JP2001033952A - Image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an image recording material in which images can be recorded by using an IR-emitting solid laser or an IR-emitting semiconductor laser and which is excellent in development latitude. SOLUTION: The image recording material 10 has, on the substrate 12, a layer 14 containing a high molecular compound insoluble in water and soluble in alkaline water and becomes more soluble to alkaline water when light or heat is applied and a layer 16 containing a photodegradable compound or a thermally decomposable compound on the layer 14. The image recording material is excellent in development latitude even when a heat-mode image recording method using an IR layer or the like is applied.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material which can be used as a lithographic printing plate precursor. In particular, it can record images in a heat mode and can directly make a plate from a digital signal of a computer or the like by using an infrared laser. The present invention relates to an image recording material which can be used as a so-called direct plate-making lithographic printing plate precursor.

[0002]

2. Description of the Related Art In recent years, with the development of solid-state lasers and semiconductor lasers having a light emitting region from near infrared to infrared, a system for directly making a plate from digital data of a computer using an infrared laser or the like has attracted attention. Examples of the lithographic printing plate material used in the system include, for example,
There is a positive type image recording material disclosed in JP-A-285275. This positive-type image recording material is a material in which a substance that absorbs light and generates heat and a dissolution inhibitor that reduces the solubility of the resin in alkaline water are added to an alkaline water-soluble resin. The dissolution inhibitor has a function of substantially reducing the solubility of the resin soluble in an aqueous alkali solution in a developing solution (alkaline aqueous solution), but loses the above function when decomposed by heat. When laser recording is performed imagewise on a lithographic printing plate precursor prepared by applying this material on a support, the function of the dissolution inhibitor is lost in the laser irradiation section, so that in the development process, It is removed, and an image portion and a non-image portion are formed. As the dissolution inhibitor, quinonediazide compounds, onium salts, compounds which are insoluble in alkaline water and capable of hydrogen bonding, and the like are known.

[0003] WO 97/39894 discloses that an image recording material using a cationic infrared absorbing dye as a dissolution inhibitor for an alkali-water-soluble resin exhibits a positive effect. The positive effect is that the infrared absorbing dye absorbs the laser light, and the heat generated by the dye absorbs the effect of suppressing the dissolution of the polymer film only in the laser-irradiated part, so that the solubility in the developing solution is reduced by the laser-irradiated part and the non-laser-irradiated part. This is an operation of forming an image portion and a non-image portion.

[0004]

However, in the above-mentioned conventional image recording materials, the solubility in a developing solution is made different by utilizing only the interaction between the materials contained in the same layer. In this case, a difference in solubility between the image area and the non-image area is hard to be obtained, that is, the discrimination between the image area and the non-image area is not sufficient, and as a result, the developing latitude is narrow. Here, the development latitude indicates an allowable range in which a good image can be formed when the alkali concentration of the alkali developer is changed.

It is an object of the present invention to provide an image recording material which can record an image using a solid-state laser or a semiconductor laser emitting infrared rays and has an excellent development latitude.

[0006]

Means for Solving the Problems To solve the above problems, the image recording material of the present invention comprises, on a support, a polymer compound insoluble in water and soluble in alkaline water,
A structure in which a first layer whose solubility in alkaline water is increased by donation of light or heat and a second layer containing a photodecomposable compound or a heat decomposable compound is provided on the first layer. .

The second layer contains a thermally decomposable compound,
The decomposition temperature of the thermally decomposable compound is preferably 50 ° C. or more and 350 ° C. or less.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an embodiment in which the image recording material of the present invention is applied to a lithographic printing plate precursor. The lithographic printing plate precursor 10 is provided with a layer 14 containing a polymer compound insoluble in water and soluble in alkaline water, and an infrared absorber, on a support 12 made of aluminum or the like. The infrared absorbing agent has a function of interacting with the polymer compound and suppressing dissolution of the polymer compound in alkaline water, and also has a property of generating heat by absorbing infrared rays and losing the function. Have. Further, a layer 16 containing a thermally decomposable compound is provided on the layer 14.

An example of a method for producing a lithographic printing plate by making a lithographic printing plate precursor 10 will be described below. When the lithographic printing plate precursor 10 is imagewise irradiated with laser from the layer 16 side by an infrared laser or the like, the infrared absorbent contained in the layer 14 of the laser irradiation part absorbs infrared rays to generate heat, and the laser irradiation part Loses the dissolution inhibiting function of the infrared absorbent. As a result, the laser irradiation portion of the layer 14 has higher solubility in alkaline water than the non-laser irradiation portion.
On the other hand, in the layer 16 as well, the heat generated by the infrared absorber in the layer 14 decomposes the thermally decomposable compound in the laser-irradiated portion of the layer 16, and as a result, the permeability of the alkaline water to the laser-irradiated portion increases. Thereafter, the lithographic printing plate precursor 10 is developed with an alkaline developer to dissolve the laser-irradiated portion in the developing solution to form a positive image and obtain a lithographic printing plate.

The lithographic printing plate precursor 10 image-irradiated with a laser has a layer 14 whose laser-irradiated portion has a higher solubility in alkaline water than a non-laser-irradiated portion, as well as having a higher solubility on the layer 14. Since the layer 16 is provided in the non-laser-irradiated portion, the developer can be prevented from penetrating into the layer 14, and the layer 14 can be further prevented from being dissolved in the developer.
On the other hand, in the laser irradiation part, the thermally decomposable compound in the layer 16 is decomposed, and the alkaline water is easily permeated. As a result, the developer can penetrate more into the layer 14 and the layer 14 Dissolution in the developer can be further promoted. Therefore, the lithographic printing plate precursor 10 is excellent in development latitude even when heat mode image recording is performed using an infrared laser or the like.

The components contained in the first and second layers constituting the image recording material of the present invention will be described below. [First Layer] The first layer contains at least a polymer compound that is insoluble in water and soluble in alkaline water.

The polymer which is insoluble in water and soluble in alkaline water (hereinafter referred to as "alkali water-soluble polymer") has an acidic group in the main chain and / or side chain in the polymer. Homopolymers, copolymers of these, or mixtures thereof. In this specification,
“Alkaline water” refers to an alkaline aqueous solution, which refers to an aqueous solution having a pH similar to that of an alkaline developer generally used for developing a lithographic printing plate.

Among them, those having acidic groups listed in the following (1) to (6) in the main chain and / or side chain of the polymer are preferred in terms of solubility in an alkaline developer and development of dissolution inhibiting ability. preferable. (1) phenol group: -Ar-OH (2) a sulfonamide _{group: -SO 2 NH-R (3} ) substituted sulfonamide-based acid group (hereinafter, referred to as "active imide group".): -SO ₂ NHCOR, - SO ₂ NH
SO ₂ R, —CONHSO ₂ R (4) Carboxylic acid group: —CO ₂ H (5) Sulfonic acid group: —SO ₃ H (6) Phosphate group: —OPO ₃ H ₂

In the above (1) to (6), Ar represents a divalent aryl linking group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.

Among the alkaline water-soluble polymers having an acidic group selected from the above (1) to (6), alkaline water-soluble polymers having (1) a phenol group, (2) a sulfonamide group and (3) an active imide group. A polymer is preferable, and an alkali water-soluble polymer having (1) a phenol group or (2) a sulfonamide group is most preferable in terms of sufficiently securing solubility in an alkaline developer, development latitude, and film strength.

(1) Examples of the alkali water-soluble polymer having a phenol group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde, and a condensation polymer of p-cresol and formaldehyde. , M- / p-condensed polymer of cresol and formaldehyde, phenol and cresol (m-, p-
Or a m- / p-mixture) and a novolak resin such as a condensation polymer of formaldehyde, and a condensation polymer of pyrogallol and acetone. Further, a copolymer obtained by copolymerizing a compound having a phenol group in a side chain can also be used. Alternatively, a copolymer obtained by copolymerizing a compound having a phenol group in the side chain can be used. Examples of the compound having a phenol group include acrylamide, methacrylamide, acrylate, methacrylate, and hydroxystyrene having a phenol group.

Specifically, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl)
Acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate , M-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (2 -Hydroxyphenyl) ethyl acrylate, 2- (3-hydroxyphenyl) ethyl acrylate, 2- (4-hydroxyphenyl) ethyl acrylate, 2- (2-hydro Shifeniru) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate, 2- (4-hydroxyphenyl) ethyl methacrylate.

The weight average molecular weight of the alkali water-soluble polymer having a phenol group is from 5.0 × 10 ^{2 to} 2.0 × 1.
0 ^4, a number average molecular weight of 2.0 × 10 ² ~1.0 × 10 ⁴
Are preferred from the viewpoint of image forming properties. These polymers may be used alone or in combination of two or more. When combined, as described in U.S. Pat. No. 4,123,279,
Polycondensates of t-butylphenol and formaldehyde, and polycondensates of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as substituents, such as polycondensates of octylphenol and formaldehyde, may be used in combination. Good.

(2) Examples of the alkali water-soluble polymer having a sulfonamide group include a polymer having, as a main constituent, a minimum structural unit derived from a compound having a sulfonamide group. Examples of the compound as described above include a compound having at least one sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and one or more polymerizable unsaturated groups in the molecule. Among them, an acryloyl group, an allyl group, or a vinyloxy group, and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group, and a low-molecular compound having in the molecule are preferable, for example, represented by the following general formulas 1 to 5 Compounds.

[0020]

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In the above formulas, X in the general formulas 1 to 5¹, X^TwoIs
Each independently represents -O- or -NR ²⁷Represents-. R^{twenty one},
R^{twenty four}Is independently a hydrogen atom or -CH_ThreeThe table
You. R^{Two Two}, R^{twenty five}, R²⁹, R³²And R³⁶Are independent
Having 1 to 12 carbon atoms which may have a substituent
Groups, cycloalkylene groups, arylene groups or arals
Represents a kylene group. R^{twenty three}, R²⁷And R³³Are independent
Has 1 to 12 carbon atoms which may have a hydrogen atom or a substituent
An alkyl group, a cycloalkyl group, an aryl group or
Represents an aralkyl group. Also, R²⁶, R³⁷Are independent
Having 1 to 12 carbon atoms which may have a substituent
Group, cycloalkyl group, aryl group, and aralkyl group
You. R²⁸, R³⁰And R³⁴Are each independently a hydrogen atom or
-CH_ThreeRepresents R³¹, R³⁵Are independently connected
Or a group having 1 to 12 carbon atoms which may have a substituent.
Alkylene group, cycloalkylene group, arylene group or
Represents an aralkylene group. Y^Three, Y^FourAre independent of each other
Represents a single bond or -CO-.

As the alkaline water-soluble polymer, among the compounds represented by the general formulas 1 to 5, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p- (Aminosulfonylphenyl) acrylamide and the like are preferred.

(3) Examples of the alkali water-soluble polymer having an active imide group include a polymer having, as a main constituent, a minimum structural unit derived from a compound having an active imide group. Examples of such compounds include compounds having at least one active imide group represented by the following structural formula and one or more polymerizable unsaturated groups in the molecule.

[0024]

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Specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be suitably used.

(4) The alkaline water-soluble polymer having a carboxylic acid group includes, for example, a minimum structural unit derived from a compound having one or more carboxylic acid groups and one or more polymerizable unsaturated groups in the molecule. Examples of the polymer may be a main component. (5) As the alkaline water-soluble polymer having a sulfonic acid group, for example, the main structural unit is a minimum structural unit derived from a compound having one or more sulfonic acid groups and one or more polymerizable unsaturated groups in the molecule. The following polymer can be mentioned. (6) The alkaline water-soluble polymer having a phosphate group includes, for example, a minimum constituent unit derived from a compound having at least one phosphate group and at least one polymerizable unsaturated group in the molecule as a main constituent component. The following polymer can be mentioned.

Among the alkaline water-soluble polymers,
(1) Alkaline water-soluble polymers having a phenolic hydroxyl group are preferred.

The alkaline water-soluble polymer has two or more kinds of the minimum structural units having the same acidic group selected from the acidic groups (1) to (6) or two or more kinds of the minimum structural units having different acidic groups. It may be a polymer obtained by copolymerizing more than one kind. As a method of copolymerization, a graft copolymerization method,
A block copolymerization method, a random copolymerization method, or the like can be used.

The copolymer is copolymerized (1) to
It is preferred that the compound having an acidic group selected from (6) is contained in the copolymer in an amount of at least 10 mol%, more preferably at least 20 mol%. 10 mol%
If it is less than 3, the developing latitude tends to be insufficiently improved. In the present invention, when a compound is copolymerized to form a copolymer, other compounds that do not contain an acidic group described in (1) to (6) above can be used as the compound. Examples of the other compounds (1) to (6) that do not contain an acidic group include the compounds listed in the following (m1) to (m12).

(M1) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (M2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
Alkyl acrylates such as hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate and N-dimethylaminoethyl acrylate; (M3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2-
Alkyl methacrylates such as chloroethyl, glycidyl methacrylate and N-dimethylaminoethyl methacrylate;

(M4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N Acrylamide or methacrylamide such as -ethyl-N-phenylacrylamide. (M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether. (M6) vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate.

(M7) styrene, α-methylstyrene,
Styrenes such as methylstyrene and chloromethylstyrene. (M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene.

(M10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide. (M12) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.

The alkali water-soluble polymer has a weight average molecular weight of 1.0 × 10 ^{3 to} 2.0 × 10 ⁵ and a number average molecular weight of 5.0 × 10 ^{2 to} 1.0 × 10 ⁵ . Are preferred in terms of sensitivity and development latitude, and the polydispersity (weight average molecular weight / number average molecular weight) is 1.1 to 10
Are preferred.

When a copolymer is used as the alkali water-soluble polymer, the main chain and / or the side chain constituting the copolymer are
Including the minimum structural unit derived from the compound having an acidic group selected from the above (1) to (6) and the acidic group of (1) to (6) constituting a part of the main chain and / or the side chain From the viewpoint of development latitude, the blending weight ratio with the other minimum structural unit is preferably from 50:50 to 5:95, and more preferably from 40:60 to 10:90.

The above-mentioned alkali water-soluble polymer may be used alone or in combination of two or more, and may be used in the total solid content of the material constituting the first layer. To 99% by weight, preferably 40 to 9% by weight.
The content is more preferably 5% by weight, and particularly preferably 50 to 90% by weight. When the amount of the alkali water-soluble polymer is less than 30% by weight, the durability of the first layer tends to deteriorate, and when it exceeds 99% by weight, the sensitivity and durability are poor. Tends to decrease.

Examples of the solvent that can be used in the synthesis of the alkaline water-soluble polymer used in the present invention include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, and ethylene glycol. 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,
Examples include ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents can be used alone or in combination of two or more.

The first layer is a layer whose solubility in alkaline water is increased by donating light or heat. In order to impart such a function to the first layer, for example, it is preferable that the first layer contains an infrared absorbent in addition to the alkali water-soluble polymer. Among the infrared absorbers, it has an onium salt type structure in that it has a function of suppressing the dissolution of the alkaline water-soluble polymer in alkaline water, and has a property of releasing or eliminating only the function irradiated with laser. Infrared absorbers are preferred. Specifically, dyes such as cyanine dyes and pyrylium salts are preferred.

Preferred dyes include, for example, JP-A-58-125246, JP-A-59-84356,
JP-A-59-202829, JP-A-60-78787
Cyanine dyes described in Japanese Patent Publication No.
And the cyanine dyes described in U.S. Pat.

Further, the near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and further, the substituted sensitizer described in US Pat. No. 3,881,924 is used. Arylbenzo (thio) pyrylium salts described in JP-A-57-142645 (U.S. Pat. No. 4,327,169).
No. 5) Trimethine thiapyrylium salts described in JP-A-58-181051, JP-A-58-220143, and JP-A-58-220143.
Nos. 9-41363, 59-84248 and 59-8
No. 4249, No. 59-146063, No. 59-146
No. 061, JP-A-5961
Cyanine dyes described in JP-A-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and Japanese Patent Publication Nos.
Pyrylium compounds described in 19702 are also preferably used.

Also preferred are near-infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and phthalocyanine dyes described in EP 916513 A2. It can be mentioned as.

Further, the anionic infrared absorber described in Japanese Patent Application No. 10-79912 can also be suitably used. The anionic infrared absorbing agent refers to a dye that substantially has no anionic structure in the mother nucleus of a dye that absorbs infrared light and has an anionic structure. For example, (c1) an anionic metal complex, (c2) anionic carbon black,
(C3) Anionic phthalocyanine, and (c4) a compound represented by the following general formula 6 and the like. The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

[0043]

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Here, the (c1) anionic metal complex refers to an anion in which the central metal and the entire ligand of the complex part which substantially absorbs light become anions.

(C2) The anionic carbon black is
Examples of the substituent include carbon black to which an anionic group such as a sulfonic acid, a carboxylic acid, and a phosphonic acid group is bonded. To introduce these groups into carbon black,
Carbon Black Handbook Third Edition (edited by The Carbon Black Association, April 5, 1995)
As described on page 12, means such as oxidation of carbon black with a predetermined acid may be employed.

(C3) Anionic phthalocyanine refers to an anionic phthalocyanine in which the anion group described in the description of (c2) above is bonded as a substituent to the phthalocyanine skeleton, and the anion as a whole is an anion.

Next, the compound (c4) represented by the general formula 6 will be described in detail. Wherein in formula 6, G _a ^-
Represents an anionic substituent, G _b represents a neutral substituent. X ^{m +} represents a cation having 1 to m valence including a proton, and m represents an integer of 1 to 6. M represents a conjugated chain,
This conjugated chain M may have a substituent or a ring structure. The conjugated chain M can be represented by the following formula.

[0048]

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In the above formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group,
It represents an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group, and these may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

Of the anionic infrared absorbers represented by the above formula 6, those having the following A-1 to A-5 are preferably used.

[0051]

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Further, cationic infrared absorbers represented by the following CA-1 to CA-44 can also be preferably used.

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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In the above structural formula, T ⁻ represents a monovalent counter anion, and is preferably a halogen anion (F ⁻ , Cl ⁻ ,
Br ^-, I ^-), a Lewis acid anion _{^{(BF 4 -, PF 6 -}} , S
bCl ₆ ⁻ , ClO ₄ ⁻ ), an alkylsulfonic acid anion,
Aryl sulfonate anion.

The alkyl of the alkyl sulfonic acid is
A linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl,
Isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, and 2-norbornyl groups be able to. Among these, straight-chains having 1 to 12 carbon atoms, 3 to 12 carbon atoms.
And a cyclic alkyl group having 5 to 10 carbon atoms is more preferred.

The aryl of the arylsulfonic acid may be one having one benzene ring, one having two or three benzene rings forming a condensed ring, and one having a benzene ring and a 5-membered unsaturated ring forming a condensed ring. Represents a formed one, and specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group, and among these, a phenyl group and a naphthyl group are more preferable. .

Further, nonionic infrared absorbers represented by the following NA-1 to NA-12 can also be preferably used.

[0072]

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[0073]

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[0074]

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[0075]

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Among the above-mentioned exemplified compounds, A-1 is particularly preferred as the anionic infrared absorber, CA-7, CA-30, CA-40 and CA-42 are preferred as the cationic infrared absorber. NA as infrared absorber
-11.

The infrared absorbing agent is preferably used in an amount of 0.01 to 50% by weight, more preferably 0.1 to 10% by weight, based on the total solid content of the material constituting the first layer. , 0.5 to 10% by weight. If the amount of the dye is less than 0.01% by weight, the sensitivity becomes low, and if it exceeds 50% by weight, the non-image area is stained during printing.

The first layer may further contain other dyes, pigments and the like for the purpose of further improving sensitivity and development latitude. Other dyes include commercially available dyes and, for example, "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, Showa 4)
A publicly known document described in a document such as "Five Years" 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, diimmonium dyes, aminium dyes, squalilium dyes, metal thiolate complexes and the like Is mentioned.

As other pigments, commercially available pigments and color index (CI) handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing Co., Ltd.) Pigment described in "Printing Ink Technology", published by CMC, 1984). For example, the types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, 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, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. 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 surface treatment method is described in "Properties and Applications of Metallic Soaps" (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 from 0.01 μm to 10 μm, more preferably from 0.05 μm to 1 μm, particularly preferably from 0.1 μm to 1 μm. When 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 when 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. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

The amount of the dye or pigment is preferably from 0.01 to 50% by weight, and more preferably from 0.1 to 10% by weight, based on the total solids of the material constituting the first layer. More preferred. In the case of dyes, the content is particularly preferably 0.5 to 10% by weight, and in the case of pigments, particularly preferably 1.0 to 10% by weight. The amount of the pigment or dye added is 0.0
If the amount is less than 1% by weight, the effect of improving sensitivity is not sufficient.

These dyes or pigments may be added to the same layer as other components, or may be added to a separate layer provided. Among the above dyes or pigments, those that absorb infrared light or near infrared light are particularly preferable.
Further, two or more dyes and pigments may be used in combination.

Various other additives can be added to the first layer. For example, other onium salts,
It is preferable to add an aromatic sulfone compound, an aromatic sulfonate compound, a polyfunctional amine compound, or the like, because the function of inhibiting the dissolution of the alkali water-soluble polymer in the developer can be improved.

Examples of the onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like. Suitable onium salts for use in the present invention include, for example, S.I. I.
Schlesinger, Photogr. Sci. E
ng. , 18, 387 (1974); S. Bal
et al, Polymer, 21, 423 (198
0) or diazonium salts described in JP-A-5-158230, U.S. Pat. Nos. 4,069,055 and 4,069,056, or JP-A-3-140140.
Ammonium salts described in JP-A No. C. Necker
et al, Macromolecules, 17,
2468 (1984), C.I. S. Wen et al,
Teh, Proc. Conf. Rad. Curing
ASIA, p478 Tokyo, Oct (1988),
US Patent No. 4,069,055 or 4,06
The phosphonium salt described in No. 9,056,

J. V. Crivello et al,
Macromolecules, 10 (6), 1307
(1977), Chem. & Eng. News, No
v. 28, p31 (1988), EP 104,1
No. 43, U.S. Pat. Nos. 339,049 and 410,2
No. 01, JP-A-2-150848 or JP-A-2-296514;
V. Crivello et al, Polymer
J. 17, 73 (1985); V. Crivell
o et al. J. Org. Chem. , 43,30
55 (1978); R. Watt et al,
J. Polymer Sci. , Polymer Ch
em. Ed. , 22, 1789 (1984); V.
Crivello et al, Polymer Bu
ll. , 14, 279 (1985); V. Criv
ello et al, Macromorecule
s, 14 (5), 1141 (1981); V. Cr
ivello et al, J. Mol. Polymer Sc
i. , Polymer Chem. Ed. , 17,287
7 (1979), European Patent Nos. 370,693 and 23
No. 3,567, No. 297,443, No. 297,442
No. 4,933,377 and 3,902,
No. 114, No. 410, 201, No. 339, 049,
No. 4,760,013, No. 4,734,444, No. 2,833,827, German Patent No. 2,904,626
No. 3,604,580 or 3,604,5
81, a sulfonium salt described in J. No. 81; V. Crivel
lo et al, Macromorecules, 1
0 (6), 1307 (1977), or J.I. V. Cr
ivello et al, J. Mol. Polymer Sc
i. , Polymer Chem. Ed. , 17,104
7 (1979), C.I. S. We
n et al, Teh, Proc. Conf. Ra
d. Curing ASIA, p478 Tokyo,
Octon (1988).

Examples of the counter ion of the onium salt include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethyl Benzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol -5-sulfonic acid, 2-
Methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, p-toluenesulfonic acid and the like can be mentioned. Among these, in particular, hexafluorophosphoric acid,
Alkyl aromatic sulfonic acids such as triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are preferred.

The onium salt is preferably added in an amount of 1 to 50% by weight, more preferably 5 to 30% by weight, based on the total solid content of the material constituting the first layer.
It is particularly preferable to add 〜30% by weight.

It is also preferable to include a dye having a large absorption in the visible light region in the first layer, since the distinction between the image area and the non-image area after image recording becomes clear. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (orient Chemical Industrial Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI
42555), methyl violet (CI4253)
5), ethyl violet, rhodamine B (CI145
170B), malachite green (CI42000),
Examples include methylene blue (CI52015), Aizen spiron blue C-RH (manufactured by Hodogaya Chemical Co., Ltd.), and dyes described in JP-A-62-293247.

The amount of the dye added is preferably 0.01 to 10% by weight based on the total solids of the material constituting the first layer.

For the purpose of further improving the sensitivity, cyclic acid anhydrides, phenols and organic acids can be added. As the cyclic acid anhydride, US Pat.
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride described in US Pat. No. 5,128;
3,6-Endoxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used.

Examples of the phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane and the like.

The organic acids include those described in JP-A-60-88.
942, JP-A-2-96755, and the like, and include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters, and carboxylic acids. acid,
Dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,
4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4
-Cyclohexene-1,2-dicarboxylic acid, erucic acid,
Lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned.

The ratio of the cyclic acid anhydride, phenols and organic acids to the total solid content of the material constituting the first layer is preferably 0.05 to 20% by weight,
It is more preferably 0.1 to 15% by weight, and 0.1 to 15% by weight.
Particularly preferred is 10% by weight.

Further, in order to improve the processing stability under development conditions, the material constituting the first layer is disclosed in
Nonionic surfactants described in JP-A-2-251740 and JP-A-3-208514;
An amphoteric surfactant such as those described in JP-A-1121044 and JP-A-4-13149 can be added.

Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, and polyoxyethylene nonyl phenyl ether.

Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl- N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like.

The ratio of the nonionic surfactant and the amphoteric surfactant to the total solid content of the material constituting the first layer is preferably 0.05 to 15% by weight, and 0.1 to 15% by weight.
More preferably, it is about 5% by weight.

A printing-out agent for obtaining a visible image immediately after heating by exposure to light, or a dye or pigment as an image coloring agent can be added to the first layer. As a baking agent,
A representative example is a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, JP-A-50-3620
Nos. 9 and 53-8128.
A combination of a naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye;
Nos. 54-74728, 60-3626, 6
Combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A Nos. 1-143748, 61-151644 and 63-58440 can be exemplified. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

Further, an epoxy compound, a vinyl ether compound, a phenol compound having a hydroxymethyl group or an alkoxymethyl group described in Japanese Patent Application No. 7-18120, and an alkali dissolution inhibitor described in Japanese Patent Application No. 9-328937. It is preferable to add a crosslinkable compound having an effect in that the printing durability by burning can be improved.

Further, a plasticizer may be added to the material constituting the first layer, if necessary, in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid Oligomers and polymers can be suitably used.

Further, in the material constituting the first layer, a surfactant for improving the coating property, for example, Japanese Unexamined Patent Publication No. Sho 62
A fluorine-based surfactant as described in JP-A-170950 can be added. The preferable addition amount is 0.0% of the total solid content of the material constituting the first layer.
It is preferably from 1 to 1% by weight, more preferably from 0.05 to 0.5% by weight.

[Second Layer] The second layer is provided on the first layer and contains a photodecomposable or thermally decomposable compound. The second layer decomposes a photodecomposable or thermally decomposable compound contained therein by light or heat (including heat generated by the donation of light) provided at the time of image recording. This layer improves the permeability of the developer. By providing the second layer on the first layer, in the non-laser-irradiated portion, the developer is prevented from penetrating into the first layer, and in the laser-irradiated portion, the developer is dispersed in the first layer. It promotes penetration into the layer, thereby improving development latitude in the development process.

The photodegradable or thermally decomposable compound is
It may be a high molecular compound or a low molecular compound. The term "photodecomposable compound" as used herein means a compound which is decomposed by applied light when light is used during image recording, and is 0.01 mJ / cm ^{2 to} 500 mJ / cm ^2.
Compounds which decompose by the donation of light are preferred. on the other hand,
The term "thermally decomposable compound" refers to a compound that is decomposed by applied heat (in the case of heat mode image recording using an infrared laser, includes heat generated by laser irradiation) when performing heat mode image recording. Is 50 ° C
The temperature is preferably not less than 350 ° C. and not more than
The temperature is more preferably 0 ° C or lower. If the decomposition temperature is lower than 50 ° C., the storage stability may decrease,
When the temperature exceeds ℃, the decomposition may be insufficient due to the supply of heat at the time of heat mode image recording, and the sensitivity may decrease. In addition, "decomposition temperature" means that when calorimetric analysis is performed,
The temperature at which the weight is reduced by half.

Examples of the polymer decomposable compound include a polymer having cyanoacrylate as a monomer unit; a polymer having styrenes such as α-methylstyrene as a monomer unit; and a (meth) acrylate monomer such as methyl methacrylate as a monomer unit. Polycarbonates such as polypropylene carbonate; celluloses such as nitrocellulose, cellulose acetate butyrate and cellulose acetate; chlorine-containing polymers such as polyvinyl chloride and polyvinylidene chloride; polymers having an azo group in the main chain; polyvinylpyrrolidone; Orthoesters; acrylonitrile or substituted acrylonitrile polymers; polyamides; polyurethanes; maleic acid resins; polythioacetones;

Among them, cyanoacrylate polymers described in JP-A-10-03164 and JP-A-10-244751; (meth) such as methyl methacrylate;
Polymer having an acrylate as a monomer unit; JP-A-06-199064, US Pat. No. 5,339,737, US Pat.
Nitrocellulose described in P5353705 and EP0580393; JP-A-07-0030.
No. 94, JP-A-10-507219, JP-A-11-6
No. 5106 and polymers having an azo group in the main chain described in JP-A-11-80523 and the like.

The high molecular weight decomposable compound has a molecular weight of 5
It is preferably at least 00, more preferably at least 1,000.

Examples of the low molecular decomposable compound include nitro compounds such as ammonium nitrate, potassium nitrate and sodium nitrate, organic peroxides, azo compounds, diazo compounds, and the like.
And hydrazine compounds. Among them, azo compounds and diazo compounds are preferably used.

When a low molecular weight compound is used as the decomposable compound contained in the second layer, the second layer may contain a binder resin. As the binder resin, styrene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
Ethyl methacrylate, butyl methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, butadiene, methylstyrene, vinyltoluene, dimethylaminoethyl acrylate, acrylic acid, methacrylic acid, isoprene,
Chloroprene, maleic anhydride, ethylene glycol acrylate such as polyethylene glycol acrylate,
Halogenated vinyl aromatics, such as chlorostyrene and bromostyrene, and homopolymers and copolymers, such as methyl vinyl ether, vinyl pyrrolidone, and urethane. Further, the alkaline water-soluble polymer may be used as the binder resin.

In the second layer, the decomposable compound is contained in an amount of 5 to 1 in the total solid content of the components constituting the second layer.
It is preferably 00% by weight, more preferably 15 to 100% by weight.

The second layer may optionally contain other components such as an infrared absorber. Examples of the infrared absorbent include the infrared absorbent exemplified as the component of the first layer.

The image recording material of the present invention can be produced by the following method. First, the first layer is formed by dissolving an alkali-water-soluble polymer constituting the first layer and, if desired, an infrared absorber or the like in a solvent, applying the solution on a suitable support, and drying. As the solvent used here,
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, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene , Water and the like, but are not limited thereto. These solvents are used alone or as a mixture.
The concentration of the components (total solids including additives) in the solvent is as follows:
Preferably it is 1 to 50% by weight. The coating amount (solid content) on the support obtained after coating and drying varies depending on the application, but when used as a photosensitive printing plate, it is generally 0.5 to 5.0 g / m ² . Is preferred.

Various methods can be used for the coating. Examples include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, roll coating, and the like. it can. The apparent sensitivity increases as the coating amount decreases, but the coating properties of the layer deteriorate.

Next, the photodecomposable compound constituting the second layer
Or a thermally decomposable compound, and optionally an infrared absorber
Is dissolved in a solvent and applied on the first layer. The solution to use
As the medium, the same solvent as that used for forming the first layer is used.
Solvents. The above components in the solvent (total including additives)
(Solid content) is preferably 0.05 to 60% by weight.
Good. The amount of coating on the support obtained after coating and drying
(Solid content) is generally 0.5 to 5.0 g / m^TwoIs preferred
New The amount of application (solid content) varies depending on the application
However, when used as a photosensitive printing plate, generally
0.01 to 2 g / m ^TwoIt is preferred that

The support is a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal (eg, aluminum, zinc, Copper) plate, plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate,
Polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper on which the metal is laminated or vapor-deposited, or plastic film.

When the image recording material of the present invention is used as a lithographic printing plate precursor, the support is preferably a polyester film or an aluminum plate. Among them, an aluminum plate having good dimensional stability and being relatively inexpensive is preferable. Particularly preferred. 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 the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum 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 is about 0.1
mm to 0.6 mm, preferably 0.15 mm to 0.1 mm.
4 mm, particularly preferably 0.2 mm to 0.3 mm.

The aluminum plate is preferably used after being roughened, but before the surface is roughened, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove rolling oil on the surface. You can also. The surface roughening treatment of the surface of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface,
This is performed by a method of electrochemically dissolving and roughening the surface and a method of chemically selectively dissolving the surface. 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 or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as required, and then subjected to an anodic oxidation treatment if necessary to enhance 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 that form 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 preferred treatment conditions for anodization vary depending on the electrolyte used, but cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, and the solution temperature is 5%.
７０70 ° C., current density 5５〜60 A / dm ² , voltage 1１〜10
It is appropriate that the voltage is 0 V and the electrolysis time is 10 seconds to 5 minutes. When the amount of the anodic oxide coating is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area is easily scratched.
When used as a printing plate, a so-called "scratch stain" in which ink adheres to a scratched portion is likely to occur.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. Examples of the hydrophilic treatment include those disclosed in U.S. Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. There is an alkali metal silicate (for example, sodium silicate aqueous solution) method. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, potassium fluorozirconate disclosed in Japanese Patent Publication No. 36-22063 and U.S. Pat.
No. 76,868, No. 4,153,461, No. 4,
For example, a method of treating with polyvinyl phosphonic acid as disclosed in Japanese Patent No. 689,272 is used.

An undercoat layer may be provided between the support and the first layer, if necessary. Examples of components constituting the undercoat layer include various organic compounds, and examples thereof include carboxymethyl cellulose; dextrin; gum arabic; phosphonic acids having an amino group such as 2-aminoethylphosphonic acid; and may have a substituent. Organic phosphonic acids such as phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid; phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid which may have a substituent and Organic phosphoric acids such as glycerophosphoric acid; organic phosphinic acids 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 triethanol Amine hydrochloride What hydroxy group amine hydrochloride with; but are selected from such as it may be used by mixing two or more. Also,
In the undercoat layer, a dissolution inhibitor such as a polyfunctional amine compound which is optionally contained in the first layer may be added.

The undercoat layer is formed by applying a solution obtained by dissolving the above organic compound and / or polyfunctional amine compound or the like in water or an organic solvent such as methanol, ethanol or methyl ethyl ketone or a mixed solvent thereof on a support. , Can be provided by drying. Further, the support is immersed in a solution obtained by dissolving the organic compound and / or polyfunctional amine compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof, and the compound is placed on the support. It can be adsorbed, then washed with water or the like, and dried to provide an undercoat layer. In the former formation method, it is preferable to use a solution in which the concentration of the organic compound and / or the polyfunctional amine compound is 0.005 to 10% by weight as the coating solution. In the latter method, the concentration of the component is 0.01 to 20.
It is preferable to use a solution of 0.1% by weight as the immersion liquid.
More preferably, a solution of 0.5 to 5% by weight is used. Further, the immersion temperature is preferably 20 to 90 ° C.
It is more preferable that the temperature is 50C. The immersion time is preferably from 0.1 second to 20 minutes, and more preferably from 2 seconds to 1 minute. The immersion liquid can be adjusted to pH 1 to 12 with a basic substance such as ammonia, triethylamine, potassium hydroxide or the like, or an acidic substance such as hydrochloric acid or phosphoric acid. When the image recording material of the present invention is used as a lithographic printing plate precursor, a yellow dye may be added to the undercoat layer in order to improve tone reproducibility.

The coating amount of the undercoat layer is 2 to 200 mg / m
^TwoIs suitable, preferably 5 to 100 mg / m^TwoIn
You. The coating amount is 2 mg / m^TwoLess than or 200m
g / m ^TwoIf it exceeds, it was used as a lithographic printing original plate.
In this case, sufficient printing durability may not be obtained.

When the image recording material of the present invention is used as a lithographic printing plate precursor, it is usually made by subjecting it to image exposure and development. Examples of the light source of the actinic ray used for the image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like. Examples of the radiation include an electron beam, an X-ray, an ion beam, and a far-infrared ray. G line, i line, Deep
-UV light, high-density energy beam (laser beam)
Is also used. Helium / neon laser, argon laser, krypton laser,
A helium-cadmium laser, a KrF excimer laser, a solid-state laser, a semiconductor laser, and the like are included. In the lithographic printing plate precursor, it is particularly preferable to perform image recording using a light source having an emission wavelength in the near infrared to infrared region,
It is particularly preferable to perform image recording using a solid laser or a semiconductor laser. In recording an image, a heat source such as a thermal head may be used.

As a developing solution and a replenishing solution used in the developing treatment, conventionally known alkaline aqueous 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,
And inorganic alkali salts such as 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, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents are used alone or in combination of two or more. In particular, it is preferable to use a silicate aqueous solution containing sodium silicate, potassium silicate, or the like as the developer. When an aqueous silicate solution is used as a developer, the developability is controlled by the ratio and concentration of silicon oxide SiO _{2 as} a component of silicate and alkali metal oxide M ₂ O (M represents an alkali metal). This is preferable because it becomes possible. For example, JP-A-54-6200
No. 4, JP-B-57-7427, and alkali metal silicates are preferred.

The lithographic printing plate precursor that has been developed using the above developer and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, or a desensitizing solution containing gum arabic and a starch derivative. . The post-processing may be performed a plurality of times by variously combining the above-described processes.

In recent years, in the plate making and printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize plate making operations. The lithographic printing plate precursor can also be made by an automatic developing machine. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a printing plate precursor, each processing solution tank and a spray device, and each pump which has been pumped while transporting the exposed printing plate precursor horizontally. The processing liquid is sprayed from a spray nozzle to perform development processing. Also, recently, in a processing solution tank filled with processing solution,
A method is also known in which a printing plate is immersed and conveyed by a submerged guide roll or the like for 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.

When developing using the automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is used.
It is known that a large amount of an image recording material (for example, a lithographic printing original plate) can be processed without replacing the developing solution in the developing tank for a long period of time by adding to the developing solution. It is preferable to use this replenishment system also when making the lithographic printing plate precursor. To the developing solution and the replenishing solution, various surfactants and organic solvents can be added as necessary for the purpose of promoting or suppressing the developing property, dispersing the developing residue and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, if necessary, reducing agents such as sodium salts and potassium salts of inorganic acids such as hydroquinone, resorcinol, sulfurous acid, and hydrogen sulfite, and further organic carboxylic acids, defoamers, and water softeners may be added to the developing solution and the replenishing solution. Can be added.

After image exposure, development, washing and / or rinsing and / or gumming, an unnecessary first layer remains on the support (for example, film edge marks on original film, etc.). In the case, the above-mentioned unnecessary layer can be erased. As for the erasing method,
For example, a method of applying an erasing liquid as described in JP-B-2-13293 to the unnecessary layer region, leaving the same for a predetermined time, and washing with water is preferable. The method of irradiating an unnecessary image portion with an actinic ray guided by an optical fiber as described in (1) and then developing the image portion can also be used.

The lithographic printing plate precursor is made into a lithographic printing plate by the above-described processing, and is subjected to a printing step after coating with a desensitizing gum if desired. For lithographic printing plates,
Burning treatment may be performed for the purpose of improving printing durability. When the lithographic printing plate is to be subjected to a burning treatment, the lithographic printing plate must be burned before the burning treatment.
No. 8062, JP-A-62-31859, JP-A-61-15
It is preferable to carry out treatment with a surface-regulating liquid as described in each publication of US Pat. As the method, a method of applying the lithographic printing plate on a lithographic printing plate with a sponge or absorbent cotton impregnated with the surface conditioning solution, or immersing the lithographic printing plate in a vat filled with the surface conditioning solution, Application by an automatic coater is applied. Further, it is more preferable that the application amount is made uniform using 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.

After drying the lithographic printing plate to which the surface conditioning liquid has been applied, the lithographic printing plate is heated to a high temperature using a burning processor (for example, a burning processor sold by Fuji Photo Film Co., Ltd .: "BP-1300") or the like. Is also good. The heating temperature and time in this case depend on the type of the component forming the image, but the heating temperature is 180 to 300 ° C.
The heating time is preferably 1 to 20 minutes.

The lithographic printing plate subjected to the burning process is as follows:
If necessary, conventional treatments such as washing with water and gumming can be performed.However, when a surface conditioning solution containing a water-soluble polymer compound or the like is used, gumming or the like can be performed. Can be omitted.

The planographic printing plate obtained by such a process is incorporated in an offset printing machine or the like and used for printing on paper or the like.

[0137]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.
However, the scope of the present invention is limited to these Examples.
There is no. In the following text, “parts” means “parts by weight”.
You. (Example 1) [Preparation of substrate] Aluminum plate having a thickness of 0.3 mm (material
1050) was degreased by washing with trichloroethylene.
After, nylon brush and 400 mesh pumice-water suspension
The surface was grained using a liquid and washed well with water. This
Plate for 9 seconds in a 25% aqueous solution of sodium hydroxide at 45 ° C
Etching by immersion, washing with water, and then 20% nitric acid
For 20 seconds and washed with water. At this time,
Etching amount is about 3g / m ^TwoMet. Next,
Using a 7% sulfuric acid as the electrolyte,
Degree 15A / dm^Two3g / m^TwoDC anodic oxide coating
And then rinsed with water, dried, and
And dried at 90 ° C. for 1 minute. Coating after drying
The coating amount of the film is 10 mg / m^TwoMet.

<Composition of Undercoat Liquid> 0.5 g of β-alanine 95 g of methanol 5 g of water

A coating solution A-1 having the following composition was prepared,
The composition was applied on the substrate so that the application amount was 1.8 g / m ² to form a first layer.

<Composition of Coating Liquid A-1> 1.0 g of m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 3500, unreacted cresol 0.5% by weight) * Alkaline water-soluble polymer compound ・ Infrared absorber (compound represented by the following structural formula 1) 0.2 g ・ Dye in which counter anion of Victoria Pure Blue BOH is changed to 1-naphthalenesulfonic acid anion 0.02 g ・ Fluorine-based interface Activator (“MegaFac F-177”, manufactured by Dainippon Ink & Chemicals, Inc.) 0.05 g ・ γ-butyrolactone 3 g ・ Methyl ethyl ketone 8 g ・ 1-methoxy-2-propanol 7 g

[0141]

Embedded image

A coating solution B-1 having the following composition was prepared,
The lithographic printing plate precursor was obtained by coating the first layer so that the coating amount was 0.3 g / m ² , and forming a second layer. <Composition of the coating solution B-1> ・ Nitrocellulose (nitrocellulose having a nitrogen content of 12%, Sigma-Aldrich Japan Co., Ltd.) 10 parts * Pyrogenic compound (decomposition temperature: 195 ° C.) ・ Infrared absorber (the structure described above) 0.3 part of acetone 350 parts of water 50 parts of water

(Example 2) A lithographic printing plate was prepared in the same manner as in Example 1 except that the coating solution B-1 used for forming the second layer in Example 1 was changed to a coating solution B-2 having the following composition. A printing plate precursor was prepared. <Composition of the coating solution B-2>-10 parts of cyanoacrylate polymer (poly-methyl-2-cyanoacrylate, weight average molecular weight 52,000) * Thermally decomposable compound (decomposition temperature: 197 ° C)-Infrared absorber (the structure described above) Compound represented by Formula 1) 0.3 part ・ 350 parts of acetonitrile ・ 50 parts of water

(Example 3) The coating liquid B-1 used for forming the second layer in Example 1 was replaced with a coating liquid B-3 having the following composition, and the coating amount was 0.05 g / m ² . Except for Example 1,
A lithographic printing plate precursor was prepared in the same manner as described above. <Composition of the coating solution B-3> 5 parts of polymethyl acrylate (weight average molecular weight 15,000, Sigma-Aldrich Japan Co., Ltd.) * Thermally decomposable compound (decomposition temperature 340 ° C) 0.3 part)-methyl ethyl ketone (350 parts)-water (50 parts)

Example 4 A lithographic printing plate was prepared in the same manner as in Example 1 except that the coating solution B-1 used for forming the second layer in Example 1 was changed to a coating solution B-4 having the following composition. A printing plate precursor was prepared. <Composition of coating liquid B-4> 3 parts of diazonium salt compound (compound represented by the following structural formula 2) 10 parts of cyanoacrylate polymer (poly-methyl-2-cyanoacrylate, weight average molecular weight 52,000) * Thermally decomposable compound (decomposition temperature: 197 ° C.) ・ Infrared absorbent (compound represented by the structural formula 1) 0.3 part ・ Acetonitrile 350 parts ・ Water 50 parts

[0146]

Embedded image

(Comparative Example 1) A lithographic printing plate precursor was produced in the same manner as in Example 1, except that the second layer was not formed.

Comparative Example 2 In Example 1, a layer was formed on the first layer by using a coating solution C-1 having the following composition instead of forming the second layer. A lithographic printing plate precursor was produced in the same manner as in Example 1. <Composition of coating liquid C-1>-Polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 1,000, partially saponified type) 10 parts-Methanol 50 parts-Water 350 parts

Example 5 [Synthesis of Copolymer as Alkaline Aqueous Solution-Soluble Polymer Compound] <Synthesis Example (Copolymer 1)> Methacrylic acid 3 was placed in a 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
1.0 g (0.36 mol), ethyl chloroformate 39.1
g (0.36 mol) and 200 ml of acetonitrile were added, and the mixture was stirred while cooling in an ice-water bath. To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped by a dropping funnel over about 1 hour. After dropping,
The ice water bath was removed and the mixture was stirred at room temperature for 30 minutes.

To the reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was poured into 1 liter of stirred water, and thereafter, stirring was continued for 30 minutes. Thereafter, the mixture was filtered to remove a precipitate, which was then washed with 500 m of water.
Then, the slurry was filtered and the obtained solid was dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.9 g).

Next, 5.04 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 100 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
0210 mol), ethyl methacrylate 2.05 g
(0.0180 mol), acrylonitrile 1.11 g
(0.021 mol) and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. 0.15 g of "V-65" (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the mixture, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. The reaction mixture was further added with N- (p-aminosulfonylphenyl) methacrylamide (5.04 g) and ethyl methacrylate (2.05 g).
g, acrylonitrile 1.11 g, N, N-dimethylacetamide 20 g, and "V-65" 0.15 g
Was dropped by a dropping funnel over 2 hours. After the addition was completed, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol was added to the mixture,
After cooling, the obtained mixture was poured into 2 liters of water while stirring the water, and after stirring the mixture for 30 minutes, the precipitate was taken out by filtration and dried to obtain 15 g of a white solid. According to gel permeation chromatography, weight average molecular weight (polystyrene standard) 53,000
0 copolymer 1 was obtained.

The following coating solution A-2 was applied to a substrate similar to that used in Example 1 so that the coating amount was 1.8 g / m ^2, and a first layer was formed on the substrate. . <Composition of the coating solution A-2>-The above-mentioned copolymer 1 1.0 g * Alkaline water-soluble polymer-Infrared absorber (compound represented by the above-mentioned structural formula 1) 0.1 g-Victoria Pure Blue BOH Dye having counter anion as 1-naphthalenesulfonic acid anion 0.02 g ・ Fluorine-based surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.) 0.05 g ・ γ-butyrolactone 8 g -Methyl ethyl ketone 8 g-1-methoxy-2-propanol 4 g

A coating solution B-5 having the following composition was prepared,
On the formed first layer, an application amount of 0.3 g / m ²
And a second layer was formed on the first layer to obtain a lithographic printing plate precursor. <Composition of the coating solution B-5> ・ Nitrocellulose (nitrocellulose having a nitrogen content of 12%, Sigma-Aldrich Japan Co., Ltd.) 10 parts * Pyrogenic compound (decomposition temperature: 195 ° C.) ・ Infrared absorber (the above structure) Compound represented by Formula 1) 0.3 part ・ Acetone 400 parts

(Example 6) The coating liquid B-5 used for forming the second layer in Example 5 was replaced with a coating liquid B-6 having the following composition, and the coating amount was reduced to 0.3 g / m ² . Example 5 except that
A lithographic printing plate precursor was prepared in the same manner as described above. <Composition of the coating solution B-2>-10 parts of cyanoacrylate polymer (poly-methyl-2-cyanoacrylate, weight average molecular weight 52,000) * Thermally decomposable compound (decomposition temperature: 197 ° C)-Infrared absorber (the structure described above) 0.3 part of a compound represented by the formula 1 400 parts of acetonitrile

(Example 7) A lithographic printing plate was prepared in the same manner as in Example 5, except that the coating solution B-5 used for forming the second layer in Example 5 was changed to a coating solution B-7 having the following composition. A printing plate precursor was prepared. <Composition of the coating solution B-7> • 5 parts of polymethyl acrylate (weight average molecular weight 15,000, Sigma-Aldrich Japan Co., Ltd.) * Thermally decomposable compound (decomposition temperature 340 ° C) • Infrared absorber (the above structural formula) 0.3 part of methyl ethyl ketone 400 parts

(Example 8) The coating liquid B-5 used for forming the second layer in Example 5 was replaced with a coating liquid B-8 having the following composition, and the coating amount was 0.1 g / m ² . Except for the above, a lithographic printing plate precursor was produced in the same manner as in Example 5. <Composition of Coating Solution B-8> • 1 part of polyazo compound (polyazo compound used in Example 1 of JP-A-11-65106) * Thermally decomposable compound (decomposition temperature: 156 ° C) • Benzyl methacrylate and methacryl Copolymer with acid (molar ratio 72:28, weight average molecular weight 70,000) 1 part • cyclohexanone 15 parts • methoxypropyl acetate 15 parts

(Comparative Example 3) A lithographic printing plate precursor was prepared in the same manner as in Example 5, except that the second layer was not formed.

(Comparative Example 4) In Example 5, a layer was formed on the first layer by using a coating solution C-2 having the following composition instead of forming the second layer. A lithographic printing plate precursor was produced in the same manner as in Example 5. <Composition of the coating liquid C-2>-10 parts of polyimide ("XU-218", manufactured by Ciba-Geigy)-350 parts of 1-methyl-2-pyrrolidinone-10 parts of water

[Performance Evaluation of Lithographic Printing Plate Precursor] The lithographic printing plate precursors of Examples 1 to 8 and Comparative Examples 1 to 4 produced as described above were evaluated for performance according to the following criteria. Table 1 shows the evaluation results.

(Image Formability: Evaluation of Development Latitude)
After the obtained lithographic printing plate precursor was exposed using a semiconductor laser having a wavelength of 840 nm, an automatic developing machine (Fuji Photo Film Co., Ltd.) was charged with a developing solution DP-4 and a rinsing solution FR-3 (1: 7). The image was developed using Fuji Photo Film Co., Ltd .: “PS Processor 900VR”. At that time, DP-
No. 4 used two levels, one diluted 1: 6 and one diluted 1:12, and measured the line width of the non-image portion obtained with each developer, and measured the laser width corresponding to the line width. The irradiation energy was determined. Then, the difference in irradiation energy of the laser between the standard 1: 6 dilution and the 1:12 dilution was recorded. The smaller the difference is, the better the development latitude is. If the difference is 20 mJ / cm ² or less, the evaluation results of the development latitude are excellent.

[0161]

[Table 1]

From the results shown in Table 1, the lithographic printing plate precursors of Examples 1 to 8 were all different from the lithographic printing plate precursors of Comparative Examples 1 to 4 in the difference in sensitivity to the developer at two dilution concentrations ( It can be seen that the difference in irradiation energy) is small and the development latitude is high. In addition, the difference in sensitivity to the developer at the two dilution concentrations was 20 mJ / cm in any of the examples.
² or less, and it was confirmed that the developing latitude was excellent.

[0163]

According to the present invention, an image recording material excellent in development latitude can be provided even when a heat mode image recording method using an infrared laser or the like is applied.

[Brief description of the drawings]

FIG. 1 is an embodiment in which the image recording material of the present invention is applied to a lithographic printing plate precursor.

[Explanation of symbols]

 Reference Signs List 10 planographic printing plate precursor 12 support 14 first layer 16 second layer

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) // B41N 1/14 B41N 1/14 F term (Reference) 2H025 AA04 AB03 AC01 AC05 AC06 AC07 AC08 AD03 BE00 BF01 BF07 BF14 BF21 BF27 BG00 CB52 CC11 DA13 DA40 2H096 AA06 AA30 BA09 BA10 BA11 CA20 EA02 EA04 EA06 EA07 EA08 KA03 KA06 2H114 AA04 AA15 BA01 BA05 DA27 DA29 DA31 DA35 FA06 GA05 GA38

Claims (2)

[Claims] 1. A first layer on a support, which contains a polymer compound insoluble in water and soluble in alkaline water, and has increased solubility in alkaline water by the provision of light or heat, An image recording material, comprising: a second layer containing a photodecomposable compound or a thermally decomposable compound on the first layer. 2. The image recording material according to claim 1, wherein the second layer contains a thermally decomposable compound, and the decomposition temperature of the thermally decomposable compound is 50 ° C. or more and 350 ° C. or less.