JPH10268517A - Negative image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative image recording material capable of forming a printing plate directly from digital data and shorting a developing time without impairing film strength incorporating a specified polymer, an acid-cross- likable compound, a light or heat acid-generator, an infrared absorber, and a low-molecular compound having a specified sulfonamide group. SOLUTION: This recording material contains the polymer having structural unit represented by formula I, the compound cross-linkable by an acid, the acid generator by light or heat, the infrared absorber, and the lower molecular compound having a sulfonamide groups represented by formula II, and in formula I and II, X<1> is an alkaline group or alkali-soluble group; Ar<1> is an aromatic hydrocarbon group; Y<1> is an N-R<3> group or a C or S atom; L<1> is a simple bond or an ester bond or a hydrocarbon group optionally having its bond; L<2> is a hydrocarbon group; R<1> is an H atom or a methyl group; R<2> is a hydrocarbon group; R<3> is an H atom or a hydrocarbon group; R<24> is a hydrocarbon group; and R<25> is an H atom or a hydrocarbon group.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material which can be used as an offset printing master, and more particularly to a lithographic printing plate for so-called direct plate making which can make a plate directly from a digital signal from a computer or the like.

2. Description of the Related Art Conventionally, as a system for directly making a plate from digital data of a computer, an electrophotographic method, a photopolymerization system using a combination of exposure by an Ar laser and post-heating, and a silver salt photosensitive material laminated on a photosensitive resin are used. And a silver master type, and a method in which the silicone rubber layer is destroyed by electric discharge or laser light. In the method using the electrophotographic method, the processes such as charging, exposure, and development are complicated, and the apparatus is complicated and large. In the above method, a post-heating step is required, and a high-sensitivity plate material is required, which makes it difficult to handle in a bright room. In the methods (1) and (2), the use of a silver salt complicates the processing and has the disadvantage of increasing the cost. Although the method described above is a method having a relatively high degree of completion, there is a problem in removing the silicone layer remaining on the plate surface. On the other hand, the development of lasers in recent years has been remarkable, and in particular, solid-state lasers and semiconductor lasers having a light-emitting region from the near infrared to the infrared have become easily available with high output and small size. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like. However, many photosensitive image recording materials that are practically useful have a photosensitive wavelength of 450 nm or less, and therefore cannot record images with these lasers. For this reason, an image recording material capable of recording an image irrespective of the wavelength of an exposure light source is desired. As a technique capable of recording an image without depending on the wavelength of an exposure light source, Japanese Patent Application Laid-Open No. 52-113219 discloses a technique of decomposing by light and heat (for example, a diazonium compound) and a technique of absorbing light and converting it to heat. A positive-working image-recording material comprising a material particle and a binder is disclosed. In this method, a diazonium compound is decomposed by heat to record an image. Further, Japanese Patent Application Laid-Open No. 58-1
Japanese Patent No. 48792 discloses a positive-type light- and heat-sensitive recording material containing thermoplastic resin particles, a light-to-heat conversion material, and a photocrosslinkable material (for example, a diazonium compound) as main components. In this case, the durability of the image is improved by utilizing the fact that the thermoplastic resin particles form an image by heat and the photocrosslinkable substance is directly decomposed by light. In direct plate making, writing is performed by scanning the beam of a laser light source, but a negative material is preferable because the writing time can be shortened. However, solid-state lasers and semiconductor lasers (heat mode) that emit light in the near-infrared to infrared region are used as exposure light sources for plate making directly from digital data from computers and the like.
A negative-type image-recording material which can be recorded with heat by using a material having good recording properties has not been known so far.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a negative-type image recording material capable of recording an image without depending on the emission wavelength of an exposure light source. By recording an image using a solid-state laser or semiconductor laser (thermal mode) with a light-emitting area, plate making can be performed directly from digital data from a computer or the like, and a heat mode that can use conventional processing equipment and printing equipment without change An object of the present invention is to provide a negative type lithographic printing plate for writable direct plate making. It is a further object of the present invention to provide a negative type image recording material capable of shortening the development time.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by using a specific low molecular compound having a sulfonamide group in combination with a specific polymer, the development time can be reduced without impairing the film strength. It has been found that a negative-type recording material capable of shortening the recording time can be obtained, and the present invention has been achieved. That is,
The above object can be achieved by the following configuration (1) of the present invention. (1) (A) a polymer having a structural unit represented by the following general formula (I), and (B) a compound cross-linked by an acid,
(C) a compound that generates an acid by light or heat, and (D)
A negative-type image recording material comprising: an infrared absorber; and (E) a low-molecular compound having a sulfonamide group represented by the following general formula (II).

Embedded image In the formula, X ¹ itself shows alkali solubility or a linking group having an alkali-soluble group. Ar
¹ represents an aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. Y ¹ represents NR ³ , an oxygen atom or a sulfur atom. n shows the integer of 1-4. L ¹ is,
It represents a single bond, an ester bond, a carboxylic acid amide bond, a sulfonic acid amide bond, an ether bond, a thioether bond or a hydrocarbon group having 20 or less carbon atoms which may contain these bonds. L ² represents a single bond or a hydrocarbon group having 20 or less carbon atoms. R ¹ represents a hydrogen atom or a methyl group. R ² represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. R ³ represents a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent.

Embedded image In the formula, R ²⁴ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent, and R ²⁵ represents a hydrogen atom, a hydrocarbon group having 20 or less carbon atoms which may have a substituent or −COR ²⁶
And R ²⁶ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [(A) Poly (A) having structural unit represented by general formula (I)
In the present invention, the structural unit represented by the general formula (I)
A polymer having a position is used. In the general formula (I), R¹
Represents a hydrogen atom or a methyl group. X¹Is itself a
Shows lucali solubility or has alkali-soluble group
Represents a linking group. Here, the alkali-soluble group is
Phonamide, Sulfonimide or Carboximide
Refers to a group containing a moiety such as —SO _Two N
H-, -NHSO_Two -, -SO_Two NHCO-, -CON
HSO_Two -, -CONHCO- and the like.
You. Ar¹Has 20 carbon atoms which may have a substituent
The following aromatic hydrocarbon groups are shown. Specifically, benzene
Ring, naphthalene ring, anthracene ring, phenanthrene ring
And the like. These aromatic hydrocarbon groups
Of which, from the viewpoints of availability and economy,
It is preferably a taren ring. Also, these aromatics
As a preferred substituent that the hydrocarbon group can have
Is a hydrocarbon group having 20 or less carbon atoms, a halogen atom,
Groups, nitro groups, carboxyl groups, carbamoyl groups, etc.
Can be mentioned. Y¹Is NR^Three, Oxygen atom or
Represents a sulfur atom;^TwoIs a carbon which may have a substituent
It represents a hydrocarbon group having a prime number of 20 or less. Where R^ThreeIs
A hydrogen atom or an optionally substituted carbon number of 20 or more
Shows the lower hydrocarbon group. R^TwoAnd R^ThreeUsed in
Preferred substituents that can be represented by a halogen atom,
Ano group, nitro group, carboxyl group, carbamoyl group,
An alkoxyl group having 20 or less carbon atoms,
Fluoroalkyl group and hydroxy having 20 or less carbon atoms
Examples include an alkyl group. N is 1 to 4
Indicates an integer. L¹Is a single bond, ester bond, carbo
Acid amide bond, sulfonic acid amide bond, ether bond
If they contain thioether bonds or these bonds
A hydrocarbon group having 20 or less carbon atoms. L^TwoIs simply
Shows a bond or a hydrocarbon group having 20 or less carbon atoms.
-From the viewpoint of economy, a single bond is preferable. What
Contact, R^TwoAnd Ar¹And R^ThreeAnd Ar¹, And R^TwoWhen
R^Three, Each forming a ring structure such as a cyclohexane ring
May be. General formula preferably used in the present invention
The polymer having the structural unit represented by (I) is as follows.
A polymer having a structural unit represented by the general formula (III)
You. In the general formula (III), the same sign as the general formula (I) is used.
The same components are denoted by the same reference numerals and description thereof is omitted.

Embedded image Wherein R ⁴ and R ⁵ may be the same or different;
It represents a hydrogen atom or a hydrocarbon group which may have a substituent and has 20 or less carbon atoms. Preferred substituents that can be used for R ⁴ and R ⁵ include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carbamoyl group,
Examples thereof include an alkoxyl group having 20 or less carbon atoms, a perfluoroalkyl group having 20 or less carbon atoms, and a hydroxyalkyl group having 20 or less carbon atoms. Note that R ⁴ and R ⁵
May form a ring structure such as a condensed benzene ring or cyclohexane ring. The polymer having the structural unit represented by the general formula (III) can be obtained by radical polymerization using a corresponding monomer represented by the general formula (IV) by a conventionally known method. In the general formula (IV), the same reference numerals as those in the general formula (III) denote the same parts, and a description thereof will be omitted.

Embedded image In the present invention, examples of the monomer represented by the general formula (IV) that is preferably used are shown below as formulas (IV-1) to (IV-13). In the following formula, R ¹ represents a hydrogen atom or a methyl group, and Z ¹ represents an oxygen atom or NH.

Embedded image

Embedded image

Embedded image In the present invention, preferred examples of the polymer having the structural unit represented by the general formula (I) include a homopolymer using only one kind of the monomer represented by the general formula (IV) and a copolymer using two or more kinds of the monomers represented by the general formula (IV). Both polymers can be used. As the polymer that can be used in the present invention, a copolymer of a monomer represented by the general formula (IV) and a conventionally known polymerizable monomer other than the monomer represented by the general formula (IV) is used. From the viewpoint of solubility in the coating solution and flexibility of the coating film,
preferable. Known monomers used in combination with such a monomer represented by the general formula (IV) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate,
-Hydroxyethyl acrylate, acrylates such as benzyl acrylate, methyl methacrylate,
Examples include methacrylates such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, and benzyl methacrylate, and acrylonitrile. The polymer having a structural unit represented by the general formula (I) of the present invention has, as a partial structure thereof, X ¹ which is a linking group having alkali solubility (for example, an acidic group or the like). The copolymer is excellent in solubility, but may be a copolymer using a monomer having another acidic group as a supplement. Examples of the monomer used include, for example,
Acrylic acid, methacrylic acid, itaconic acid, maleic acid,
N- (2-carboxyethyl) acrylamide, N-
(2-carboxyethyl) methacrylamide, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide, carboxystyrene, maleimide, N- (phenylsulfonyl) acrylamide, N- (phenylsulfonyl) methacrylamide, N
-(Tolylsulfonyl) acrylamide, N- (tolylsulfonyl) methacrylamide, N- (chlorophenylsulfonyl) acrylamide, N- (chlorophenylsulfonyl) methacrylamide, N- (sulfamoylphenyl) acrylamide, N- (sulfamoylphenyl) ) Methacrylamide, N- (methylsulfamoylphenyl) acrylamide, N- (methylsulfamoylphenyl) methacrylamide, N- (phenylsulfamoylphenyl) acrylamide, N- (phenylsulfamoylphenyl) methacrylamide, N- (tolylsulfamoylphenyl) acrylamide, N- (tolylsulfamoylphenyl) methacrylamide, N-
[(Chlorophenylsulfamoyl) phenyl] acrylamide, N-[(chlorophenylsulfamoyl) phenyl] methacrylamide, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxynaphthyl) acrylamide, N- (hydroxynaphthyl) methacrylamide and the like. Further, although not an acidic group, sodium salt of p-styrenesulfonic acid, 2-acrylamide-2-
A monomer containing a salt of a strong acid such as an alkali metal salt of methylpropanesulfonic acid, a tetraalkylammonium salt, and a potassium salt of 3-sulfopropylacrylate can improve the solubility in water, and as a result, an aqueous developer of an image recording material can be obtained. It is preferable as a component of the copolymer because it can improve the developability of the copolymer. The proportion of the structural unit represented by the general formula (I) contained in the copolymer using these is as follows:
It is preferably 20 to 95% by weight, more preferably 30 to 90% by weight. Further, the weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000,
The number average molecular weight is preferably at least 1,000, more preferably in the range of 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably in the range of 1.1 to 10. These polymers may be any of a random polymer, a block polymer, a graft polymer and the like, but are preferably a random polymer. As the solvent used when synthesizing the polymer used in the present invention, for example,
Tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol,
Ethanol, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate , Methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more. As the radical polymerization initiator used for synthesizing the polymer used in the present invention, known compounds such as an azo initiator and a peroxide initiator can be used. The polymers used in the present invention may be used alone or as a mixture. These polymers are used in an amount of 20 to 95% by weight, preferably 40% by weight, based on the total solid content of the image recording material.
It is added to the image recording material at a ratio of about 90% by weight. When the addition amount is less than 20% by weight, the strength of the image portion is insufficient when an image is formed. When the amount exceeds 95% by weight, no image is formed. [(B) Thermal crosslinking agent] The thermal crosslinking agent suitably used in the present invention is a compound having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups or vinyl ether groups in the molecule. Preferably, these crosslinkable functional groups are compounds directly bonded to an aromatic ring. Specific examples include methylol melamine, resole resin, epoxidized novolak resin, and urea resin. Further, compounds described in "Crosslinking Agent Handbook" (written by Shinzo Yamashita and Tosuke Kaneko, Taiseisha Co., Ltd.) are also preferable. In particular, a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule is preferable because the strength of the image area when an image is formed is good. A specific example of such a phenol derivative is a resole resin. However, these thermal crosslinking agents are, of course, unstable to heat, and the storage stability after the preparation of the image recording material is not so good. On the other hand, a phenol derivative having 4 to 8 benzene nuclei, at least one phenolic hydroxyl group and at least two groups represented by the formula (V) in a molecule has good stability during storage. Is most preferably used in the present invention.

Embedded image R ^{6 in the} above (V) represents a hydrogen atom, an alkyl group or an acyl group, and examples of the alkyl group include a methyl group, an ethyl group,
An alkyl group having 1 to 4 carbon atoms, such as -propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or t-butyl group, and acyl groups such as formyl group, acetyl group, and butyryl group , A benzoyl group, a cinnamoyl group and a valeryl group are preferred. Further, a substituted alkyl group having 1 to 4 carbon atoms such as a methoxyethyl group, a methoxypropyl group, a hydroxyethyl group, and a hydroxypropyl group can be used. Phenol derivatives usable in the present invention include known phenol compounds, for example,
Nos. 289946, 3-179353, 3
JP-200252, JP-A-3-128959, JP-A-3-200254, JP-A-5-158233,
The phenol compound described in JP-A-5-224409 and formaldehyde are mixed at a temperature of about 0 to 80 ° C, preferably 10 to 60 ° C in a strong alkaline medium with a temperature of 1 to 3 ° C.
By reacting for 0 hour, one having R ⁶ ＨH can be obtained. Thereafter, under further acidic conditions, an alcohol having 1 to 4 carbon atoms, a substituted alcohol, an acid halide, or an acid anhydride,
By reacting at 0 to 80 ° C for 1 to 30 hours, R
⁶ = Alkyl and acyl are obtained. alcohol,
The temperature when reacting with the substituted alcohol is 20 to 80 ° C.
The temperature at the time of reacting with an acid halide or an acid anhydride is preferably from 0 to 30 ° C. Specific examples of the phenol derivative that can be used in the present invention include the following general formulas (VI) to (VI).
Examples include, but are not limited to, compounds represented by (XIII). These phenol derivatives are
They may be used alone, or two or more kinds may be used in combination.
-60% by weight, preferably 0.5-20% by weight.
Further, a compound having from 1 to 3 benzene nuclei and having a phenolic hydroxyl group and a group represented by the formula (V) causes a decrease in the inking property and development acceptability. Desirably does not substantially contain these compounds. More specifically, the content is preferably 5% by weight or less, more preferably 3% by weight or less, and most preferably 0% by weight in the negative type image recording material.

Embedded image

Embedded image

Embedded image

Embedded image ^{Wherein, R 7 ~R 9, R 14} , R 22, R 23 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, R ^10,
R ¹⁸ to R ²¹ represents a hydrogen atom or an alkyl group, R ¹¹ to R
¹³ represents a hydrogen atom, a halogen atom or an alkyl group;
^{15 to} R ¹⁷ represent a single bond, an alkylene group which may have a substituent, an alkenylene group, a phenylene group, a naphthylene group, a carbonyl group, an ether group, a thioether group, an amide bond, or a combination of two or more thereof. , Y represents a group represented by the general formula (V), and a, b, c, d, x,
y represents an integer of 0 to 3, but a + b + c + d + x + y
Is an integer of 2 to 16, and k, l, m, and n each represent an integer of 0 to 3, but not all 0, and e, f,
g, h, p, q, r, s, t, and u each represent an integer of 0 to 3, and z represents 0 or 1. The general formulas (VI) to (XIII)
As a more specific example of the compound represented by the following, for example, those having the following structures may be mentioned.

Embedded image

Embedded image

Embedded image

Embedded image In the formula, Y ^{2 to} Y ¹³ each represent a hydrogen atom or a group represented by the formula (V).
And preferably all are groups represented by the formula (V). Other thermal crosslinking agents suitably used in the present invention include aldehyde and ketone compounds. Preferably, it is a compound having two or more aldehydes or ketones in the molecule. These thermal crosslinking agents may be used alone or in combination of two or more. In the present invention, the thermal crosslinking agent is used in an amount of 5 to 70% by weight, preferably 10 to 65% by weight, based on the total solid content of the image recording material. If the added amount of the thermal crosslinking agent is less than 5% by weight, the film strength of the image area at the time of image recording deteriorates, and if it exceeds 70% by weight, it is not preferable from the viewpoint of storage stability. [(C) Acid Generator] In the present invention, the acid generator is a compound which is decomposed by light or heating at 100 ° C. or more to generate an acid. Examples of the generated acid include p-acids such as sulfonic acid and hydrochloric acid.
It is preferable that Ka is a strong acid of 2 or less. Examples of the acid generator suitably used in the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts. Specifically, US4,7
08, 925 and the compounds described in JP-A-7-20629. In particular, iodonium salts having sulfonate ions as counter ions, sulfonium salts,
Diazonium salts are preferred. As the diazonium salt,
The diazonium compound described in U.S. Pat. No. 3,867,147, the diazonium compound described in U.S. Pat.
The diazo resin described in each publication of 102457 is also preferable. US5, 135, 838 and US5, 2
Benzyl sulfonates described in US Pat. Further, active sulfonic acid esters and disulfonyl compounds described in JP-A Nos. 2-100054, 2-100055 and 8-9444 are also preferable. Besides, haloalkyl-substituted S-triazines described in JP-A-7-271029 are also preferable. These compounds may be used alone or in combination of two or more. These compounds are used in an amount of 0.01 to 0.01% based on the total solid content of the image recording material.
It is added to the image recording material in a proportion of 50% by weight, preferably 0.1 to 25% by weight, more preferably 0.5 to 15% by weight. If the amount is less than 0.01% by weight, no image can be obtained. On the other hand, if the amount exceeds 50% by weight, non-image areas are stained during printing. [(D) Infrared absorber] In the present invention, it is necessary to use an infrared absorber in combination in order to efficiently perform recording with an infrared laser. The infrared absorber used in the present invention is a dye or pigment that effectively absorbs infrared rays having a wavelength of 760 nm to 1200 nm, and preferably has a wavelength of 760 nm to 1200 nm.
It is a dye or pigment having an absorption maximum at 60 nm to 1200 nm. As the dye, commercially available dyes and known dyes described in literatures such as "Dye Handbook" (edited by The Society of Synthetic Organic Chemistry, Japan, 1970) can be used. Specifically, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes Is mentioned. Preferred dyes include, for example, JP-A-58-12524.
No. 6, JP-A-59-84356, JP-A-59-202
No. 829, JP-A-60-78787 and the like, and methine dyes described in JP-A-58-173696, JP-A-58-181690 and JP-A-58-194595. JP-A-58-11279
No. 3, JP-A-58-224793, JP-A-59-48
187, JP-A-59-73996, JP-A-60-5
2940, JP-A-60-63744 and the like, naphthoquinone dyes described in JP-A-58-112792 and the like, British Patent 43
And the cyanine dyes described in U.S. Pat. Further, a near infrared absorption sensitizer described in U.S. Pat. No. 5,156,938 is also suitably used.
No. 881,924, substituted arylbenzo (thio) pyrylium salts, JP-A-57-142645 (U.S. Pat. No. 4,327,169), trimethinethiapyrylium salts, JP-A-58-181051. 58-2
No. 20143, No. 59-41363, No. 59-842
No. 48, No. 59-84249, No. 59-146063
And the cyanine dyes described in JP-A-59-216146, the pentamethine thiopyrylium salt described in U.S. Pat. No. 4,283,475, and the like. 5-13514
And the pyrylium compounds disclosed in JP-A-5-19702 are also preferably used. Another preferred example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes. Examples of the pigment used in the present invention include commercially available pigments and color index (CI) handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986) and "Printing Ink Technology" published by CMC, 1984). As the type of pigment, black pigment, yellow pigment, orange pigment, brown pigment, red pigment,
Examples include purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments,
Chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments,
Isoindolinone pigments, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments,
Natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used. Preferred among these pigments is carbon black. These pigments may be used without surface treatment, or may be used after surface treatment. Examples of the surface treatment include a method of surface coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Can be considered. The above surface treatment methods are described in “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986).
Annual). Pigment particle size is 0.01μm ~
It is preferably in the range of 10 μm,
More preferably, it is in the range of 1 μm, especially 0.1 μm.
It is preferably in the range of μm to 1 μm. If the particle size of the pigment is less than 0.01 μm, the dispersion is not preferred in terms of stability in the coating solution for the image recording layer, and if it exceeds 10 μm, the uniformity of the image recording layer is not preferred. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Detail is,
It is described in "Latest Pigment Application Technology" (CMC Publishing, 1986). These dyes or pigments are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the image recording material.
10 to 10% by weight, particularly preferably 1.0 to 10
It can be added to the image recording material in a proportion of% by weight. If the amount of the pigment or the dye is less than 0.01% by weight, the sensitivity is lowered, and if it exceeds 50% by weight, the non-image area is stained during printing. These dyes or pigments may be added to the same layer as other components, or a separate layer may be provided and added thereto. In general, in the case of a visible light sensitizer,
Its mechanism of action is "sensitizer" (edited by Katsumi Tokumaru and Shin Okawara,
As described in Kodansha Co., Ltd., etc., it is said to be due to energy transfer or electron transfer. However, the mechanism of action of infrared sensitizers is not sufficiently clear. For example, it is said that the infrared absorber absorbs infrared rays and then generates heat to thermally decompose the acid generator. [(E) Low molecular weight compound having sulfonamide group] In the present invention, a low molecular weight compound having a sulfonamide group represented by the general formula (II) is used. In the formula, R ²⁴ represents an optionally substituted hydrocarbon group having 20 or less carbon atoms;
²⁵ is a hydrogen atom, substituted showed the following hydrocarbon group or -COR ²⁶ which may 20 carbon atoms, R ²⁶ is a hydrocarbon group having not more than carbon atoms 20 which may have a substituent Show.
Preferred substituents which may be used in R ²⁴ to R ^26, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carbamoyl group, of 20 or less alkoxyl group, a perfluoroalkyl group and a carbon number of 20 or less carbon atoms carbon atoms And 20 or less hydroxyalkyl groups. In the present invention, examples of the low molecular weight compound having a sulfonamide group suitably used are represented by formulas (II-1) to
The compound (II-8) is described below. In the following formula, R ²⁷
Represents a hydrogen atom or a methyl group, and Z ² represents an oxygen atom or N
H is shown.

Embedded image

Embedded image The weight average molecular weight of the low molecular weight compound having a sulfonamide group is preferably 2000 or less. [Others] Various additives may be further added to the image recording material of the present invention, if necessary. For example, a polyfunctional monomer having two or more radically polymerizable ethylenic double bonds in the molecule can be added. Such compounds include ethylene glycol di (meth)
Of acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol and dipentaerythritol Tri-, tetra- or hexa (meth) acrylate and the like can be mentioned. The addition amount of these polyfunctional monomers is 30% by weight or less in the image recording material. Alkyl ethers (eg, ethyl cellulose, methyl cellulose) for improving coatability, surfactants (eg, fluorine-based surfactants), plasticizers for imparting film flexibility and abrasion resistance (For example, tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate,
Tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added. The amount of these additives varies depending on the purpose of use, but is generally 0.5 to 30% by weight based on the total solids of the image recording material. In order to obtain a visible image immediately after the heat generated by the exposure, an organic dye capable of forming a salt with a compound which releases an acid by the heat generated by the exposure can be used. Specifically, JP-A-50-36
No. 209 and No. 53-8128, salt-forming organic dyes capable of forming a salt with o-naphthoquinonediazide-4-sulfonic acid halogenide.
Examples thereof include salt-forming organic dyes capable of forming a salt with the trihalomethyl compound described in JP-A-3-36223 and JP-A-54-74728. Dyes other than the salt-forming organic dyes described above can also be used as colorants for images. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS,
Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue,
Crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI4
5170B), malachite green (CI4200)
0), methylene blue (CI52015) and the like. These dyes can also be used as salt-forming organic dyes. The dye is used in an amount of 0 to Used in weight percent additions. In the image recording material of the present invention, each of the above components is coated on a support using a solvent that dissolves or disperses these components. As the solvent used here,
Methanol, ethanol, isopropyl alcohol, n
-Butyl alcohol, t-butyl alcohol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ethyl, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy There are -2-propyl acetate, N, N-dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, ethyl acetate, methyl lactate, ethyl lactate and the like, and these solvents are used alone or in combination. Further, a mixed solvent obtained by adding a small amount of water or a solvent that does not dissolve a phenol derivative such as toluene or a high molecular compound to these solvents or a mixed solvent is also suitable. The concentration (solid content) of the above components in the solvent is as follows:
1 to 50% by weight. The temperature at which the liquid obtained by dissolving or dispersing each of the above components in these solvents is applied to a support and the applied layer is dried is preferably from 50C to 120C. The drying method may be pre-drying at a low temperature, followed by drying at a high temperature, or directly at a high temperature by selecting an appropriate solvent and concentration, but since it is a heat-sensitive recording material, it should be dried at a high temperature of 150 ° C or higher. Is not preferred. Although the amount of application varies depending on the application, for example, a photosensitive lithographic printing plate (thermosensitive lithographic printing plate) generally has a solid content of 0.1%.
5-3.0 g / m < ² > is preferable. The photosensitivity increases as the coating amount decreases, but the physical properties of the photosensitive film deteriorate. If necessary, a mat or a mat layer may be provided on the photosensitive film, or an undercoat layer may be provided. Examples of the support on which the image recording material of the present invention is applied include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), for example, aluminum (including aluminum alloy), zinc, Plates of metal such as copper, such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. It includes a plastic film, a paper or plastic film on which all the genus are laminated or vapor-deposited, and the like. Among these supports, it is preferable to use a polyester film or an aluminum plate. Particularly, an aluminum plate is preferable because it is extremely stable in dimension. Further, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable. Further, in the case of a support having a metal, particularly aluminum having a surface, it is desirable to perform an appropriate hydrophilic treatment. As such a hydrophilization treatment, for example, an aluminum surface is subjected to wire brush graining,
Mechanical methods such as brush graining, ball graining, etc., which roughen with a nylon brush while pouring a slurry of abrasive particles, chemical graining using HF, AlCl ₃ , or HCl as an etchant, electrolysis using nitric acid or hydrochloric acid as an electrolytic solution After graining the surface by graining or complex graining that combines these surface roughening methods, etching is performed with an acid or alkali as necessary, and then sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromium It is preferable to provide a strong passivation film on the aluminum surface by performing anodic oxidation with a DC or AC power supply in an acid, sulfamic acid or a mixed acid thereof. Although the aluminum surface is hydrophilized by such a passivation film, if necessary, U.S. Pat. No. 2,714,066 and U.S. Pat.
No. 181 461, silicate treatment (sodium silicate, potassium silicate), U.S. Pat.
No. 46,638, potassium fluoride zirconate treatment; U.S. Pat. No. 3,201,247, phosphomolybdate treatment; British Patent 1,108,559. Alkyl titanate treatment, the polyacrylic acid treatment described in DE 1,091,433,
No. 134,093 and British Patent 1,230,44
7, a polyvinylphosphonic acid treatment described in JP-B-44-6409, a phytic acid treatment described in U.S. Pat. No. 3,307,951, JP-A-58-1689
No. 3, 58-18291, a composite treatment comprising a hydrophilic organic polymer compound and a divalent metal, having a sulfonic acid group described in JP-A-59-101651. Those subjected to hydrophilization treatment by undercoating of a water-soluble polymer are particularly preferred. Other hydrophilic treatment methods include silicate electrodeposition described in U.S. Pat. No. 3,658,662. As a light source of the active light beam used for image exposure, for example, a mercury lamp, a metal halide lamp, a xenon lamp,
There are chemical lamps, carbon arc lamps and the like. The radiation includes an electron beam, an X-ray, an ion beam, a far infrared ray, and the like. Also, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) can be used. Examples of the laser beam include a helium / neon laser, an argon laser, a krypton laser, a helium / cadmium laser, and a 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-state laser and a semiconductor laser are particularly preferable. As the developer and replenisher for the negative-working image recording material of the present invention, conventionally known aqueous alkaline solutions can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium, ammonium, sodium hydroxide,
And inorganic alkali salts such as ammonium, potassium and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine,
Organic alkali agents such as n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, and pyridine are also used. These alkali agents are used alone or in combination of two or more. Various surfactants and organic solvents can be added to the developing solution and the replenishing solution as required for the purpose of promoting or suppressing the developing property, dispersing the developing gas and increasing the ink affinity of the printing plate image area. Preferred surfactants include
Examples include anionic, cationic, nonionic and amphoteric surfactants. Further, the developing solution and the replenisher, if necessary, hydroquinone, resorcinol, sulfurous acid, reducing agents such as sodium salts and potassium salts of inorganic acids such as bisulfite,
Further, an organic carboxylic acid, an antifoaming agent, and a water softener can be added. Among these developing solutions, particularly preferred are, for example, JP-A-54-62004 and JP-B-Sho 5-62004.
JP-A-7-7427, and a developer composition comprising benzyl alcohol, an anionic surfactant, an alkali agent and water described in JP-A-51-77401. 53-44202, a developer composition comprising an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite; water described in JP-A-55-155355; And a developer composition containing an organic solvent having an solubility of 10% by weight or less at room temperature, an alkali agent and water. When using the image recording material of the present invention as a printing plate, after developing using the developer and the replenisher, washing water, a rinsing solution containing a surfactant and the like,
It is preferable to carry out post-treatment with a desensitizing solution containing gum arabic and a starch derivative. These processes can be used in various combinations for post-processing. In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally includes a developing section and a post-processing section, and includes a device for transporting a printing plate, each processing solution tank and a spray device, and transports the exposed printing plate horizontally while pumping each plate. The processing liquid is sprayed from a spray nozzle to perform development processing. Recently, a method is also known in which a printing plate is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

The present invention will be described below in detail with reference to examples.
However, the present invention is not limited to these.Of low molecular weight compound [SA-1] having a sulfonamide group
Synthesis 500 ml volume of a flask equipped with a stirrer and cooling tube
To 4-acetamidobenzenesulfonyl chloride 3
7.39 g (0.16 mol) and acetonitrile 100 m
and stirred under an ice-water bath. 2, 5
24.51 g (0.16 mol) of dimethoxyaniline and
17.81 g (0.176 mol) of triethylamine was added to
A solution dissolved in 100 ml of setonitrile is dripped little by little
did. After dropping, remove the ice water bath and stir at room temperature for 1 hour.
Stirred. After completion of the stirring, the reaction solution is poured into 1.1 liter of water.
And acidified with sulfuric acid. The precipitate is collected by filtration and
Washed. By drying the obtained solid under reduced pressure,
4-acetamidobenzenesulfonylamino-2,5-
52.3 g of dimethoxybenzene were obtained. Next, the stirrer
And a 200 ml flask equipped with a condenser
-Acetamidobenzenesulfonylamino-2,5-di
Methoxybenzene 24.53 g, concentrated sulfuric acid 7.08 g,
Add ethanol 100ml and water 10ml, 1.5 hours
Heated to reflux. After heating is completed, the reaction solution is
2.8 g was added to an aqueous solution in which 500 ml of water was dissolved.
The precipitate was collected by filtration and washed with water. The solid obtained
Is dried under reduced pressure to give 4-aminobenzenesulfo.
Nilamino-2,5-dimethoxybenzene 20.93 g
I got Next, 300 m equipped with a stirrer and a cooling pipe
In a 1-liter flask, add 4-aminobenzenesulfonylua
20.93 g of mino-2,5-dimethoxybenzene, acetic acid
Add 6.68 g of sodium and 100 ml of acetone,
The mixture was stirred in an ice water bath. Add this mixture to methacrylic acid
7.1 g of lid was added dropwise little by little. After dripping, ice water bath
Was removed and the mixture was stirred at room temperature for 1 hour. After stirring, react
The liquid was poured into 500 ml of water. Collect the precipitate by filtration
And washed with water. Drying the obtained solid under reduced pressure
From 4-methacryloylaminobenzenesulfonylua
22.40 g of mino-2,5-dimethoxybenzene were obtained.
Was. This compound was designated as [SA-1]. Of low molecular weight compound [SA-2] having a sulfonamide group
Synthesis Reaction of p-toluenesulfonic acid chloride with aniline
To synthesize N-phenyl-p-toluenesulfonamide
And [SA-2].Low molecular weight compound containing a sulfonamide group [SA-3]
Synthesis of Triene benzenesulfonamide and benzoyl chloride
The reaction is carried out in the presence of tylamine to give N-benzoylbenzenes.
Rufonamide was synthesized and designated as [SA-3]. Of binder [BP-1] Radical polymerization of the aforementioned [SA-1] by a conventionally known method
Then, a homopolymer of [SA-1] was synthesized, and [BP-
1]. When the weight average molecular weight was measured, 54,
000 (polystyrene standard).Synthesis of binder [BP-2] Condensation of m-cresol and formaldehyde under acidic conditions
Reaction, and a novolak resin having a weight average molecular weight of 4000
It was synthesized and was referred to as [BP-2].Synthesis of Crosslinking Agent [KZ-1] 1- [α-methyl-α- (4-hydroxyphenyl) d
Tyl] -4- [α, α-bis (4-hydroxyphenyl
20 g of potassium hydroxide solution
(10%) dissolved in 100 ml. The reaction solution is
1 hour while stirring 60 ml of marine (37%) at room temperature
It dripped over. The reaction was stirred at room temperature for a further 6 hours.
After that, the solution was poured into an aqueous sulfuric acid solution to cause crystallization. The obtained pe
After thoroughly washing the paste-like precipitate with water, 30 ml of methanol
Cross-linking agent in the form of white powder by recrystallization using
[KZ-1] was obtained. The yield was 20 g. Got
The compound was analyzed by NMR for 1- [α-methyl-α- (4-H
Droxyphenyl) ethyl] -4- [α, α-bis (4
-Hydroxyphenyl) ethyl] benzene
It was found to be a roll compound. Reversed phase HPLC
Ram: Shimpac CLC-ODS (Shimadzu Corporation)
Manufactured), solvent: methanol / water = 60/40 → 90/10
The purity of the hexamethylol compound was 92%.

Embedded image Synthesis of Crosslinking Agent [KZ-2] Condensation reaction between bisphenol A and formalin under basic conditions
In response, a resole resin with a weight average molecular weight of 2,000 was synthesized.
Thus, a crosslinking agent [KZ-2] was obtained. Example 1 0.30 mm thick aluminum plate (material
1050) after trichlorethylene washing and degreasing,
Nylon brush and 400 mesh pamistone-water suspension
The surface was grained using the solution, and washed well with water. This
Plate for 9 seconds in a 25% aqueous solution of sodium hydroxide at 45 ° C
After immersion, etching and washing with water, 2% HNO _Three
For 20 seconds and washed with water. At this time,
Etching amount is about 3g / m^TwoMet. Next, this plate
% H_TwoSO_FourCurrent density 15A / dm^Twoso
3g / m^TwoAfter the DC anodic oxide film of
Was. Next, apply the following undercoat liquid to this aluminum plate,
Dried at 80 ° C. for 30 seconds. The amount of coating after drying is 10mg
/ M^TwoMet. Undercoat solution β-alanine 0.1 g Phenylphosphonic acid 0.05 g Methanol 40 g Pure water 60 g Next, the following solution [P-1] was prepared, and this solution was
And applied at 100 ° C
After drying for minutes, a negative type lithographic printing plate material [P-1] was obtained.
Weight after drying is 1.5 g / m^TwoMet. Solution [P-1] Low molecular weight compound having a sulfonamide group [SA-1] 0.25 g Binder [BP-1] 1.6 g Crosslinking agent [KZ-1] 0.4 g 2-methoxy-4-phenylaminobenzene 0.10 g of diazonium Hexafluorophosphate Infrared absorber [SK-1] (Structural formula shown below) 0.10 g Megafac F-177 0.06 g (Fluorine-based surfactant manufactured by Dainippon Ink and Chemicals, Inc.) ) Methyl ethyl ketone 15 g 1-methoxy-2-propanol 5 g Methyl alcohol 7 g

Embedded image The obtained negative type lithographic printing plate material [P-1] was treated with a wavelength of 83
Exposure was performed with a semiconductor laser emitting infrared light of about 0 to 850 nm. After the exposure, the panel heater was used at 110 ° C for 15 minutes.
Heat treatment was performed for seconds. Subsequently, development was performed with a developer DP-4 (1: 8) manufactured by Fuji Photo Film Co., Ltd. At this time, the time until the unexposed portion was completely removed was measured.
It was 0 seconds. Furthermore, using this printing plate, Heidel K
When printing was performed by an OR-D machine, 50,000 printed matters were obtained. Comparative Example 1 A negative type lithographic printing plate [Q-1] was prepared in exactly the same manner as in the solution [P-1] used in Example 1, except that [SA-1] was not used. The obtained planographic printing plate material [Q-1] was exposed to laser light, heated and developed in the same manner as in Example 1. When developing, the time until the unexposed portion was completely removed was measured.
Seconds. Furthermore, using this printing plate, Heidel KO
As a result of printing with an RD machine, 50,000 printed matters were obtained. (Comparative Example 2) In the solution [P-1] used in Example 1, except that benzoic acid was used instead of [SA-1], a negative type planographic printing plate [Q-2] was used. It was created. The obtained lithographic printing plate material [Q-2] was exposed to laser light, heated and developed in the same manner as in Example 1. Upon development, the time required to completely remove the unexposed portions was 10 seconds. Furthermore, using this printing plate,
Printing on a Heidel KOR-D machine yielded only 35,000 copies. From Example 1 and Comparative Examples 1 and 2,
It can be seen that when the recording material of the present invention is used, the developing speed can be improved without deteriorating the printing durability during printing. (Example 2) The following solution [P-2] was prepared, and this solution was applied to an undercoated aluminum plate prepared in (Example 1), and dried at 100 ° C for 1 minute for negative type lithographic printing. Plate material [P-2] was obtained. Weight after drying is 1.5 g / m
^{Was 2} . Solution [P-2] Low-molecular compound [SA-2] having a sulfonamide group 0.25 g Binder [BP-2] 1.6 g Crosslinking agent [KZ-1] 0.4 g 2-methoxy-4-phenylaminobenzene 0.10 g of diazonium Hexafluorophosphate Infrared absorbent [SK-1] 0.10 g Megafac F-177 0.06 g (manufactured by Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) methyl ethyl ketone 15 g 1- Methoxy-2-propanol 5 g Methyl alcohol 7 g The obtained lithographic printing plate material [P-2] was exposed to laser light, heated and developed in the same manner as in Example 1. When developed, when the time until the unexposed part was completely removed was measured,
6 seconds. Furthermore, using this printing plate, Heidel K
As a result of printing with an OR-D machine, 25,000 sheets of printed matter were obtained. Comparative Example 3 A negative type lithographic printing plate [Q-3] was prepared in exactly the same manner as in the solution [P-2] used in Example 2, except that [SA-2] was not used. The obtained planographic printing plate material [Q-3] was exposed to laser, heated and developed in the same manner as in Example 2. When developing, the time until the unexposed portion was completely removed was measured.
Seconds. Furthermore, using this printing plate, Heidel KO
As a result of printing with an RD machine, 25,000 printed matters were obtained. (Comparative Example 4) In the solution [P-2] used in Example 2, except that bisphenol A was used instead of [SA-2], a negative type lithographic printing plate [Q-
4]. Obtained planographic printing plate [Q-4]
Was exposed to laser, heated and developed in the same manner as in Example 2. Upon development, the time required for the unexposed portions to be completely removed was 6 seconds. Furthermore, when this printing plate was used for printing on a Heidel KOR-D machine,
Only 15,000 prints were obtained. From Example 2 and Comparative Examples 3 and 4, it can be seen that when the recording material of the present invention was used, the developing speed could be improved without deteriorating the printing durability during printing. (Example 3) The following solution [P-3] was prepared, and this solution was applied to an undercoated aluminum plate prepared in (Example 1), and dried at 100 ° C for 1 minute for negative type lithographic printing. Plate material [P-3] was obtained. Weight after drying is 1.5 g / m
^{Was 2} . Solution [P-3] Low-molecular compound [SA-3] having a sulfonamide group 0.25 g Binder [BP-1] 1.0 g Binder [BP-2] 0.6 g Crosslinking agent [KZ-2] 0.4 g 0.10 g of 2-methoxy-4-phenylaminobenzenediazonium Hexafluorophosphate Infrared absorbent [SK-1] 0.10 g Megafac F-177 0.06 g (manufactured by Dainippon Ink and Chemicals, Inc. Surfactant) Methyl ethyl ketone 15 g 1-methoxy-2-propanol 5 g Methyl alcohol 7 g The obtained lithographic printing plate material [P-3] was exposed to laser light, heated, and developed in the same manner as in Example 1. When developed, when the time until the unexposed part was completely removed was measured,
8 seconds. Furthermore, using this printing plate, Heidel K
When printing was performed by an OR-D machine, 40,000 sheets of printed matter were obtained. (Comparative Example 5) A negative planographic printing plate [Q-5] was prepared in exactly the same manner as in the solution [P-3] used in Example 3, except that [SA-3] was not used. The obtained lithographic printing plate material [Q-5] was exposed to laser, heated and developed in the same manner as in Example 3. When developing, the time until the unexposed portion was completely removed was measured.
Seconds. Furthermore, using this printing plate, Heidel KO
As a result of printing with an RD machine, 40,000 sheets of printed matter were obtained. (Comparative Example 6) In the solution [P-3] used in Example 3, except that toluene sulfonic acid was used instead of [SA-3], the negative type lithographic printing plate [Q
-6]. The obtained planographic printing plate material [Q-6]
Was exposed to laser, heated and developed in the same manner as in Example 3. Upon development, the time required for the unexposed portions to be completely removed was measured, and was 8 seconds. Furthermore, when this printing plate was used for printing on a Heidel KOR-D machine,
Only 27,000 prints were obtained. From Example 3 and Comparative Examples 5 and 6, it can be seen that when the recording material of the present invention was used, the developing speed could be improved without deteriorating the printing durability during printing.

According to the present invention, a plate can be directly made from digital data of a computer or the like by recording using a solid-state laser and a semiconductor laser that emit infrared light.
Further, it is possible to provide a negative image recording material capable of shortening the development time without impairing the film strength.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/033 G03F 7/033

Claims (1)

[Claims] (A) a polymer having a structural unit represented by the following general formula (I), (B) a compound capable of crosslinking by an acid, (C) a compound capable of generating an acid by light or heat,
A negative-type image recording material comprising: (D) an infrared absorber; and (E) a low-molecular compound having a sulfonamide group represented by the following general formula (II). Embedded image In the formula, X ¹ itself shows alkali solubility or a linking group having an alkali-soluble group. Ar
¹ represents an aromatic hydrocarbon group having 20 or less carbon atoms which may have a substituent. Y ¹ represents NR ³ , an oxygen atom or a sulfur atom. n shows the integer of 1-4. L ¹ is,
It represents a single bond, an ester bond, a carboxylic acid amide bond, a sulfonic acid amide bond, an ether bond, a thioether bond or a hydrocarbon group having 20 or less carbon atoms which may contain these bonds. L ² represents a single bond or a hydrocarbon group having 20 or less carbon atoms. R ¹ represents a hydrogen atom or a methyl group. R ² represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. R ³ represents a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Embedded image In the formula, R ²⁴ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent, and R ²⁵ represents a hydrogen atom, a hydrocarbon group having 20 or less carbon atoms which may have a substituent or −COR ²⁶
And R ²⁶ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent.