesulfonic acid)
0.01 g of esterified product of naphthoquinone 1,2-diazide-5-sulfonylcroid and pyrogallol-acetone resin
Fluorosurfactant 0.05g
(Product name: MegaFuck F-177, manufactured by Dainippon Ink & Chemicals, Inc.)
Methyl ethyl ketone 8g
1-methoxy-2-propanol 4g

[Photosensitive material D]
(Production of support)
<Aluminum plate>
Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.001 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 mass%, Ti: It contains 0.03% by mass, and the balance is prepared using Al and an inevitable impurity aluminum alloy. After the molten metal treatment and filtration, an ingot having a thickness of 500 mm and a width of 1200 mm is obtained by a DC casting method. Produced. After the surface was shaved with a chamfering machine with an average thickness of 10 mm, the temperature was kept constant at 550 ° C. for about 5 hours, and when the temperature dropped to 400 ° C., rolling with a thickness of 2.7 mm using a hot rolling mill A board was used. Furthermore, after performing heat processing using a continuous annealing machine at 500 degreeC, it finished by cold rolling to 0.24 mm in thickness, and obtained the aluminum plate of JIS1050 material. After making this aluminum plate into width 1030mm, it used for the surface treatment shown below.

<Surface treatment>
The surface treatment was performed by continuously performing the following various treatments (a) to (j). After each treatment and washing with water, the liquid was removed with a nip roller.

(A) Mechanical surface roughening treatment While supplying a suspension of a polishing agent (pumice) having a specific gravity of 1.12 and water as a polishing slurry liquid to a surface of an aluminum plate, mechanical roughening is performed by a rotating nylon nylon brush. Surface treatment was performed. The average particle size of the abrasive was 30 μm, and the maximum particle size was 100 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 45 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.

(B) Alkali etching treatment The aluminum plate obtained above was subjected to an etching treatment by spraying using an aqueous solution having a caustic soda concentration of 2.6% by mass, an aluminum ion concentration of 6.5% by mass and a temperature of 70 ° C. / M ^{2 was} dissolved. Then, water washing by spraying was performed.

(C) Desmutting treatment Desmutting treatment was performed by spraying with a 1% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut treatment was a waste liquid from a step of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.

(D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 10.5 g / L aqueous solution of nitric acid (containing 5 g / L of aluminum ions and 0.007% by mass of ammonium ions) at a liquid temperature of 50 ° C. The AC power source waveform is electrochemical roughening treatment using a trapezoidal rectangular wave alternating current with a time ratio TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave alternating current. Went. Ferrite was used for the auxiliary anode.
The current density was 30 A / dm ² at the peak current value, and the amount of electricity was 220 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Then, water washing by spraying was performed.

(E) Alkaline etching treatment An aluminum plate is dissolved in an aqueous solution having a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate by 0.50 g / m ^2. The smut component mainly composed of aluminum hydroxide generated when the electrochemical surface roughening process is performed using the alternating current of the previous stage is removed, and the edge portion of the generated pit is melted to smooth the edge portion. I made it. Then, water washing by spraying was performed.

(F) Desmut treatment Desmut treatment was performed by spraying with a 15% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (containing 4.5% by weight of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used for the desmut treatment was a waste liquid from a step of performing an electrochemical surface roughening treatment using alternating current in a nitric acid aqueous solution.

(G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 5.0 g / L aqueous solution (containing 5 g / L of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform is subjected to electrochemical surface roughening using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1. went. Ferrite was used for the auxiliary anode.
The current density was 25 A / dm ² at the peak current value, and the amount of electricity was 50 C / dm ² in terms of the total amount of electricity when the aluminum plate was the anode. Then, water washing by spraying was performed.

(H) Alkali etching treatment An aluminum plate was sprayed using an aqueous solution having a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C., and the aluminum plate was dissolved at 0.10 g / m ² . Removes the smut component mainly composed of aluminum hydroxide that was generated when electrochemical roughening treatment was performed using the alternating current of the previous stage, and also melted the edge part of the generated pit to smooth the edge part. did. Then, water washing by spraying was performed.

(I) Desmutting treatment A desmutting treatment by spraying was performed with a 25% by weight aqueous solution of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by weight of aluminum ions), followed by washing with water by spraying.

(J) Anodizing treatment Anodizing treatment was performed using an anodizing apparatus to obtain a lithographic printing plate support. Sulfuric acid was used as the electrolytic solution supplied to the first and second electrolysis units. All electrolytes had a sulfuric acid concentration of 170 g / L (containing 0.5 mass% of aluminum ions) and a temperature of 38 ° C. Then, water washing by spraying was performed. The final oxide film amount was 2.7 g / m ² .
The Ra of the support obtained by the above treatment was 0.45.

〔undercoat〕
Next, the following undercoat liquid was applied to this aluminum support with a wire bar, and dried at 90 ° C. for 30 seconds using a hot air drying apparatus. The coating amount after drying was 10 mg / m ² .

<Undercoat liquid>
A copolymer of ethyl acrylate and 2-acrylamido-2-methyl-1-propane sulfonic acid sodium salt in a molar ratio of 75:15 0.1 g
・ 2-aminoethylphosphonic acid 0.1g
・ Methanol 50g
・ Ion exchange water 50g

(Photosensitive layer)
Next, the following photosensitive layer coating solution [P-1] was prepared and applied to the above-mentioned undercoated aluminum plate using a wire bar. Drying was performed at 122 ° C. for 43.5 seconds using a hot air drying apparatus to form a photosensitive layer. The coating amount after drying was 1.4 g / m ² .

<Photosensitive layer coating solution [P-1]>
・ Infrared absorber (IR-1) 0.08g
-Polymerization initiator (OS-1) 0.25g
・ Dipentaerythritol hexaacrylate 1.00g
-Binder polymer (BT-1) 1.00g
・ Ethyl violet chloride 0.04g
・ Fluorine surfactant 0.03g
(Megafuck F-780-F Dainippon Ink & Chemicals, Inc.)
・ Methyl ethyl ketone 10.4g
・ Methanol 4.83g
・ 10.4 g of 1-methoxy-2-propanol

  The structures of the infrared absorber (IR-1), the polymerization initiator (OS-1), and the binder polymer (BT-1) used in the photosensitive layer coating solution are shown below.

[Protective layer (overcoat layer)]
On the surface of the photosensitive layer, a mixed aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) and polyvinylpyrrolidone (BASF Corp., Rubiscol K-30) is applied using a wire bar. It was dried at 125 ° C. for 75 seconds with a drying apparatus. The content of PVA was 85% by mass, and the coating amount (coating amount after drying) was 2.45 g / m ² . The surface dynamic friction coefficient was 0.45.
A photosensitive lithographic printing plate 1 was obtained as described above.

[Photosensitive material E]
A 0.3 mm thick material 1S aluminum plate was thoroughly washed with water, etched by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water, then neutralized with 20% nitric acid, and washed with water. . This was subjected to an electrolytic surface roughening treatment in a 1.5% nitric acid aqueous solution with an electric quantity at the anode of 270 coulomb / dm ² using a sinusoidal alternating current under the condition of VA = 12.7V. When the surface roughness was measured, it was 0.30 μm (Ra indication). Subsequently, after dipping in a 30% aqueous sulfuric acid solution and desmutting at 40 ° C. for 2 minutes, a cathode was placed on the grained surface in a 33 ° C., 20% aqueous sulfuric acid solution at a current density of 5 A / dm ² . When anodized for 50 seconds, the thickness was 2.7 g / m ² .
On the aluminum plate thus treated, an intermediate layer coating solution having the following composition was applied, a dry coating mass was applied to 2 mg / m ^2, and dried at 100 ° C. for 3 minutes.

<Coating liquid for intermediate layer>
A solution in which the following composition was mixed and stirred, exotherm was observed after about 5 minutes, and after reacting for 60 minutes, 20,000 g of methanol was added.

Methanol 100g
DDP-8 (phosphate compound: manufactured by Nikko Chemical) 15g
10g of water
Phosphoric acid 5g
Tetraethoxysilane 50g
3-Methacryloxypropyltriethoxysilane 50g

On this undercoat layer, a high-sensitivity photopolymerizable composition 1 having the following composition was applied so that the dry coating mass was 1.5 g / m ² and dried at 100 ° C. for 90 seconds to form a photosensitive layer.

<Photopolymerizable composition 1>
1.8g of ethylenically unsaturated bond-containing compound (A1)
Linear organic polymer binder (B1) 1.5g
Sensitizer (C1) 0.15 g
Photoinitiator (D1) 0.2g
β-phthalocyanine (F1) dispersion 0.2 g
Fluorine-based nonionic surfactant Megafac F177 (manufactured by DIC) 0.03g
Methyl ethyl ketone 10g
10g of propylene glycol monomethyl ether acetate

A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) was applied on the photopolymerizable photosensitive layer thus formed so that the dry coating weight was 2.5 g / m ^2. And dried at 100 ° C. for 90 seconds to obtain a photosensitive material E.

[Processing of Examples 1 to 10]
As shown in Table 1, Table 2, Table 3, Table 4, and Table 5, continuous processing was performed using the replenishing method of the present invention to evaluate developer sensitivity stability. The evaluation of the development sensitivity stability was performed according to how much the image density of an image having a gradation density of 50% exposed by halftoning the photosensitive material changes after the development processing. The results are shown in Table 8.

[Processing of Comparative Examples 1 to 20]
As shown in Table 1, Table 2, Table 3, Table 4, and Table 5, continuous processing was performed using the area aging reference replenishment method and the conductivity reference replenishment method to evaluate developer sensitivity stability. The evaluation of the development sensitivity stability was performed according to how much the image density of an image having a gradation density of 50% exposed by halftoning the photosensitive material changes after the development processing. The results are shown in Table 8.

なお、比較例１１で使用した電導度基準補充方式は特開昭６４−２１４５１号（ＵＳ４，８８２，２４６）に記載の方法を使用した。

The conductivity reference replenishment method used in Comparative Example 11 was the method described in JP-A No. 64-21451 (US Pat. No. 4,882,246).

According to the above evaluation, Examples using the method of the present invention were used for Comparative Examples 1 to 20 in which the change in 50% gradation density exceeded the allowable range of −1.0% to + 1.0%. In 1 to 10, it was confirmed that the change in the 50% gradation density was within the allowable range.
According to the present invention, even if the conductivity sensor of the automatic developing apparatus breaks down, it can be temporarily operated in the area aging method, so that it is not necessary to completely stop the apparatus, and the decrease in the processing amount of the photosensitive material can be minimized. . As a result, the product cost can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a configuration diagram of a first embodiment of an automatic developing apparatus for performing a developing replenisher replenishing method of the present invention. It is a flowchart which shows the 1st control content by the control apparatus in the developing replenisher replenishment method of this invention. It is a flowchart (the 1) which shows the 2nd control processing by the control apparatus in the development replenisher replenishment method of this invention. It is a flowchart (the 2) which shows the 2nd control processing by the control apparatus in the developing replenisher replenishment method of this invention. It is a flowchart (the 1) which shows the 3rd control processing by the control apparatus in the developing replenisher replenishment method of this invention. It is a flowchart (the 2) which shows the 3rd control processing by the control apparatus in the development replenisher replenishment method of this invention. It is a flowchart (the 3) which shows the 3rd control processing by the control apparatus in the developing replenisher replenishment method of this invention. It is a block diagram of 2nd Embodiment of the automatic developing apparatus which implements the developing replenisher replenishment method of this invention.

Explanation of symbols

2,100 Automatic developing device 4,112 PS plate 6,122 Developing unit 20,118 Developing tank 50 Control device 51a Control ROM
51b Control RAM
52 Time measuring unit 53 Replenishment diluent storage tanks 55 and 266 Replenishment stock solution storage tanks 73 and 262 Conductivity sensors 74 and 264 Replenishment stock solution supply pump 76 Replenishment diluent supply pumps 90 and 91 Replenishment piping

Claims (4)

Development of a photosensitive lithographic printing plate automatic developing device that develops a large number of exposed photosensitive lithographic printing plates with a developer containing an electrolyte and replenishes the developer replenisher to keep the developer activity constant. A replenisher replenishment method comprising:
The developer conductivity is measured at predetermined intervals, and an amount of development replenisher based on a predetermined replenishment amount set value is replenished as a time-dependent replenisher every fixed time. Replenishing the amount of development replenisher based on a predetermined processing replenishment amount as a processing replenisher, and calculating the conductivity calculation value from the amount of the replenisher over time and the amount of the processing replenisher,
When the predetermined replenishment method set value is a value indicating the conductivity method, based on the result of comparing the conductivity calculation value and the measured value of the developer conductivity, the replenishment amount set value with time Increase or decrease the processing replenishment amount set value,
In the photosensitive lithographic printing plate automatic developing device, the replenishment method setting value does not increase or decrease the replenishment amount setting value with time and the processing replenishment amount setting value when the replenishment method setting value is not a value indicating the conductivity method. Development replenisher replenishment method. Development of a photosensitive lithographic printing plate automatic developing device that develops a large number of exposed photosensitive lithographic printing plates with a developer containing an electrolyte and replenishes the developer replenisher to keep the developer activity constant. A replenisher replenishment method comprising:
The developer conductivity value is measured every predetermined period, and the predetermined replenishment amount set value is integrated into the replenishment amount integrated value every predetermined time, and predetermined for each plate processing of a certain area. The processing replenishment amount set value is added to the processing replenishment amount integrated value, the replenisher replacement rate that is the ratio of the replenishment amount in the developer in the developing tank is calculated, and the replenishment over time that is the ratio of the replenisher over time in the developer in the developer tank After the ratio is calculated, when the total amount of the replenishment amount integrated value with time and the processing replenishment amount integrated value exceeds a predetermined minimum replenishment amount value,
When the predetermined replenishment method setting value is a value indicating the conductivity method, the following (A-1), (A-2), (A-3), (A-4), (A-5), (A-6) is executed, and when the replenishment method set value is not a value indicating the conductivity method, the following (B-1) and (B-2) are executed. A developing replenisher replenishing method for a printing plate automatic developing apparatus.
(A-1) Measure the elapsed time from the previous replenishment time to the present time, calculate the first conductivity calculation value from the elapsed time and the replenisher replacement rate,
(A-2) changing the replenishment amount setting value with time and the processing replenishment amount setting value according to the result of comparing the first conductivity calculation value and the measured developer conductivity value,
(A-3) calculating a second conductivity calculation value using the replenisher replacement rate and the replenishment ratio with time,
(A-4) changing the replenishment amount setting value with time and the processing replenishment amount setting value according to a result of comparing the second conductivity calculation value and the measured developer conductivity value,
(A-5) Replenish the developer in the developing tank with a replenisher of the total amount of the replenishment amount integrated over time and the processing replenishment amount integrated value;
(A-6) The integrated replenishment amount with time and the processing replenishment amount integrated value are initialized.
(B-1) replenishing the developer in the developing tank with a replenisher of a total amount of the replenishment amount integrated value over time and the processing replenishment amount integrated value;
(B-2) The integrated replenishment amount with time and the integrated replenishment amount with processing are initialized. When the conductivity value within the appropriate range of the developer activity is calculated in advance as the target conductivity value, and immediately after the start of the operation of the automatic developing device, the predetermined replenishment method setting is a value indicating the conductivity method , Execute (C-1), (C-2), (C-3), (C-4)
3. The developer replenisher is replenished to the developer according to a time during which the automatic developing device has been stopped when the replenishment method set value is not a value indicating an electrical conductivity method. Development replenisher replenishment method of the photosensitive lithographic printing plate automatic developing apparatus.
(C-1) Measure the conductivity of the developer at fixed intervals.
(C-2) When the measured developer conductivity value is lower than the target conductivity value, a predetermined amount of developer replenisher is replenished to the developer,
(C-3) Update the target conductivity value with the replenishment,
(C-4) Repeat (C-1), (C-2), and (C-3) until the developer conductivity value exceeds the target conductivity. A photosensitive lithographic printing plate automatic developing apparatus that develops a plurality of exposed photosensitive lithographic printing plates with a developer containing an electrolyte and maintains constant developer activity,
A development processing unit for developing the photosensitive lithographic printing plate with a developer;
Conductivity measuring means for measuring the conductivity of the developer;
Developer replenishing means for replenishing the developer with a developer replenisher;
4. A photosensitive lithographic printing plate automatic developing apparatus, comprising: a developing replenisher replenishing method according to claim 2, wherein the developing replenisher is replenished to the developer.

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