JPH06183171A - Dumpening water additive for lithography - Google Patents

Abstract

PURPOSE:To improve liquid stability, safety, and wettability by respectively containing an organic solvent of a specific boiling point and at least one kind of a compound expressed by the specific formula by each specific ratio in the title additive for off-set printing. CONSTITUTION:0.05-10wt.% of an organic solvent of liquid in 1atm. at 20 deg.C, and 150 deg.C or higher boiling point, propylene glycol, etc., and 0.001-5wt.% of at least one kind of a compound as expressed by the formula I- the formula VII are incorporated. In the formulas, R<1>-R<3> is a hydrogen atom, a 1-4C alkyl group, a hydroxyalkyl group, the halogen atom, etc., R<4>-R<11> is a 1-12C alkyl group, a 1-4C benzyl group, etc., R<12>-R<16> is the hydrogen atom, a 1-6C alkyl group, a hydroxyalkyl group, etc., R<17> is a hydrogen atom, a 1-12C alkyl group, etc., M<1>-M<6> is an alkali metal, the hydrogen atom, etc., Z is N, P, B, and (n) is an integer of 1-5. X<1> indicates counter ion, which is an anion when Z is N or P, and a cation when it is B. X<2> indicates an anion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fountain solution additive useful in an offset printing method for a lithographic printing plate.

[0002]

2. Description of the Related Art Lithographic printing is a printing method that skillfully utilizes the property that water and oil are essentially immiscible. The printing plate surface has an area that receives water and repels oil-based ink, and a surface that repels water and is oil-based. The former is a non-image area and the latter is an image area. The fountain solution expands the surface chemical difference between the image area and the non-image area by wetting the non-image area with an aqueous solution containing a desensitizing agent, and the ink repulsion and the image area of the non-image area are increased. Has the effect of increasing the ink receptivity of the ink. Conventionally known dampening water components include alkali metal salts or ammonium salts of dichromic acid, phosphoric acid or salts thereof, such as ammonium salts, gum arabic, colloid substances such as carboxymethyl cellulose (CMC), and the like. There is an aqueous solution that combines the ingredients of. However, the fountain solution containing these components has a drawback that it is difficult to uniformly wet the non-image area of the plate, which sometimes causes stains on the printed matter, and requires considerable skill in controlling the supply amount of the fountain solution. It costs.

In order to improve this drawback, a Dahlgren system has been proposed in which an aqueous solution containing about 20 to 25% by volume of isopropyl alcohol is used as dampening water. According to this method, the non-image area is well wetted, the amount of dampening water is small, the balance of the supply amount of printing ink and water is easy to adjust, and the dampening water in the printing ink is easily adjusted. Has a number of advantages in terms of workability and accuracy of the obtained printed matter, such as a reduction in the emulsification amount of the ink and a better transfer of the printing ink to the blanket.

However, since this isopropyl alcohol easily evaporates, a special device for keeping the concentration of isopropyl alcohol contained in the fountain solution constant is required, which is expensive in terms of price. In addition, isopropyl alcohol has a peculiar unpleasant odor,
There is a problem in terms of toxicity, which is not preferable in the work environment. In addition, dampening water to which this isopropyl alcohol was added,
Even when it is applied to offset printing using a normal water stick, there is a problem that isopropyl alcohol evaporates on the roller and the plate surface, so that the effect cannot be exhibited. Further, in recent years, there has been a great increase in social concern about industrial pollution, the regulation of emission of chromium ions in wastewater has become strict, and the use of organic solvents such as isopropyl alcohol tends to be regulated in terms of safety and hygiene. Therefore, an additive as an alternative component to isopropyl alcohol that does not contain these components has been desired. In order to achieve these objects, compositions containing various surfactants have been proposed, but when these are used as fountain solution, in order to adjust their surface tension to 35 to 50 dynes / cm. Had to keep the surfactant concentration in the fountain solution fairly high. In actual lithographic printing, since the ink / water moves violently under the high-speed rotating ink roll, printing plate, and fountain solution supply roll, water may adhere to the ink film, However, the combination of the surfactants proposed above was not sufficient to completely eliminate these problems. Further, there is a drawback that the fountain solution containing these surfactants is easily foamed by transportation or agitation in a circulation system for supplying to a printing machine.

By the way, in US Pat. No. 3,877,372,
A solution containing a mixture of ethylene glycol monobutyl ether and at least one of hexylene glycol and ethylene glycol is described. U.S. Pat. No. 4,278,467 discloses n-hexoxydiethylene glycol, n-hexoxyethylene glycol, 2-ethyl-1,3-hexanediol, n-butoxyethylene glycol acetate, n-butoxydiethylene glycol acetate, 3-butoxy-2. A fountain solution containing at least one propanol is described. JP-A-57-199693 discloses 2-ethyl-1,3-
Wet water containing hexanediol and at least one of completely water-soluble propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, hexylene glycol, triethylene glycol, tetraethylene glycol, tripropane glycol, and 1,5-pentanediol. The water is listed. Since these fountain solution compositions do not contain isopropyl alcohol, they are advantageous in terms of safety and hygiene, but it can be said that the non-image area during printing is completely wet in the planographic printing plate using an anodized aluminum plate as a support. , Especially in high-speed printing, the non-image area becomes dirty, the shape of the halftone image area is not normal,
There is a problem that the so-called halftone image portion becomes entangled, which becomes large and becomes uneven. Furthermore, 2-ethyl-
The solubility of 1,3-hexanediol in water was insufficient, which was disadvantageous in obtaining a concentrated concentrated fountain solution additive.

Further, these isopropyl alcohol substitute compounds are generally high-boiling point organic solvents, and when water evaporates, the high-boiling point organic solvent remains as a residue and has a serious defect of immersing the image area of the lithographic printing plate. Was newly found. Furthermore, it is necessary to mix and use a large amount of water in order to satisfy the Fire Defense Law regulations (less than 40% of organic solvent, flash point 40 ° C or higher, combustion point 60 ° C or higher), but especially at this time the liquid stability is unstable. It had a problem that it was easy to become.

[0007]

Therefore, the object of the present invention is to eliminate the toxicity and drawbacks of the above-mentioned conventional fountain solution additives, and to require no special skill in printing work.
The supply amount can be easily adjusted, and not only the printing plate, especially an aluminum plate is electrochemically roughened to prevent stains or blinding of the printing plate using an anodized support. Provide a dampening water additive that is excellent in economic efficiency and liquid stability, does not impair the image area of the printing plate, complies with the regulations of the Fire Service Law and Occupational Safety and Health Act, and has excellent plate surface wettability. Especially.

[0008]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have solved the above object easily by using the following fountain solution additive for lithographic printing. The inventors have found out what can be done and reached the present invention. That is, the present invention comprises 0.05 to 10% by weight of an organic solvent having a boiling point of 150 ° C. or more and a liquid at 20 ° C. at 1 atm and at least one compound represented by the following general formulas [I] to [VII]. It is a fountain solution additive characterized by containing 0.001 to 5% by weight.

[0009]

[Chemical 2]

(In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (including linear and branched ones), and a hydroxyalkyl having 1 to 4 carbon atoms. Group, hydroxyl group, halogen atom (for example, chlorine atom,
Bromine atom), a mercapto group, -SO ₃ M ^4, or -
COOM ⁵ is shown. R ^{4 to} R ¹¹ are each independently an alkyl group having 1 to 12 carbon atoms (including linear, branched and cyclic ones), a hydroxyalkyl group having 1 to 4 carbon atoms,
Benzyl group or substitution (eg, alkyl group having 1 to 4 carbon atoms such as methyl group, hydroxyl, halogen, etc.)
Alternatively, it represents an unsubstituted phenyl group. R ^{12 to} R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (including linear and branched ones), a hydroxyl group, and —SO ₃
M6 represents a hydroxyalkyl group having 1 to ⁶ carbon atoms. R ¹⁷ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (including linear and branched ones), or 1 carbon atom.
~ 12 hydroxyalkyl groups are shown. M ^{1 to} M ⁶ are each a hydrogen atom, an alkali metal (Na, K, etc.) or NH
_{Shows 4} . Z represents N, P or B. X ¹ represents a counter ion, the anion is when Z is N or P (e.g., chloride, bromide, halide ions such as iodide ion, nitrate ion, sulfate ion, phosphate ion, hydroxide ion, PF ₆ ^-, BF ₄ ^{− and the} like), when Z is B, it represents a cation (for example, an alkali metal ion such as Li ⁺ , Na ⁺ , K ⁺ or NH ₄ ⁺ ), and X ² is an anion (for example, as described above). Examples are included.) n shows the integer of 1-5. The particularly preferable organic solvent is a compound represented by the following general formula [VIII]. General formula [VIII] _{^{R 18 O- (CH 2 -CH (}} CH 3) -O) m -H formula R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is from 1 to 20 Indicates an integer.

The pressure used in the present invention is 20 at one atmospheric pressure.
The organic solvent having a boiling point of 150 ° C. or higher which is a liquid at 0 ° C. is a compound that improves the wettability of the water supply roller and raises and stabilizes the plate surface, and specific compounds include propylene glycol, dipropylene glycol, Tripropylene glycol, tetrapropylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetrapropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether , Tetrapropylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether , Tripropylene glycol monopropyl ether, tetrapropylene glycol monopropyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monoisopropyl ether, tripropylene glycol monoisopropyl ether, tetrapropylene glycol monoisopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monobutyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monoisobutyl ether, tetrapropylene glycol monoisobutyl ether, propylene glycol Call mono t-butyl ether, dipropylene glycol mono t-butyl ether, tripropylene glycol mono t-butyl ether, tetrapropylene glycol mono t-butyl ether, molecular weight 200
1000 polypropylene glycol and monomethyl ether, monoethyl ether, monopropyl ether and isopropyl ether, monobutyl ether, monoisobutyl ether, monotertiary butyl ether, etc. of these compounds are mentioned.

Compounds preferably used in the above compounds are as follows. When R ¹⁸ is a hydrogen atom or a methyl group, m is 1-10.
Is preferable, and when R ¹⁸ is ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl group, etc., m is preferably 1-5.
These compounds may be used alone or in combination of two or more kinds. In particular, in the vibration jet method, 1% by weight of the above compound alone or a combination of two or more compounds may be used.
A compound having a dynamic surface tension of 55 dyne / cm or less in cm second is preferably used. The range which can be suitably used in the present invention is 0.1 to 10% by weight, more preferably 0.5 to 5.0% by weight.

General formulas [I] to [VII] used in the present invention
Specific examples of the compound shown in] include benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, benzoic acid, salicylic acid, isophthalylsulfonic acid, gallic acid, phenolsulfonic acid,
Thiosalicylic acid, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium sulfate, tetraphenylphosphonium nitrate, sodium tetraphenylboron, tetra n-butylphosphonium iodide, tetra n-butylphosphonium bromide, Tetra-n-butylphosphonium chloride,
Tetra-n-butylphosphonium sulfate, tetra-n-butylphosphonium nitrate, tetrabutylammonium sulfate, tetrabutylammonium nitrate, ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetrabutylphosphonium hydroxide, tetrabutylphosphonium Phosphate, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, diphenylphosphonium chloride, benzyltriphenylphosphonium chloride, tetratolylphosphonium bromide, bis [(benzyl) (diphenyl) phosphorandiyl] ammonium chloride, 1,2- Bis (diphenylphosphino) ethane bromide, 4- (butylphenyl) -2-hydroxy Nzensuruhon acid, 4- (butylphenyl) benzenesulfonic acid, and diphenyl ether sulfonic acid. Further, these alkali metal salts (Na, K, Li salts), ammonium salts, butylisoquinolinium bromide, methylisoquinolinium chloride and the like can be mentioned.

These compounds completely prevent the deterioration phenomenon of the image portion of the printing plate due to the residue of the solvent generated by the evaporation of water, which is a major defect of the use of the high boiling point solvent, and enhance the protection of the image portion. The effect is specifically exhibited, and stable printing can be performed. The preferred range of use is 0.01-5% by weight
Is. Further, two or more of these compounds may be used in combination, and specific examples of the combination thereof include a combination of the compound represented by the general formula (I) and the compound represented by the general formula (III). The fountain solution additive of the present invention may further contain the following components, if necessary. The fountain solution additive is generally marketed in the form of a concentrate. Also in the present invention, the stability of the liquid over time when concentrated, for example, −
It is necessary to prevent liquid separation and liquid turbidity even under 5 ° C. conditions or 50 ° C./80% RH conditions. The liquid turbidity is a phenomenon in which, when the temperature of a transparent aqueous solution is gradually raised, the micelles in the solution are dehydrated to form giant micelles and the solution becomes cloudy, which is generally called cloud point phenomenon. It is useful to use an auxiliary agent that suppresses this phenomenon.

Examples of the auxiliary agent for concentration used in the present invention include 3-methoxybutanol, 3-ethoxybutanol, 3-propoxybutanol and 3-methyl-3-.
Methoxybutanol, 3-methyl-3-ethoxybutanol, 3-methyl-3-propoxybutanol, diacetone alcohol, tetrahydrofurfuryl alcohol,
Examples include hexylene glycol, dimethyl sulfoxide, γ-butyrolactone, 2-ethyl-1,3-hexanediol and derivatives thereof, so-called cellosolve-based solvents such as ethylene glycol monobutyl ether, and the like. These compounds are stored at low temperature (-1 to -10 ° C)
Alternatively, it effectively suppresses the separation of the liquid and the cloud point phenomenon which are likely to occur during high temperature storage (30 to 50 ° C.). These concentration aids may be used alone or in combination of two or more. The preferably used range is 5 to 20% by weight. If necessary, the fountain solution additive of the present invention further comprises (a) a surfactant,
Ingredients such as (b) antiseptic, (c) rust inhibitor, and (d) colorant can be added.

(A) Surfactant When a surfactant is used in combination with the additive of the present invention, it effectively contributes as an auxiliary agent for improving the wettability of the plate surface. For example, as anionic surfactants, fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene Sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salts, N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, Sulfated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate ester salts, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, fatty acid monoglyceride Acid ester salts, polyoxyethylene alkyl phenyl ether sulfuric acid ester salts, polyoxyethylene styryl phenyl ether sulfuric acid ester salts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphoric acid ester salts, polyoxyethylene alkylphenyl ether phosphoric acid ester salts, styrene- Examples thereof include partially saponified products of maleic anhydride copolymers, partially saponified products of olefin-maleic anhydride copolymers, and naphthalene sulfonate formalin condensates. Among these, dialkyl sulfosuccinates, alkyl sulfate ester salts and alkyl naphthalene sulfonates are particularly preferably used.

As the nonionic surfactant, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial ester , Sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester Kind,
Polyglycerin fatty acid partial ester, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial ester, fatty acid diethanolamide, N,
Examples thereof include N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides and the like. In addition, a fluorine-based surfactant and a silicon-based surfactant can also be used. Among them, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used. Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, and the like. Others include fluorine-based surfactants,
Silicon-based surfactants and the like can be mentioned. The content of these surfactants is 0.001 to 1% by weight, preferably 0.001 to 0.5% by weight, in consideration of foaming.

(B) Preservatives Preservatives preferably used in the fountain solution additive of the present invention include, for example, phenol or its derivative, formalin, imidazole derivative, sodium dehydroacetate, benzisothiazoline derivative, 4-isothiazoline- Examples thereof include 3-one derivatives, benzotriazole derivatives, amidine or guanidine derivatives, quaternary ammonium salts, pyridine, quinoline or guanidine derivatives, diazine or triazole derivatives, oxazole or oxazine derivatives, and the like. The preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the types of bacteria, molds, yeasts, but with respect to the fountain solution composition, 0.001- The range of 5% by weight is preferable, and it is preferable to use two or more kinds of preservatives which are effective against various molds, bacteria and yeasts in combination. The fountain solution composition of the present invention can be obtained by using the above components as water, preferably demineralized water, that is, an aqueous solution dissolved in pure water. A concentrated solution can be prepared if necessary. When the concentrated solution is used, it is economically preferable to use it by diluting it with tap water, well water, etc. 10 times to 1000 times.

(C) Anticorrosive agent Further, the dampening water additive of the present invention may contain an anticorrosive agent for preventing metal corrosion. For example, thiosalicylic acid, benzotriazole, 5-methylbenzotriazole, 5-methoxybenzotriazole, 4-chlorobenzotriazole, 4-bromobenzotriazole, 4-
Bromo-6-methylbenzotriazole, 4-bromo-
6-trifluoromethyl benzotriazole etc. are mentioned. These compounds may be used alone or in combination of two or more. The addition amount varies depending on the compound used, but is usually 0.0001 to 1% by weight, preferably 0.001 to 1% by weight.
It is in the range of 0.5%. (D) Colorant A colorant may be added to the fountain solution additive of the present invention so that it can be colored. Among the dyes, food dyes can be preferably used. For example, as a yellow pigment, CI No. 19
140, 15985, CI No. 161 as red dye
85, 45430, 16255, 45380, 4510.
0, CI No. 42640 as a purple dye, CI Nos. 42090 and 73015 as a coloring dye, and CI No. 42095 as a green dye. Further, as the defoaming agent, a silicon defoaming agent is preferable. Among them, emulsified dispersion type and solubilized type can be used. The preferable addition amount is in the range of 0.0001 to 1% by weight.

[0020]

INDUSTRIAL APPLICABILITY The fountain solution additive of the present invention has extremely good printability and does not impair the image on the printing plate even though a high boiling solvent is used. In addition, the stability of the liquid over time and the suitability for concentration are excellent, and legal regulations such as the Fire Service Law and the Occupational Safety and Health Law are sufficiently satisfied, and a stable printed matter can be obtained.

[0021]

EXAMPLES Next, the present invention will be described more specifically by way of examples. Unless otherwise specified,% means% by weight. Examples 1 to 5 and Comparative Examples 6 to 7 were used as dampening water additives, and combinations of acidic type [a] and alkaline type [b] were used as dampening water compositions used. Each of them was prepared as a concentrated liquid, and the dampening water was diluted 1: 100 with tap water.
5% of the concentrate additive of Comparative Examples 6 and 7 was added and mixed to prepare a test solution. The test results are summarized in Tables 3 and 4. Although the fountain solution has a reference composition, it is possible to use the commercially available dampening solution. Test method The print version is for positive use FPS (Fuji Photo Film Co., Ltd.)
Positive type PS plate) and negative FNNA3 (Fuji Photo Film Co., Ltd. negative type PS plate) are exposed using solid parts and halftone dots 5%, 10% and 30% film, and the plate making method is shown in Table 1. Then, it was attached to a Komori Lithrone printing machine (equipped with Komorimatic) and printed using Toyo Ink Mark V-Black ink.

[0022]

[Table 1] [Table 1] ─────────────────────────────────── Printing plate plate making method ─ ────────────────────────────────── FPS PS automatic processor 800EII, positive developer DP-4 ^* ( Make a plate using 8 times diluted with water) and Positive Finisher FP (2 times diluted with water) ─────────────────────────── ───────── FNNA3 PS automatic processor 800EII, negative developer DN-3C ^* (2 times diluted with water), negative finisher FN-2 (2 times diluted with water) ─────────────────────────────────── *: All are made by Fuji Photo Film Co., Ltd. <Test used Damping water composition> [a] Acidic Thailand Dampening water Pure water 873g Arabian gum (14 ° Baume aqueous solution) 50 Citric acid 20 Potassium pyrophosphate 7 Diammonium phosphate 20 Magnesium nitrate 30 Working solution 1: 100 dilution [b] Alkaline type dampening water Pure water 850g Metakei Sodium acid 15 Potassium pyrophosphate 5 Hexylene glycol 100 Working solution 1: 200 dilution In addition, acidic type dampening water is in the range of pH 5.0 to 5.5, alkaline type dampening water is in the range of pH 10 to 11 Or K
Prepared with OH.

[0023]

[Table 2] [Table 2] ─────────────────────────────────── Component Example Comparative Example ─ ────────────────────────────────── 1 2 3 4 5 6 7 ────────── ────────────────────────── Wettability Fluoropolyene glycol monobutyl ether 250-200-100 250 100 Improver difluoroethylene glycol monomethyl ether-200-200 100-100 Fluoroglycol mono Fluoroether--50 50 50-50 Adjuvant 3-Methyl-3-methoxybutanol 145-70 70 150 145 150 Tetrahitrofurfuryl alcohol-145 70 70---Surfactant * Fluoronic L '31 5 5--5 5-** LASOSOL B80--1----Image stable tetraphenylphosphonium bro Mide 5 5 2.5 2.5 5--Agent Tetrabutylphosphonium bromide--2.5 2.5---p-Toluenesulfonic acid Na 5 5 5 5 10--Preservative 4-isothiatholin-3-one derivative 1 1 1 1 1 1 1 Dehitochloroacetate Na--1 1---Anticorrosion agent Benzotriazole 0.1-0.1 0.1 0.1 0.1 0.1 5-Methoxybenzimimizosol-0.1 0.1 0.1---Colorant Food Blue No. 2--0.1----Pure water Add pure water to make 1000 ml ───────────────────────────────────

Evaluation of printability at that time and deterioration of image area of solid part and 30% halftone part of PS plate after a little more dampening water was supplied and stopped for 60 minutes before stopping the printing machine (plate Tobi) was observed. The results are shown in Table 3. a. Metering roll stains: Check the degree of ink stains on the water metering roll. good. A A little inferior. B Inferior C b. Bleedability: Ink (Dainippon Ink Co., Ltd. graph
After printing 5000 and 10000 sheets using Beni S), the operation of the printing machine is stopped and the extent to which the ink in the image area is bleeding into the non-image area is examined. Almost no bleeding. A There is some blurring. B There is a lot of bleeding. C

C. Emulsification: When printing 10,000 sheets,
Check the emulsified state of the ink on the ink roll. good. A A little bad. B Bad. C d. Continuous stability: 1000 using fresh water as dampening water
Printing 0 sheets, obtaining the amount of dampening water that does not cause stains (minimum amount of water), printing using various types of dampening water at this minimum amount of water, and printing until stains on the printed matter occur. Judge by the number of sheets. 10000 sheets or more A 1000 to 3000 sheets B less than 3000 sheets C e. Deterioration of image area After leaving the printing machine for 60 minutes, the deterioration of the solid area and 30% halftone dot area is visually judged. No problem A Slightly deteriorated B Deteriorated C As a result of testing the fountain solution suitability of this example, (a) metering stain, (b) bleeding property, (c) emulsifying property, (d) continuous stability and (e) ) It was excellent in any deterioration of the image area, and a good printed matter was obtained.

[0026]

[Table 3] [Table 3] ─────────────────────────────────── Actual Examples Comparative Examples ── ───────────────────────────────── fountain solution acidic alkaline acidic alkaline alkaline ────────── ───────────────────────── Plate Positive Negative Positive Negative ──────────────────── ─────────────── Sample 1 2 3 4 5 6 7 ──────────────────────────── ───────── Metering roll dirt A A A A A A A A Ink bleeding property A A A A A A A A A Emulsifying property A A A A A A A A A Continuous stability A A A A A A A A Image part Degradation A A A A-B A C B-C ─────────── ───────────────────────

Subsequently, the printing machine was stopped and the solid portion of the PS plate
5 μl, 10 μl, 20 μl and 50 μl of the respective dampening water were added dropwise to the image portion of the 0% halftone dot portion using a syringe and left for 60 minutes. After that, printing was restarted and deterioration of the image area was evaluated. The results are shown in Table 4.

[0028]

[Table 4] [Table 4] ───────────────────────────────── Actual example ratio Comparative example ─── ────────────────────────────── Dampening water acidic alkaline acidic alkaline alkaline ───────────── ───────────────────── Plate positive negative negative positive negative ───────────────────────── ──────── Sample 1 2 3 4 5 6 7 ───────────────────────────────── 5 μl A A A A A A C B 10 μl A A A A A A C B 20 μl A A A A A A A C C 50 μl A A A to B A A C C ────────────────── ──────────────── A No problem B Some deterioration (ring shape There) degradation of the sample 1-5 殆 N etc. image area as compared with sample 6 and 7 examples of C degradation Comparative Example was not observed, was completely protected.

Claims (2)

[Claims] 1. A liquid at 20 ° C. at 1 atmosphere,
A lithographic printing plate characterized by containing 0.05 to 10% by weight of an organic solvent having a boiling point of 150 ° C. or higher and 0.001 to 5% by weight of at least one compound represented by the following general formulas [I] to [VII]. Immersion water additive for printing. [Chemical 1] (In the formula, R ^{1 to} R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom, a mercapto group, —SO ₃ M .R ⁴ to R indicating a ⁴ or -COOM ⁵
Each ¹¹ independently represents an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a benzyl group, or a substituted or unsubstituted phenyl group. R ¹² ~ R
¹⁶ is each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, —SO ₃ M ⁶ , and 1 to 6 carbon atoms.
Is a hydroxyalkyl group. R ¹⁷ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a carbon atom having 1 to 12 carbon atoms.
Is a hydroxyalkyl group. M ^{1 to} M ⁶ each represent a hydrogen atom, an alkali metal or NH ₄ . Z represents N, P or B. X ¹ represents a counter ion, Z is N or P
Represents an anion, Z represents B represents a cation, and X ² represents an anion. n shows the integer of 1-5. ) 2. The fountain solution additive according to claim 1, wherein the organic solvent having a boiling point of 150 ° C. or more and which is a liquid at 20 ° C. at one atmospheric pressure is a compound represented by the following general formula [VIII]. General formula [VIII] _{^{R 18 O- (CH 2 -CH (}} CH 3) -O) m -H formula R ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is from 1 to 20 Indicates an integer.