JPH10193554A - Negative type image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative type image recording material having excellent film strength of a recorded image and satisfactory plate wear resistance at the time of printing with small contamination at the time of printing due to small residual coating film of a non-image part after image recording by directly engraving from digital data. SOLUTION: The negative type image recording material comprises (A) a polymer having a unit represented by a formula, (B) compound crosslinked by an acid, and (C) compound decomposed by light or heat to generate acid such as sulfonic acid where X1 indicates a bond group exhibiting by itself alkali solubility or having an alkali soluble group, Ar1 shows 20-0C aromatic hydrocarbon group which may have a substituent, Y1 indicates N-R, oxygen atom or sulfur atom, n indicates integer of 1 to 4, L1 indicates 20-0C hydrocarbon group which may have a single bond, ester bond, amide carboxylate bond, amide sulfonate bond, ether bond, thioether bond or these bonds, L2 shows single bond or 20-0C methyl group, R1 indicates hydrogen atom or methyl group, R2 indicates 20-0C hydrocarbon group which may have substituent, and R3 shows hydrogen atom or 20-0C hydrocarbon group which may have substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lithographic printing plate material, a color proof, an image recording material which can be used as a photoresist and a color filter. In particular, the present invention relates to an image recording material that can be directly made by scanning an infrared laser based on a digital signal from a computer or the like and that can be used as a so-called direct plate making lithographic printing plate material.

[0002]

2. Description of the Related Art Conventionally, a system for directly making a plate from digital data of a computer includes (1) an electrophotographic method, (2) a photopolymerization system for exposing using a laser emitting blue or green light, (3) ) A silver salt laminated on a photosensitive resin, and (4) a silver salt diffusion transfer method have been proposed.

However, in the case of using the electrophotographic method of (1), the process of image formation such as charging, exposure and development is complicated, and the apparatus is complicated and large. Also,
In the case of the photopolymerization system (2), since a plate material having high sensitivity to blue or green light is used, handling in a bright room becomes difficult. The methods (3) and (4) have drawbacks in that processing such as development is complicated because silver salts are used, and silver is contained in the processing waste liquid.

On the other hand, the development of lasers in recent years has been remarkable, and in particular, solid-state lasers and semiconductor lasers that emit infrared light having a wavelength of 760 nm to 1200 nm have become easily available with high output and small size. These lasers are very useful as a recording light source when making a plate directly from digital data of a computer or the like. However, many photosensitive recording materials that are practically useful have a photosensitive wavelength in the visible light range of 760 nm or less, and therefore cannot record images with these infrared lasers. Therefore, a material that can be recorded by an infrared laser is desired.

As an image recording material recordable by such an infrared laser, there is a recording material comprising an onium salt, a phenol resin and a spectral sensitizer described in US Pat. No. 4,708,925. However, this image recording material is expressed by an onium salt and a phenol resin,
It is a positive type utilizing the effect of suppressing dissolution in a developer.
On the other hand, as a negative type image recording material, JP-A-7-206 is used.
No. 29, an onium salt, a resole resin,
There is a recording material comprising a novolak resin and an infrared absorber. This image recording material is a positive type only by laser exposure, and a negative image can be obtained by performing a heat treatment after the laser exposure. Generally, in order to obtain a negative image, it is a principle that a non-exposed portion serving as a non-image portion does not leave a coating film after development, but in an image recording material described in JP-A-7-20629, If the heat treatment after exposure is made mild, the positive-type properties of the recording material are less likely to be lost, and the coating film is more likely to remain on the unexposed portions. Therefore, a printing plate material using such an image recording material has a problem that stains are likely to occur during printing. Further, in a printing plate using this image recording material, the film strength of the image portion is insufficient, and as a result, the printing durability during printing is insufficient.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a negative type image recording material which can be directly made from digital data of a computer or the like by recording using a solid-state laser and a semiconductor laser emitting infrared rays. To provide. Further, another object of the present invention is to reduce the remaining coating film in the non-image area after image recording, to reduce stains during printing, and to further improve the film strength of the recorded image and improve the printing durability during printing. To provide a negative image recording material.

[0007]

Means for Solving the Problems The present inventor paid attention to the constituent components of a negative-type image recording material, and as a result of diligent studies, it was found that the above object can be achieved by using a polymer having a specific functional group as a binder. And completed the present invention. That is, the present invention provides: (A) a polymer having a structural unit represented by the following general formula (I);
Compound cross-linked by acid (hereinafter referred to as thermal cross-linking agent)
And (C) a compound capable of generating an acid by light or heat (hereinafter, referred to as an acid generator).

Formula (I)

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In the formula, X ₁ represents alkali-soluble itself 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 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.

In the negative type image recording material of the present invention,
The light- or heat-irradiation decomposes the acid generator (C) in the irradiated portion to generate an acid. The strong acid group generated here causes the (B) thermal cross-linking agent and (A) represented by the general formula (I). By promoting a crosslinking reaction with a polymer having a structural unit, image recording, that is, plate making is performed, but this polymer has a good crosslinking property. Therefore, a strong coating film is formed. Moreover, it does not become a positive type by exposure. Therefore, in the case of light irradiation, a good negative image can be formed even if the post-heating is mild. Further, since this polymer has an alkali-soluble bonding group in a structural unit, the plate material in the non-image area is effectively removed by alkaline water or the like, and a good printing plate having a small remaining coating film in the non-image area. Can be obtained.

[0011]

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
Shows alkali solubility or has an alkali soluble group.
Is shown. Here, the alkali-soluble group is
Sulfonamide, sulfonimide or carboxylic acid
Refers to a group containing a moiety such as _Two
NH-, -NHSO_Two-, -SO_TwoNHCO-, -CO
NHSO_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 these, from the viewpoint of availability and economy,
It is preferably a phthalene ring. Also, these fragrances
As a preferred substituent which the group hydrocarbon group can have,
Hydrocarbon groups having 20 or less carbon atoms, halogen atoms,
Ano group, nitro group, carboxyl group, carbamoyl group, etc.
Can be mentioned.

Y ₁ represents NR ₃ , an oxygen atom or a sulfur atom, and R ₂ has 2 carbon atoms which may have a substituent.
Indicates 0 or less hydrocarbon groups. Here, R ₃ represents a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents that can be used in R ₂ and R ₃ include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carbamoyl group, an alkoxyl group having 20 or less carbon atoms, a perfluoroalkyl group having 20 or less carbon atoms, and a carbon number And 20 or less hydroxyalkyl groups. N represents an integer of 1 to 4. L ₁ is a single bond, an ester bond, a carboxylic acid amide bond, a sulfonic acid amide bond, an ether bond,
It represents 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, and is preferably a single bond from the viewpoint of availability and economy. Note that R ₂ and Ar _1, R ₃ and Ar ₁ , and R ₂ and R 1
_3. Each may form a ring structure such as a cyclohexane ring.

The polymer having a structural unit represented by the general formula (I) suitably used in the present invention is a polymer having a structural unit represented by the following general formula (II). In the general formula (II), the same reference numerals as those in the general formula (I) denote the same parts, and a description thereof will be omitted.

Formula (II)

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In the formula, R ₄ and R ₅ may be the same or different and represent a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent. R ₄ and R
Preferred substituents that can be used in ₅ include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carbamoyl group, an alkoxyl group having 20 or less carbon atoms, a perfluoroalkyl group having 20 or less carbon atoms, and a hydroxy having 20 or less carbon atoms. Examples include an alkyl group. 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 (II) can be obtained by radical polymerization using a corresponding monomer represented by the general formula (III) by a conventionally known method. In the general formula (III), the general formula (I
The same reference numerals as in (I) denote the same parts, and a description thereof will be omitted.

Formula (III)

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

[0019]

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[0020]

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[0021]

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In the present invention, as the preferable polymer having the structural unit represented by the general formula (I), a homopolymer using only one kind of the monomer represented by the above general formula (III) or two or more kinds thereof may be used. Both copolymers used can be used.

The polymer which can be used in the present invention is a copolymer of a monomer represented by the general formula (III) and a conventionally known polymerizable monomer other than the monomer represented by the general formula (III). It is preferable to use from the viewpoint of solubility in a coating solution and flexibility of a coating film. Known monomers used in combination with such a monomer represented by the general formula (III) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl Acrylates, acrylates such as benzyl acrylate, methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, 2-
Examples include methacrylates such as 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 its partial structure, X ₁ which is a linking group having alkali solubility (for example, an acidic group). The copolymer is excellent in solubility in alkaline water, but may be a copolymer using a monomer having another acidic group as a supplement. Examples of the monomer used include 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- (methylsulfur) Famoylphenyl) 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- (hydroxy Phenyl) methacrylamide, N- (hydroxynaphthyl) acrylamide, N- (hydroxynaphthyl) methacrylamide and the like.

Also, although not an acidic group, sodium salts of p-styrenesulfonic acid, alkali metal salts of 2-acrylamido-2-methylpropanesulfonic acid, tetraalkylammonium salts, potassium salts of 3-sulfopropylacrylate, etc. A monomer containing a salt of a strong acid can improve the solubility in water and, as a result, can improve the developability of an image recording material in an aqueous developing solution.

The proportion of the structural unit represented by the general formula (I) contained in the copolymer using these is preferably 20 to 95% by weight, more preferably 30 to 90% by weight.
% By weight.

The weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, more preferably Is 200
The range is from 0 to 250,000. Polydispersity (weight average molecular weight /
(Number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.

These polymers are random polymers,
Any of a block polymer and a graft polymer may be used, but a random polymer is preferable.

Examples of the solvent used for synthesizing the polymer used in the present invention include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, -Methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-
Examples include 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 when 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 4% 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 0 to 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, alkoxymethyl, epoxy 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 cross-linking agents are naturally unstable to heat, and the storage stability of the image recording material after storage is not very good. In contrast,
A phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule, containing 3 to 5 benzene nuclei, and further having a molecular weight of 1,200 or less,
It has good stability during storage and is most preferably used in the present invention. The alkoxymethyl group has 6 carbon atoms.
The following are preferred. Specifically, a methoxymethyl group,
Preference is given to ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl and t-butoxymethyl. Further, alkoxy-substituted alkoxymethyl groups such as 2-methoxyethoxymethyl group and 2-methoxy-1-propoxymethyl group are also preferable. Specifically, Japanese Patent Application Laid-Open Nos.
-64285 and EP632003A1.

Other thermal crosslinking agents suitably used in the present invention include aldehyde and ketone compounds. Preferably, the compound has 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 70% by weight based on the total solid content of the image recording material.
Used at an addition amount of 65% by weight. 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. The generated acid is preferably a strong acid having a pKa of 2 or less, such as sulfonic acid and hydrochloric acid. 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, US 4,708,925 and JP-A-7-2062
No. 9 can be mentioned. Particularly, an iodonium salt, a sulfonium salt, and a diazonium salt having a sulfonate ion as a counter ion are preferable. Examples of the diazonium salt include diazonium compounds described in U.S. Pat. No. 3,867,147, diazonium compounds described in U.S. Pat. No. 2,632,703, and JP-A-1-10245.
No. 6 and JP-A-1-102457 are also preferable. US5, 135,
Benzyl sulfonates described in 838 and US Pat. No. 5,200,544 are also preferred. Further, Japanese Patent Laid-Open No. 2-1
00005, JP-A-2-100055 and Japanese Patent Application No. 8
Active sulfonic acid esters and disulfonyl compounds described in No. -9444 are also preferable. In addition, JP-A-7
Also preferred are haloalkyl-substituted S-triazines described in -271029. These compounds may be used alone or in combination of two or more. These compounds are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 2% by weight based on the total solid content of the image recording material.
5% by weight, more preferably 0.5 to 15% by weight, is added to the image recording material. 0.01% by weight
If it is less than, an image cannot be obtained. On the other hand, if the amount exceeds 50% by weight, non-image areas are stained during printing.

[Spectral Sensitizer] In the present invention, the above-mentioned acid generator is decomposed by light or heat to generate an acid. In the case where the acid generator is decomposed by light and irradiation with light that can be absorbed by the acid generator (for example, ultraviolet light), it is not particularly necessary to use a spectral sensitizer. However, when irradiating light that is not absorbed by the acid generator or light that is hardly absorbed,
It is necessary to add a spectral sensitizer. As the sensitizer used when irradiating visible light, a known sensitizer conventionally used for a photoradical polymerization type image recording material can be used. Specifically, for example, eosins described in JP-A-4-219756, JP-A-2-244050 and Japanese Patent Application No. 7-2313 are disclosed.
Dyes having a thiazolidinone skeleton described in No. 3 are exemplified. Although the image recording material of the present invention does not contain a radically polymerizable polyfunctional monomer,
The reason why the sensitizer effective in the photoradical polymerization type is also effective in the present invention is not clear.

The main object of the present invention is to record an image with a laser emitting infrared light. In order to efficiently perform recording with an infrared laser, it is necessary to use an infrared absorber in combination as a spectral sensitizer. The infrared absorber used in the present invention has a wavelength of 760 nm to 1200 nm.
Is a dye or pigment that effectively absorbs infrared rays, and is preferably a dye or pigment having an absorption maximum at a wavelength of 760 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, published in 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, those described in
Cyanine dyes described in JP-A-8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, etc .;
No. 96, JP-A-58-181690, JP-A-58-1
No. 94595, etc., methine dyes described in
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940 and JP-A-60-63744;
Squarylium dyes described in No. 12792, etc.,
Cyanine dyes described in British Patent 434,875 and the like can be mentioned.

Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also preferable. Pyrylium salt, JP-A-57-142645
No. (U.S. Pat. No. 4,327,169) described in JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, and JP-A-59-41363.
Nos. -84248, 59-84249, 59-14
Pyrylium compounds described in JP-A Nos. 6063 and 59-146061, cyanine dyes described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fairness 5-13
Pyrylium compounds disclosed in JP-A-514 and JP-A-5-19702 are also preferably used.

Further, as another preferred example of the dye, US Pat. No. 4,756,993 discloses a compound represented by the formula (I):
Near-infrared absorbing dyes described as (II) can be mentioned.

Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

The pigment used in the present invention includes:
Commercial Pigment and Color Index (CI) Handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
Can be used.

The pigments include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. Specifically, insoluble azo pigments, azo lake pigments, condensation azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyeing 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 being subjected to a surface treatment, or may be used after being subjected to a 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),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
When it is less than m, the dispersion is not preferable in terms of stability in the coating solution for the image recording layer, and when it exceeds 10 μm, it is not preferable in terms of uniformity of the image recording layer.

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. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

These dyes or pigments are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 50% by weight, based on the total solid content of the image recording material.
To 10% by weight, particularly preferably 0.5 to 10% in the case of a dye.
% By weight, particularly preferably 1.0 to 10% by weight in the case of a pigment.
In the image recording material. 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, the mechanism of action is as described in “sensitizers” (edited by Katsumi Tokumaru and Shin Okawara, Kodansha Co., Ltd.) and the like. And so on. 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.

[Other Components] In the present invention, various compounds other than these may be further added, if necessary.
For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BO
S, 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 (CI. 42555), methyl violet (CI. 42535), ethyl violet, rhodamine B (CI. 145170B), malachite green (CI. 42000), methylene blue (C.
I. 52015) and the dyes described in JP-A-62-293247. These dyes are preferably added because the image area and the non-image area can be easily distinguished after image formation. The amount of addition is 0.01 to 10% by weight based on the total solid content of the image recording material. Further, in the image recording material of the present invention,
Japanese Patent Application Laid-Open No.
Nonionic surfactants described in JP-A-2-251740 and JP-A-3-208514;
No. 21044 and JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonyl phenyl ether and the like. Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N, N- Betaine type (for example,
(Trade name: Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the image recording material is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer may be added to the image recording material of the present invention, if necessary, in order to impart flexibility to the coating film. For example, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, and the like are used.

In the image recording material of the present invention, a known polymer such as a novolak resin or an acrylate resin may be added in addition to the polymer having the structural unit represented by the general formula (I). A preferable addition amount is 40 in the image recording material.
% By weight or less.

In the image recording material of the present invention, each of the above components is usually dissolved in a solvent and applied on a suitable support. As the solvent used herein, 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, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyllactone, toluene, water and the like. However, the present invention is not limited to this. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight.
The amount of coating (solid content) on the support obtained after coating and drying varies depending on the application, but generally 0.5 to 5.0 g / m ² is preferred for a lithographic printing plate material.
Various methods can be used as the method of coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the image recording film deteriorate.

In the image recording material of the present invention, a surfactant for improving coating properties, for example, JP-A-62-1
No. 70950 can be added. The preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the image recording material.

[Support] The support on which the image recording material of the present invention can be applied is a dimensionally stable plate-like material such as paper or plastic (eg, polyethylene, polypropylene, polystyrene, etc.). Laminated paper,
Metal plates (eg, aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate,
Cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited.

Preferred examples of the support include a polyester film and an aluminum plate. Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in aluminum alloys include silicon, iron, manganese,
Copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The total content of foreign elements in the alloy is 10% by weight or less. Aluminum which is particularly preferred in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. 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, particularly preferably 0.2 mm to 0.3 mm. When an aluminum plate is used as the support, the surface is preferably subjected to a surface roughening treatment for the purpose of improving the adhesion of the recording layer formed on the surface. Before roughening the aluminum plate,
Optionally, for removing rolling oil on the surface, for example,
A degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like is performed.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening the surface. Is selectively dissolved. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. Further, as an electrochemical surface roughening method, there is a method of performing an alternating current or a direct current in a hydrochloric acid or nitric acid electrolyte.
Further, a method combining both of them can be used as disclosed in JP-A-54-63902.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to an anodic oxidation treatment, if necessary, in order to increase the water retention and abrasion resistance of the surface. You. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes forming a porous oxide film can be used, and generally, 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 the electrolyte.

The conditions of the anodizing treatment vary depending on the electrolyte used, and thus cannot be specified unconditionally. In general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C.
Current density 5 to 60 A / dm ^2, voltage 1 to 100 V, which is an electrolyzing time of 10 seconds to 5 minutes.

When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient, and the non-image area of the lithographic printing plate is easily damaged, and the scratched area during printing has an ink. The so-called "scratch dirt" to which is adhered easily occurs.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. U.S. Pat. No. 2,714,075 discloses a hydrophilic treatment that can be used in the present invention.
No. 66, No. 3,181,461, No. 3,280,7
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in No. 34 and 3,902,734. In this method, the support is immersed or electrolytically treated with an aqueous solution of sodium silicate. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063, U.S. Pat.
No. 6,868, No. 4,153,461, No. 4,6
For example, a method of treating with polyvinyl phosphonic acid as disclosed in JP-A-89,272 is used.

[Others] Before applying the image recording material of the present invention, an undercoat layer can be provided on the support, if necessary. As the undercoat layer component, various organic compounds are used, and examples thereof include phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid; and phenylphosphonic acid optionally having a substituent. Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid; optionally substituted phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphinic acid such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent; amino acids such as glycine and β-alanine; and hydrochloric acid of triethanolamine Amine with hydroxyl group such as salt -Alanine hydrochloride salt, it may be used by mixing two or more. It is also preferable to undercoat the aforementioned diazonium compound. The coating amount of the organic undercoat layer is suitably from ² to 200 mg / m ² .

As described above, a lithographic printing plate using the image recording material of the present invention can be prepared. This lithographic printing plate material can be recorded by radiation emitted from various light sources. For example, recording can be performed with ultraviolet light, visible light, or infrared light. These light sources may be lamps,
It may be a laser. Further, thermal recording by a thermal head is also possible. In the present invention, it is preferable that the image is exposed by an ultraviolet lamp or a solid-state laser or a semiconductor laser that emits infrared rays having a wavelength of 760 nm to 1200 nm. In the present invention, the developing treatment may be performed immediately after the exposure, or a heat treatment may be performed between the exposure step and the developing step. When performing the heat treatment, it is preferable that the heat treatment is performed within a range of 60 ° C. to 150 ° C. for 5 seconds to 5 minutes. As a heating method, various conventionally known methods can be used. For example, a method using a panel heater or a ceramic heater, a method using a lamp, and the like are included. Specifically, the method described in Japanese Patent Application No. 8-94197 is exemplified. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

When the lithographic printing plate material according to the present invention is subjected to a heat treatment in the form of an image, an acid is generated by the heat, and the acid initiates a crosslinking reaction by the crosslinking agent. Further, the heat promotes the crosslinking reaction. On the other hand, when light irradiation is performed in the form of an image, the acid generator generates an acid by the light, and the acid initiates a crosslinking reaction by the crosslinking agent. It will be further promoted. The heating here exerts a considerable accelerating effect even if the degree of heating is gentle compared to the above-mentioned heat treatment alone. Therefore, in this plate making process, it is preferable to use a combination of light irradiation and heat treatment or only heat treatment.

After performing a heat treatment as required, the image recording material of the present invention is preferably developed with water or an alkaline aqueous solution. When an alkaline aqueous solution is used, a conventionally known alkaline aqueous solution can be used as a developer and a replenisher for the image recording material of the present invention. For example,
Sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, Inorganic alkali salts such as sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Also, monomethylamine, dimethylamine,
Trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, etc. Organic alkaline agents are also used.

These alkali agents are used alone or in combination of two or more. An example of a particularly preferable developer among these alkaline agents is an aqueous solution of a silicate such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and the concentration of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O which are the components of the silicate. An alkali metal silicate described in JP-B-57-7427 is effectively used.

When developing using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is added to the developing solution to replace the developing solution in the developing tank for a long time. It is known that a large amount of lithographic printing plate material can be processed without the need. This replenishment system is also preferably applied in the present invention.

Various surfactants, organic solvents and the like can be added to the developing solution and the replenishing solution, if necessary, for the purpose of accelerating or suppressing the developing property, dispersing the developing residue and improving the ink affinity of the printing plate image area. . Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred organic solvents include benzyl alcohol and the like. It is also preferable to add polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof.

Further, the developing solution and the replenisher may contain, if necessary, an inorganic salt-based reducing agent such as hydroquinone, resorcin, sodium and potassium sulfites or bisulfites, an organic carboxylic acid, an antifoaming agent, and hard water. Softeners can also be added.

Examples of such a developer containing a surfactant, an organic solvent, a reducing agent and the like include, for example, those described in
Benzyl alcohol described in No. 77401,
A developer composition comprising an anionic surfactant, an alkali agent and water, comprising an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite as described in JP-A-53-44202; Developer composition,
Examples thereof include a developer composition containing an organic solvent, an alkali agent, and water having a solubility in water of 10% by weight or less at room temperature described in JP-A-55-155355. Used for

The printing plate developed using the developing solution and the replenisher described above is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. You. As the post-processing when the image recording material of the present invention is used as a printing plate material, these processings can be used in various combinations.

In recent years, in the plate making / printing industry, automatic developing machines for printing plate materials 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 material, each processing solution tank, and a spray device. The developing process is performed by spraying each pumped processing liquid from a spray nozzle. Recently, a method is also known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like into a processing liquid tank filled with a processing liquid to perform processing. In such automatic processing,
Processing can be performed while replenishing each processing solution with a replenisher according to the processing amount, 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 lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitized gum if desired. Is subjected to a burning process. When burning a lithographic printing plate, before burning,
No. 2518, No. 55-28062, JP-A-62-3
It is preferable to treat with a surface-regulating liquid as described in JP-A Nos. 1859 and 61-159655.

As the method, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied onto a lithographic printing plate,
A method in which a printing plate is immersed in a vat filled with a surface conditioning liquid to apply the printing plate, an application using an automatic coater, or the like is applied. Further, it is preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. The application amount of the surface conditioning liquid is generally 0.03 to 0.8 g / m ^2.
(Dry weight) is appropriate.

The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then burned (for example,
It is heated to a high temperature by a burning processor (BP-1300) sold by Fuji Photo Film Co., Ltd. The heating temperature and time in this case depend on the type of the component forming the image, but may be 1 to 180 ° C. to 300 ° C.
A range of up to 20 minutes is preferred.

The lithographic printing plate subjected to the burning treatment can be subjected to a conventional treatment such as washing with water or gumming, if necessary. When a liquid is used, a so-called desensitizing treatment such as gumming can be omitted.

The lithographic printing plate obtained by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0080]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In a flask having a capacity of 500 ml equipped with a polymer [BP-1] synthesis stirrer and a condenser, 4-acetamidobenzenesulfonyl chloride 3 was added.
7.39 g (0.16 mol) and acetonitrile 100 m
and stirred under an ice-water bath. 2, 5
A solution of 24.51 g (0.16 mol) of dimethoxyaniline and 17.81 g (0.176 mol) of triethylamine in 100 ml of acetonitrile was added dropwise little by little. After the addition, the ice water bath was removed and the mixture was stirred at room temperature for 1 hour. After completion of the stirring, the reaction solution was poured into 1.1 liter of water, and acidified with sulfuric acid. The precipitate was collected by filtration and washed with water. By drying the obtained solid under reduced pressure,
4-acetamidobenzenesulfonylamino-2,5-
52.3 g of dimethoxybenzene were obtained.

Next, a stirrer and a cooling pipe were installed.
In a flask having a capacity of 0 ml, the obtained 4-
24.53 g of acetamidobenzenesulfonylamino-2,5-dimethoxybenzene, 7.08 g of concentrated sulfuric acid, 100 ml of ethanol and 10 ml of water were added, and the mixture was heated under reflux for 1.5 hours. After completion of the heating, the reaction solution was added to an aqueous solution in which 2.8 g of sodium hydroxide was dissolved in 500 ml of water.
The precipitate was collected by filtration and washed with water. The resulting solid was dried under reduced pressure to give 4-aminobenzenesulfonylamino-2,5-dimethoxybenzene 20.93 g.
I got

Next, 30 units equipped with a stirrer and a cooling pipe were installed.
In a flask having a capacity of 0 ml, the obtained 4-
Aminobenzenesulfonylamino-2,5-dimethoxybenzene (20.93 g), sodium acetate (6.68 g) and acetone (100 ml) were added, and the mixture was stirred in an ice water bath. To this mixture, 7.1 g of methacrylic chloride was added dropwise little by little. After the addition, the ice water bath was removed and the mixture was stirred at room temperature for 1 hour. After completion of the stirring, the reaction solution was poured into 500 ml of water. The precipitate was collected by filtration and washed with water. The obtained solid was dried under reduced pressure to obtain 22.40 g of 4-methacryloylaminobenzenesulfonylamino-2,5-dimethoxybenzene.

Further, a device equipped with a stirrer and a cooling pipe was used.
8.69 g of N, N-dimethylacetamide was placed in a flask having a capacity of 00 ml, and heated to 75 ° C. under a nitrogen stream.
While stirring the inside of the flask, 13.18 g of 4-methacryloylaminobenzenesulfonylamino-2,5-dimethoxybenzene and 1.71 of ethyl methacrylate were obtained.
g, V-601 (azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.)
0.0576 g, and N, N-dimethylacetamide 2
6.05 g of the mixture was added dropwise over 2.5 hours. After dropping, 0.0576 g of V-601 was added again, and the mixture was stirred at 75 ° C for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, 50 ml of methanol was added, and the mixture was poured into 1 liter of water with stirring. The precipitate was collected by filtration and dried under reduced pressure to obtain 14.6 g of the polymer [BP-1] of the present invention.
When the weight average molecular weight was measured by GPC,
It was 40,000 (polystyrene standard).

Synthesis of Polymer [BP-2] Sodium p-styrenesulfonate was converted to the corresponding sulfonic acid chloride using thionyl chloride, and then converted to 3,5-
By reacting with dimethoxyaniline, 3,5-dimethoxy (p-styrylsulfonyl) aniline was synthesized. Further, copolymerization with styrene was performed to obtain a polymer [BP-2] used in the present invention. The weight-average molecular weight was determined by GPC.
Was 111,000 (polystyrene standard).

Synthesis of Polymer [BP-3] p-Dimethoxybenzene was reacted with chlorosulfonic acid to obtain 2,5-dimethoxybenzenesulfonic acid. This was converted into a sodium salt, and then reacted with thionyl chloride to give the corresponding sulfonic acid chloride, and then reacted with 4-aminophenol to obtain 4- (2,5-dimethoxyphenylsulfonylamino) phenol. Next, it is reacted with methacrylic acid chloride in the presence of sodium acetate,
(2,5-Dimethoxyphenylsulfonylamino) phenyl methacrylate was synthesized. Further, copolymerization with butyl acrylate and methacrylic acid was performed to obtain a polymer [BP-3] used in the present invention. The weight average molecular weight measured by GPC was 87,000 (polystyrene standard).

Synthesis of Polymer [BP-4] p-Dimethoxybenzene was reacted with chlorosulfonic acid to obtain 2,5-dimethoxybenzenesulfonic acid. This was converted to a sodium salt, and then reacted with thionyl chloride to form the corresponding sulfonic acid chloride, and then reacted with aqueous ammonia to obtain 2,5-dimethoxybenzenesulfonamide. Next, N- (2,5-dimethoxyphenylsulfonyl) methacrylamide was synthesized by reacting with methacrylic chloride in the presence of a base. Further, copolymerization with benzyl methacrylate was performed to obtain a polymer [BP-4] used in the present invention. The weight-average molecular weight was determined by GPC.
Was 109,000 (polystyrene standard).

Synthesis of Polymer [BP-5] 2-Aminothiophenol was monomethylated with methyl tosylate and then reacted with 4-acetamidobenzenesulfonyl chloride to obtain 4- (2-methylthiophenylaminosulfonyl) acetanilide. . next,
Solvolysis with sulfuric acid in aqueous ethanol, 4- (2-
Methylthiophenylaminosulfonyl) aniline,
Reaction with methacrylic chloride in the presence of a base,
[4- (2-Methylthiophenyl) aminosulfonylphenyl] methacrylamide was synthesized. Also, 2,6-
N- [4- (2,6-dimethoxyphenyl) carbonylaminosulfonylphenyl] methacrylamide was synthesized from dimethoxybenzoic acid and N- (4-aminosulfonylphenyl) methacrylamide. Copolymerization of the two synthesized monomers and methyl methacrylate was performed to obtain a polymer [BP-5] used in the present invention. The weight average molecular weight measured by GPC was 109,000 (polystyrene standard).

Synthesis of Polymer [BP-6] After converting 2,6-dimethoxybenzoic acid into acid chloride, it was reacted with aqueous ammonia to obtain 2,6-dimethoxybenzoic acid amide. This was obtained from p-styrenecarboxylic acid
-Reaction with styrene carboxylic acid chloride in the presence of a strong base to give N- (2,6-dimethoxyphenylcarbonyl)-
p-Styrene carboxylic acid amide was synthesized. Also, N,
N-dimethylamino-o-aniline was reacted with m-nitrobenzenesulfonyl chloride to obtain 3- (2-dimethylaminophenyl) aminosulfonylaniline.
After reducing this, it is reacted with methacrylic acid chloride in the presence of a base to give N- [3- (2-dimethylaminophenyl).
[Aminosulfonylphenyl] methacrylamide was synthesized. The polymer [BP-6] used in the present invention is obtained by copolymerizing two synthesized monomers with methyl acrylate.
I got The weight average molecular weight measured by GPC was 96,000 (standard polystyrene).

[0089]

[Table 1]

[0090]

[Table 2]

Example 1 0.30 mm thick aluminum
Plate (material 1050) washed with trichloroethylene
After degreased, nylon brush and 400 mesh pumice
Ton-grain the surface with a water suspension and wash well with water.
Washed. This plate was washed at 25 ° C with 25% aqueous sodium hydroxide.
After immersion in the solution for 9 seconds, etching and washing with water,
2% HNO _ThreeFor 20 seconds and washed with water. Sand at this time
The amount of etching on the dressing surface is about 3 g / m^TwoMet. Next
7% H_TwoSO_FourCurrent density 15
A / dm^Two3g / m^TwoDC anodized film
Then, it was washed with water and dried. Next, apply the following primer to this aluminum plate
The solution was applied and dried at 80 ° C. for 30 seconds. After drying
Covering amount is 10mg / m^TwoMet.Undercoat liquid β-alanine 0.1 g Phenylphosphonic acid 0.05 g Methanol 40 g Pure water 60 g

Next, the following solution [P] was prepared, and this solution was applied to the above-mentioned primed aluminum plate.
Dried at 0 ° C for 1 minute to form a negative type lithographic printing plate [P-1]
I got The weight after drying was 1.5 g / m ² .

Solution [P] Polymer [BP-1] 1.6 g Thermal crosslinking agent [N-1] 0.4 g Acid generator [S-1] 0.15 g Infrared absorber [K-1] 0.10 g Mega FAK-177 0.06 g (Dainippon Ink and Chemicals, Inc., fluorine-based surfactant) Methyl ethyl ketone 15 g 1-methoxy-2-propanol 5 g Methyl alcohol 7 g

The thermal crosslinking agent [N-1] and the acid generator [S
-1] and the structure of the infrared absorbent [K-1] are shown below.

[0095]

Embedded image

[0096]

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[0097]

Embedded image

The obtained negative type lithographic printing plate material [P-1]
Was exposed to ultraviolet light. After the exposure, a heat treatment was performed at 90 ° C. for 20 seconds using a panel heater, and then a developer, DP-4 (1: 8), and a rinse liquid FR, manufactured by Fuji Photo Film Co., Ltd.
-3 (1: 7) through an automatic processor. Next, Gum GU-7 manufactured by Fuji Photo Film Co., Ltd.
The plate was processed at (1: 1) and printed with a Heidel KOR-D machine. At this time, when the number of obtained good printed matter was observed, 52,000 good printed matter was continuously obtained,
During that time, no problematic prints were observed. No stain was observed on the non-image portions of these printed materials.

Example 2 The negative type lithographic printing plate [P-1] obtained in Example 1 was exposed to a semiconductor laser emitting infrared light having a wavelength of about 830 to 850 nm. After exposure,
After a heat treatment at 90 ° C. for 20 seconds with a panel heater, a developer, DP-4 (1: 1) manufactured by Fuji Photo Film Co., Ltd.
8) Processing was carried out through an automatic developing machine charged with a rinsing liquid FR-3 (1: 7). Then, the plate was treated with gum GU-7 (1: 1) manufactured by Fuji Photo Film Co., Ltd.
Printing was performed with an RD machine. Observation of the number of good prints obtained at this time revealed that 50000 good prints were obtained. No stain was observed in the non-image area.

(Examples 3 to 8) Solutions used in Example 1
In [P], by changing the type of the polymer of the present invention, 6
Various types of solutions [P-2] to [P-7] were prepared. This solution
Each of the solutions was coated with the primed aluminum alloy used in Example 1.
Negative plate.
Printing plate materials [P-2] to [P-7] were obtained. Weight after drying
1.5g / m ^TwoMet. Solutions [P-2] to [P-
Table 7 shows the polymers used in [7].

[0101]

[Table 3]

The obtained negative type lithographic printing plate material [P-2]
To [P-7] were exposed with a semiconductor laser emitting infrared light having a wavelength of about 830 to 850 nm. After the exposure, a heat treatment was performed at 90 ° C. for 20 seconds with a panel heater, and then a developer, DP-4 (1: 8) and a rinsing solution FR-3 (1: 7) manufactured by Fuji Photo Film Co., Ltd. were charged. Processed through an automatic processor. Next, Gum GU-7 manufactured by Fuji Photo Film Co., Ltd.
The plate was processed at (1: 1) and printed with a Heidel KOR-D machine. Table 3 shows the results. In each case, 50,000 or more printed matters were obtained. In all of the prints, no stain was observed in the non-image area.

(Comparative Example 1) Solution [P] used in Example 1
, A solution [Q-1] was prepared using a polymer having the following structure instead of the polymer [BP-1]. This solution was applied to the undercoated aluminum plate used in Example 1 and dried at 100 ° C. for 1 minute to obtain a negative type lithographic printing plate [Q-1]. Weight after drying is 1.5
g / m ² . Obtained lithographic printing plate material [Q-1]
Was image-formed and printed in the same manner as in Example 2. Observation of the number of good prints obtained at this time revealed that only 28,000 prints were obtained. No stain was observed in the non-image area. The polymer used corresponds to the polymer [BP-1] of the present invention without the methoxy substituent (Y ₁ -R ₂ ).

[0104]

Embedded image

From Examples 2 to 8 and Comparative Example 1, it can be seen that the lithographic printing plate material using the negative type image recording material of the present invention has excellent printing durability during printing.

(Examples 9 to 11) A 0.30 mm thick
Luminium plate (material 1050) washed with trichlorethylene
After cleaning and degreasing, use a nylon brush and 400 mesh
Pumiceton-use a water suspension to grain the surface,
It was washed with water. This plate is heated at 45 ° C in 25% sodium hydroxide
Immersed in aqueous solution for 9 seconds, etched and washed with water,
2% HNO _ThreeFor 20 seconds and washed with water. this
The amount of etching of the grained surface at the time is about 3 g / m^TwoSo
Was. Next, this plate was subjected to current density using 7% H2 SO4 as an electrolyte.
Degree 15A / dm^Two3g / m^TwoDC anodized film
I did. Then, 1% aqueous solution of 2.5% sodium silicate at 70 ° C
After immersion for a minute, it was washed and dried. Next on this aluminum plate
The following undercoat liquid was applied and dried at 80 ° C. for 30 seconds. Dry
20mg / m coating amount after drying ^TwoMet.Undercoat liquid Dibutylnaphthalene sulfonate of 4-diazodiphenylamine, phenoxyacetic acid and formaldehyde condensate 0.1 g Methanol 100 g

Next, in the following solution [R], three kinds of solutions [R-1] to [R-3] were prepared by changing the types of the polymer and the thermal crosslinking agent of the present invention. Each of the solutions was applied to the above-mentioned aluminum plate, dried at 100 ° C. for 1 minute, and used for negative planographic printing plates [R-1] to [R-3].
I got The weight after drying was 1.6 g / m ² .

Solution [R] polymer 1.6 g Thermal cross-linking agent 0.4 g Acid generator [S-2] 0.15 g Infrared absorbing agent (trade name: NK-3508, 0.10 g Japan Photographic Pigment Research Institute Co., Ltd.) Dye in which the counter ion of Victoria Pure Blue BOH is converted to 1-naphthalene-sulfonic acid 0.05 g Fluorinated surfactant (trade name: Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.06 g Methyl ethyl ketone 15 g 1-Methoxy-2-propanol 5 g Methyl alcohol 7 g The compounds used in the solutions [R-1] to [R-3] are shown in Table 4.

[0109]

[Table 4]

The obtained negative type lithographic printing plate material [R-1]
[R-3] was exposed to a solid-state laser YAG laser that emits infrared rays having a wavelength of about 1064 nm. After exposure, heat treatment was performed in an oven at 100 ° C. for 15 seconds, and then automatic development was performed using a developer, DP-4 (1: 8) and a rinse solution FR-3 (1: 7) manufactured by Fuji Photo Film Co., Ltd. Processed through machine. Next, Gum GU-7 manufactured by Fuji Photo Film Co., Ltd.
The plate was processed at (1: 1) and printed with a Heidel KOR-D machine. At this time, the number of good prints obtained was observed. Table 4 shows the results. In each case, 50,000 or more printed matters were obtained. In all of the prints, no stain was observed in the non-image area.

[0111]

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[0112]

Embedded image

[0113]

Embedded image

(Comparative Example 2) In the solution [R-1] used in Example 9, a novolak resin obtained by reacting m-cresol and formaldehyde under acidic conditions instead of the polymer [BP-1] (Weight average molecular weight 2
500), and in the same manner as in Example 9, a negative type lithographic printing plate material [S-1] was prepared. The resulting lithographic printing plate material [S-1] was formed and printed in the same manner as in Example 9. Observation of the number of good prints obtained at this time revealed that only 21,000 prints were obtained. Further, a slight stain was observed in the non-image area.

According to Examples 9 to 11 and Comparative Example 2, the lithographic printing plate material using the negative type image recording material of the present invention was excellent in printing durability at the time of printing and reduced in stain on the non-image area. It turns out that it is also excellent.

[0116]

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-type image recording material which is excellent in printing durability at the time of printing and hardly stains a non-image portion.

Claims (1)

[Claims] (A) a polymer having a structural unit represented by the following general formula (I), (B) a compound capable of being crosslinked by an acid, and (C) a compound capable of generating an acid by light or heat. A negative type image recording material characterized by the above-mentioned. General formula (1) 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 a single bond, an ester bond, a carboxylic acid amide bond,
A sulfonic acid amide bond, an ether bond, a thioether bond or a carbon number of 20 which may contain these bonds
The following hydrocarbon groups are shown. 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. [0001]