JP2001215693A - Image forming material and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming material which suppresses the leaching and peeling of an image area due to wiping with a cleaner in printing work using a photosensitive planographic printing plate, and a stain due to an erased fringe caused by the use of a correcting fluid, and a method of producing the image forming material. SOLUTION: The image forming material has an image forming layer on the substrate, the image forming layer contains a novolak resin, an IR absorber and a compound containing repeating units of formula 1 (where A is H or a 1-4C alkyl; X is an alkylene; and Y is a group substituted by carboxyl or its salt, sulfo, its salt, phosphonoxy, dialkylphosphonoxy, trialkoxysilyl or alkyldialkoxysilyl) and the image forming material forms an image by laser exposure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material having a so-called positive type image forming layer which is solubilized by actinic light and a method for producing the same. More specifically, an image is formed by exposure to infrared rays such as a semiconductor laser. The present invention relates to an image forming material suitable for a positive photosensitive lithographic printing plate and the like and a method for producing the same.

[0002]

2. Description of the Related Art Conventional image forming materials, especially positive photosensitive lithographic printing plates, are generally obtained by applying an image forming layer using a novolak resin as a binder on an aluminum support. In such a photosensitive lithographic printing plate, the image forming layer of the image area may be gradually melted or peeled off from the support due to a cleaner wiping operation during the printing operation. It is known to use an acrylic resin as a binder resin in order to increase the resistance to such chemicals. However, this method did not sufficiently improve the chemical resistance. Further, in the photosensitive lithographic printing plate, unnecessary images or image portions requiring deletion correction may occur, so that correction is necessary. Correctors for removing such unnecessary image portions are described in JP-A-54-89806 and JP-B-5-2321. However, even when such a correction agent is used, a so-called erase fringe stain, that is, a portion where the ink adheres linearly around the applied correction liquid, cannot be completely suppressed.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to improve elution and peeling of an image area due to a cleaner wiping operation during a printing operation using a photosensitive lithographic printing plate, and to further reduce an erase fringe stain caused by using a correction liquid. And a method of manufacturing the same.

[0004]

The object of the present invention has been attained by the following constitutions.

1) An image forming layer is provided on a support, and the image forming layer contains a novolak resin, an infrared absorber, and a compound containing a repeating unit represented by the general formula (1),
An image forming material, which forms an image by laser exposure.

2) An image forming layer is provided on a support, and the image forming layer is composed of a novolak resin, an infrared absorber, and a compound represented by the general formula (1)
From a compound containing a repeating unit represented by the general formula (1) selected from a group in which Y is substituted with a carboxyl group, a sulfo group, and a phosphonoxy group, and an organic amine compound, an organic aniline compound, an alkali metal hydroxide, and an alkali metal salt. An image-forming material containing at least one selected compound and forming an image by laser exposure.

3) an image forming layer on a support, the image forming layer containing a novolak resin, an infrared absorber, and a compound containing a repeating unit represented by the general formula (2);
An image forming material, which forms an image by laser exposure.

(4) The image forming material as described in (1), (2) or (3) above, wherein the solubility of the exposed portion in an alkaline aqueous developer is changed by laser exposure.

(5) The image-forming material as described in (1), (2) or (3) above, which contains a compound which generates an acid by being decomposed in the image-forming layer and a compound which is decomposed by the presence of the acid. .

(6) The image-forming material as described in (1), (2) or (3) above, which contains a compound which generates an acid when decomposed in the image-forming layer and a compound which cross-links due to the presence of the acid. .

7) A coating solution obtained by adding a novolak resin, an infrared absorber, and a compound containing a repeating unit selected from the general formula (1) or (2) to a support. A method for producing an image forming material.

8) On a support, a novolak resin, an infrared absorber, a repeating unit represented by the general formula (1) selected from a group in which Y in the general formula (1) is substituted by a carboxyl group, a sulfo group, and a phosphonoxy group At least one compound selected from a compound containing a unit, an organic amine compound, an organic aniline compound, an alkali metal hydroxide and an alkali metal salt.
A method for producing an image forming material, comprising applying a coating liquid obtained by adding a seed.

Hereinafter, the present invention will be described in detail. In the general formula (1), examples of the group substituted by the carboxyl group represented by Y or a salt thereof include an alkoxy group,
Aryloxy groups. Hereinafter, specific examples of the general formula (1) will be shown, but the present invention is not limited thereto.

[0014]

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[0016]

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[0017]

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The repeating unit of the formula (1) is preferably contained in the resin in an amount of 1 to 20 mol%, more preferably 1 to 5 mol%. Further, the content of the repeating unit of the general formula (1) contained in the image forming layer is 0.1.
001 to 0.01 mmol / g. As Y contained in the repeating unit of the general formula (1), a sulfo group is preferable. When Y is an acid group, it is preferably present in the form of a salt. This is remarkable and preferable when the image forming layer contains an acid-reactive compound such as an acid-decomposable or acid-crosslinkable compound.

The organic amine compound according to claim 2 is specifically diethanolamine, triethanolamine, trioctylamine, diethylamine, dimethylethanolamine, ditetylethanolamine, triethylamine, ethylhexylamine, propylamine, butylamine, methoxypropylamine. , Diaminopropane, diisopropylethylamine, cyclohexylamine, dicyclohexylamine, dibutylethanolamine.

As the organic aniline compound, aniline,
N, N-dimethylaniline, N, N-diethylaniline, aminobenzonitrile, aminobenzoic acid, anisidine, N-ethylaniline, diaminodiphenyl ether, N, N-dimethyltoluidine, toluidine, nitroaniline, nitrotoluidine, phenylenediamine, Phenetidine, xylidine, and cresidine.

Examples of the alkali metal hydroxide include lithium hydroxide, potassium hydroxide and sodium hydroxide.
Examples of the alkali metal salt include potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium citrate.

These compounds are usually used in an amount of from 0.001 to 0.
It is preferable to add 1% by mass. Specific examples of the general formula (2) are shown below.

[0023]

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Hereinafter, examples of comparative compounds of the compound containing a repeating unit represented by formula (1) or (2) will be described.

[Synthesis of Comparative Compound R1] In a 100 ml three-necked flask, 25 ml of propylene glycol monomethyl ether (PGM) was placed, and 3.5 g of N-hydroxyphenylacrylamide was further placed under a nitrogen atmosphere.
(0.023 mol), 3.0 g of methyl methacrylate
(0.030 mol), 1.51 g of methacrylonitrile
After dissolving 0.18 g of azobisisobutyronitrile (0.023 mol), the temperature was maintained at 75 ° C. for 6 hours with stirring. Then, after adding 0.004 g of hydroquinone, it was kept at 80 ° C. while reducing the pressure with an evaporator. When the PGM began to be distilled, the pressure reduction and heating were stopped, and this was used as a PGM solution of the compound R1.

Hereinafter, the monomers are replaced with the compositions shown in the following table,
In the same manner, compounds R2 and C1 to C22 containing a repeating unit represented by the general formula (1) or (2) were synthesized.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

The synthesis of F1 to F4 in Tables 3 and 4 is as follows. [Synthesis of F1] The following amino compound G1, 0.208m
was dissolved in 180 ml of ethyl acetate, and 0.208 m
ol of potassium carbonate was dissolved in 50 ml of water. Here, 50 ml of ethyl acetate in which 0.208 mol of methacrylic acid chloride was dissolved was added dropwise at 25 ° C. over 30 minutes. After leaving overnight, the target F1 was obtained by depositing, filtering and drying with a large amount of water.

Similarly, the following amino compounds G2 to G4
Were used to synthesize F2 to F4.

[0033]

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The infrared absorbing agent of the present invention has a wavelength of 70
Infrared absorbers having absorption at 0 nm or more, carbon black, magnetic powder and the like can be used. Particularly preferred infrared absorbers have an absorption peak at 700 to 850 nm,
This is an infrared absorber having a peak molar extinction coefficient ε of 10 ⁵ or more.

As the infrared absorber, cyanine dyes,
Squarium dyes, croconium dyes, azurenium dyes, phthalocyanine dyes, naphthalocyanine dyes, polymethine dyes, naphthoquinone dyes, thiopyrylium dyes, dithiol metal complex dyes, anthraquinone dyes, indoaniline metal complex dyes, And intermolecular CT dyes.

As an infrared absorbing agent, JP-A-63-1
39191, 64-33547, JP-A-1-16
Nos. 0683, 1-280750, 1-229334
No. 2, No. 2-2074, No. 3-26593, No. 3-
Nos. 30991, 3-34891, 3-36093
No. 3-36094, No. 3-36095, No. 3-
Compounds described in JP-A-42281 and JP-A-3-103476 are also included.

In the present invention, as the infrared absorbing agent,
A cyanine dye represented by the following general formula (I) or (II) is particularly preferred.

[0038]

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In the formula, Z ₁ and Z ₂ each represent a sulfur atom, a selenium atom or an oxygen atom, and X ₁ and X ₂ each form an optionally substituted benzo-fused ring or naphtho-fused ring. And R ₃ and R ₄ each represent a substituent, and one of R ₃ and R ₄ has an anionic dissociable group. R ₅ , R ₆ , R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms, a hydrogen atom or a halogen atom. L represents a chain of conjugated bonds having 5 to 13 carbon atoms.

The cyanine dyes represented by the general formula (I) or (II) include those in which the general formula (I) or (II) forms a cation and has a counter anion. in this case,
As the counter anion, Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , B
And alkylboron such as F ₄ ⁻ and t-butyltriphenylboron.

In the general formulas (I) and (II), the number of carbon atoms (n) in the chain of conjugated bonds represented by L is determined when a laser emitting infrared light is used as a light source for image exposure. It is preferable to select an effective value according to the transmission wavelength of the light. For example, Y at an emission wavelength of 1060 nm
When an AG laser is used, n is preferably 9 to 13. The conjugate bond may have an arbitrary substituent, and the conjugate bond may form a ring with a plurality of substituents.

In the general formulas (I) and (II), the ring represented by X ₁ and the ring represented by X ₂ can have any substituent. Halogen atom as the substituent, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, (the M hydrogen atom or an alkali metal atom) -SO ₃ M and -COOM is a group selected from the preferred .

R ₃ and R ₄ are each an optional substituent,
Preferably an alkoxy group of 1 to 5 alkyl groups or carbon atoms of 1 to 5 carbon _{atoms; - ((CH 2) n} -O-)
_{k - (CH 2) m OR} (n and m are each an integer of 1 to 3, k
Represents 0 or 1, and R represents an alkyl group having 1 to 5 carbon atoms. One of R ₃ and R ₄ is —R—SO ₃ M and the other is —
R—SO ₃ ⁻ (R represents an alkyl group having 1 to 5 carbon atoms, M represents an alkali metal atom); or one of R ₃ and R ₄ represents —
R-COOM other hand is -R-COO ^- (R is an alkyl group having 1 to 5 carbon atoms, M represents an alkali metal atom.)
It is. As for R ₃ and R ₄ , one of R ₃ and R ₄ is -R-SO ₃ ^- or -R-COO ^- and the other is -R-SO ₃ M or -R-COOM from the viewpoint of sensitivity and developability. Is preferred.

Cyanide represented by formula (I) or (II)
Dyes use semiconductor lasers as the light source for image exposure
750-900nm, YAG laser
Absorb at 900-1200nm when using
Shows a peak, ε> 1 × 10 ^FiveHas a molar extinction coefficient of
Are preferred.

Representative specific examples of the infrared absorbent used in the present invention, including the general formula (I) or (II), are shown below, but are not limited thereto.

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[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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The addition amount of the infrared absorber is 0.01 to 10% by mass, preferably 0.1 to 5% by mass.

These infrared absorbers can of course be synthesized by a known method, but the following commercially available products can also be used.

Nippon Kayaku: IR750 (anthraquinone type); IR002, IR003 (aluminum type);
R820 (polymethine type); IRG022, IRG03
3 (diimmonium-based); CY-2, CY-4, CY-
9, CY-10, CY-20 Mitsui Toatsu: KIR103, SIR103 (phthalocyanine); KIR101, SIR114 (anthraquinone); PA1001, PA1005, PA1006, S
IR128 (metal complex type) Dainippon Ink and Chemicals: Fastogen blue 812
0 Midori Kagaku: MIR-101, 1011, 1021 Others are also commercially available from companies such as Nippon Kogaku Dyestuffs, Sumitomo Chemical, Fuji Photo Film.

In the present invention, as the compound which generates an acid by decomposition (hereinafter, referred to as an acid generator), an organic halogen compound is preferable in view of sensitivity in image formation by infrared exposure and storability of the image forming material. As the organic halogen compound, a triazine having a halogen-substituted alkyl group and an oxadiazole having a halogen-substituted alkyl group are preferable, and an s-triazine having a halogen-substituted alkyl group is particularly preferable.

Specific examples of oxadiazoles having a halogen-substituted alkyl group are described in JP-A-54-74728.
And 2-halomethyl-1,3,4-oxadiazole compounds described in JP-A Nos. 55-24113, 55-77742, 60-3626 and 60-138439. Preferred examples of the 2-halomethyl-1,3,4-oxadiazole-based acid generator are shown below.

[0065]

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S- having a halogen-substituted alkyl group
As the triazine, a compound represented by the following general formula (III) is preferable.

[0067]

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In the general formula (III), R represents an alkyl group, a halogen-substituted alkyl group, a phenylvinylene group which may be substituted with an alkoxy group or an aryl group (for example, phenyl group, naphthyl group, etc.) or a substituted product thereof. And X represents a halogen atom. Examples of compounds of the s-triazine acid generator represented by the general formula (III) are shown below.

[0069]

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[0070]

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In the present invention, the content of the acid generator can be varied widely depending on its chemical properties and the composition or physical properties of the image forming layer of the image forming material of the present invention. About 0.1 to 2 based on mass
The range of 0% by mass is appropriate, preferably from 0.2 to 10%.
% By mass.

The compounds which are decomposed by the presence of an acid used in the present invention (hereinafter referred to as acid-decomposable compounds) are specifically described in JP-A-48-89003 and JP-A-5-12071.
No. 4, No. 53-133429, No. 55-12995
Compounds having a C--O--C bond described in JP-A Nos. 55-126236 and 56-17345, and Si-O- compounds described in JP-A Nos. 60-37549 and 60-112446. Compound having C bond, JP-A-60
Other acid-decomposable compounds described in JP-A-3625 and JP-A-60-10247. Further, Japanese Patent Application Laid-Open No. 62-222
No. 246, compounds having an Si--N bond, carbonates described in JP-A-62-251743, orthocarbonates described in Japanese Patent Application No. 60-251744, Orthotitanate described in JP-A-280841;
Orthosilicate described in 280842, acetal and ketal described in JP-A-63-10153, compounds having a CS bond described in JP-A-62-244038, and the like. .

Of the above, Japanese Patent Application Laid-Open No. Sho 53-13342
No. 9, 56-17345, 60-12446
No. 60-37549, No. 63-10153 and Japanese Patent Application No. 60-251744.
Compounds having a C bond, compounds having a Si-OC bond, orthocarbonates, acetals, ketals, and silyl ethers are preferred.

Among them, JP-A-53-13342
JP-A-63-10, an organic polymer compound having an acetal or ketal moiety in the main chain described in JP-A No. 9 and whose solubility in a developer is increased by the action of an acid;
The following structural unit described in No. 153

[0075]

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Compounds having the formula and which can be decomposed by an acid are particularly preferred. Specific examples of the acid-decomposable compound used in the present invention include the compounds described in the above publications and specifications. The method for synthesizing the compound is described in each of the above-mentioned publications and in the specification.

In the present invention, the acid-decomposable compound is-
A compound having a (CH ₂ CH ₂ O) _n -group (n represents an integer of 2 to 5) is preferable from the viewpoint of balance between sensitivity and developability. Further, among these compounds, a compound in which the number of chains n of the ethyleneoxy group is 3 or 4 is particularly preferable. The above-(CH
Specific examples of the compound having a ₂ CH ₂ O) _n -group include a condensation product of dimethoxycyclohexane, benzaldehyde and a substituted derivative thereof with any of diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol. Can be

In the present invention, as the acid-decomposable compound, a compound represented by the following formula (IV) is preferred from the viewpoint of sensitivity and developability. In the general formula (IV), R and R ₁
And the alkyl group represented by R ₂ may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, and a pentyl group. Group, ethoxy group, propoxy group, isopropoxy group, butoxy group, tert-butoxy group, pentoxy group and the like, and the sulfo group and the carboxyl group include salts thereof.
Among the compounds represented by the general formula (IV), a compound in which m and n are 1 or 2 is particularly preferable. The compound represented by the general formula (IV) can be synthesized by a known method.

[0079]

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In the present invention, the content of the acid-decomposable compound is 5 to the total solid content of the composition for forming the image forming layer.
It is preferably from 70 to 70% by mass, particularly preferably from 10 to 50% by mass. One type of acid-decomposable compound may be used,
Mixtures of more than one species may be used.

In the present invention, the compound capable of crosslinking in the presence of an acid (hereinafter referred to as an acid crosslinking compound) is an amino compound having at least two alkoxymethyl groups, methylol groups, acetoxymethyl groups and the like as functional groups, for example, hexamethylol Melamine, melamine derivatives (hexamethoxymethylated melamine (Cimel 300 series (1) manufactured by Mitsui Cyanamid Co., Ltd.)), benzoguanamine derivatives (methyl / ethyl mixed alkylated benzoguanamine resin (Cimel 1100 manufactured by Mitsui Cyanamid Co., Ltd.)
Series (2)), etc.), glycoluril derivatives (tetramethylol glycoluril (Cymel 1100 series (3) manufactured by Mitsui Cyanamid Co., Ltd.)), and alkoxymethyl group, methylol group as a functional group,
At least disubstituted aromatic compounds having an acetoxymethyl group and the like, for example, 1,3,5-triacetoxymethylbenzene, 1,2,4,5-tetraacetoxymethylbenzene, etc., are described in Polym. Maste
r. Sci. Eng. , 64, 241 (1991).

As the acid crosslinking compound, in addition to the above, resole resins and furan resins can also be used. Further, an acrylic resin synthesized from monomers including the following monomers can be used.

N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylol acrylamide, N, N-dimethylol methacrylamide, N
-(2-hydroxyethyl) acrylamide, N- (2
-Hydroxyethyl) methacrylamide, N, N-di (2-hydroxyethyl) acrylamide, N, N-di (2-hydroxyethyl) methacrylamide, N-hydroxymethyl-N- (2-hydroxyethyl) acrylamide, N -Hydroxymethyl-N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether, vinylbenzyl alcohol, α-methylvinylbenzyl alcohol, vinylbenzyl acetate, α-
An embodiment in which any one of methylvinylbenzyl acetate, vinylphenethyl alcohol, α-methylvinylphenethyl alcohol, vinylphenethyl acetate, and α-methylvinylphenethyl acetate is copolymerized in an amount of 1 to 50 mol%, preferably 5 to 30 mol%. .

The content of the acid crosslinking compound of the present invention is preferably from 5 to 60% by mass, particularly preferably from 10 to 30% by mass, based on the total solid content of the composition for forming the image forming layer. One kind of the acid crosslinking compound may be used alone, or two or more kinds may be used as a mixture.

In the present invention, various known UV absorbers can be used, for example, salicylic acid type,
Benzophenone-based, benzotriazole-based, cyanoacrylate-based and the like can be mentioned, and specific examples of these are shown below.

P-tert-butylphenyl salicylate p-octylphenyl salicylate phenyl salicylate 2,4-dihydroxybenzophenone 2-hydroxy-4-methoxybenzophenone 2-hydroxy-4-octoxybenzophenone 2-hydroxy-4-dodecyloxybenzophenone 2 2,2'-Dihydroxy-4-methoxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 2-hydroxy-4-methoxy-5-sulfobenzophenone 2- (2'-hydroxy-5'-methoxyphenyl) Benzotriazole 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole 2- (2'-hydroxy-3 ', 5'-di-tert-
Butylphenyl) benzotriazole 2- (2'-hydroxy-3'-tert-butyl-
5'-methylphenyl) -5-benzotriazole 2- (2'-hydroxy-3 ', 5'-di-tert-
(Butylphenyl) -5-chlorobenzotriazole 2- (2'-hydroxy-3 ', 5'-di-tert-
Amylphenyl) benzotriazole 2- (2'-hydroxy-3 ', 5'-bis (α, α'
Dimethylbenzylphenyl))-5-chlorobenzotriazole Preferred among these ultraviolet absorbers are benzophenone-based, benzotriazole-based, and cyanoacrylate-based ones.

These ultraviolet absorbers may be used alone or in combination of two or more. The amount of the ultraviolet absorber to be added is selected in consideration of the laser light source (absorption wavelength, intensity) to be used.
It is preferably in the range of 0.01 to 10 g per ² and particularly preferably in the range of 0.1 to 5 g.

Further, in the present invention, compounds represented by the following general formulas (V) to (VIII) can be contained in the image forming layer as a visible image dye.

[0089]

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In the general formulas (V) to (VIII), R ₁ to
R ₃ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylhydroxy group, or an alkyloxy group, X represents a halogen atom, an anion molecule, and Y represents a sulfur atom or an oxygen atom.

The alkyl group represented by R _{1 to} R ₃ has 1 to 1 carbon atoms.
It is a linear or branched alkyl group having 5 carbon atoms, and preferably has 1 to 3 carbon atoms. The alkoxy group is preferably a methoxy group, an ethoxy group, or a butoxy group, the alkylhydroxy group is preferably a hydroxymethyl group, a hydroxyethyl group, and the alkyloxy group is a methoxymethyl group, a methoxyethyl group, or an ethoxymethyl group. And an ethoxyethyl group. X is a halogen atom or an anion molecule. As the halogen atom, chlorine, bromine or iodine is preferable.
/ ₂ ZnCl ₂ or the like is preferable, but there is no particular limitation.

The amount of the compound represented by any of formulas (V) to (VIII) added to the image forming layer is 0.1
The mass is preferably from 10% by mass to 10% by mass, more preferably from 0.5% by mass to 5% by mass.

The absorption maximum of the exposure wavelength of the compounds represented by the general formulas (V) to (VIII) may be any wavelength as long as it is preferable to have a visible image. Therefore, there is no limitation as long as the wavelength does not absorb the wavelength in this region. However, it is very preferable to respond to a wavelength of 400 to 700 nm in order to achieve the effects of the present invention.

Specific examples of the compounds represented by formulas (V) to (VIII) are shown below, but the present invention is not limited to them.

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Examples of the novolak resin which functions as a binder in the present invention include phenol-formaldehyde resin, cresol-formaldehyde resin, and
Phenol as described in US Pat.
Cresol / formaldehyde copolycondensate resins, and copolycondensate resins of p-substituted phenol and phenol or cresol and formaldehyde, as described in JP-A-55-127553.

In the image forming layer, in addition to the novolak resin,
An acrylic resin can be contained. The acrylic resin is a polymer having acrylic acid, methacrylic acid, or an ester thereof as a constituent unit, and is preferably a polymer having a monomer unit represented by the following general formula (IX).
Novolak resin is 20 to 80% by mass based on the image forming layer.
The acrylic resin is preferably contained in the range of 1 to 50% by mass, more preferably 5 to 30% by mass, based on the image forming layer.

[0098]

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In the formula (IX), R ₁ and R ₂ each represent a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or a carboxyl group, and is preferably a hydrogen atom.
R ₃ represents a hydrogen atom, a halogen atom such as a chlorine atom or a bromine atom, or an alkyl group such as a methyl group or an ethyl group, and is preferably a hydrogen atom or a methyl group. R ₄ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a phenyl group or a naphthyl group.

Y represents a phenylene group or a naphthylene group including those having a substituent; examples of the substituent include an alkyl group such as a methyl group and an ethyl group; a halogen atom such as a chlorine atom and a bromine atom; a carboxyl group; Examples thereof include an alkoxy group such as an ethoxy group, a hydroxyl group, a sulfo group, a cyano group, a nitro group, an acyl group, and the like, and preferably have no substituent or are substituted with a methyl group.

X is a divalent organic group linking a nitrogen atom and an aromatic carbon atom, and n represents an integer of 0 to 5, and is preferably 0.

The polymer having the structural unit represented by the general formula (IX) is more specifically exemplified by the following (a) to (f)
Can be represented by

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In (a) to (f), R _{1 to} R ₅ each represent a hydrogen atom, an alkyl group or a halogen atom;
m, n, l, k and s represent mol% of each structural unit.

A preferred embodiment of the present invention is an embodiment in which the image forming layer contains a novolak resin and a nonionic surfactant. As nonionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer,
Sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkyl alkanolamide, polyethylene glycol and the like can be mentioned. The novolak resin is preferably contained in the range of 20 to 80% by mass based on the image forming layer, and the nonionic surfactant is used in the image forming layer.
It is preferably contained in the range of 0.01 to 10% by mass, and more preferably in the range of 0.1 to 1.0% by mass.

The image forming layer of the present invention may contain 0.001 to 5% by mass of a fluorine-containing surfactant.
This is preferable from the viewpoint of preventing the generation of stains in the non-image portion due to aging.
Examples of the fluorine-based surfactant include the following compounds.

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As the fluorinated surfactant, commercially available products can be used. For example, Surflon “S-381”, “S
-382 "," SC-101 "," SC-102 ",
"SC-103", "SC-104" (all manufactured by Asahi Glass Co., Ltd.), Florard "FC-430", "FC-4"
31 ”and“ FC-173 ”(both are fluorochemical-
Sumitomo 3M Ltd.), F-top "EF35
2, "EF301", "EF303" (all manufactured by Shin-Akita Kasei Co., Ltd.), "Shbego Fuller" 8035,
“8036” (all manufactured by Schwegman), “BM1
000 "," BM1100 "(all manufactured by BM Himmy), MegaFac" F-171 "," F-17 "
7 "(all manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

In the present invention, the fluorine content of the fluorine-containing surfactant is 0.05 to 2%, preferably 0.1 to 1%.
%. The amount added to the protective layer is 0.001 to 10
% Is preferred. The above-mentioned fluorine-based surfactants can be used alone or in combination of two or more, and can be used in combination with other surfactants.

A lipophilic resin can be added to the image forming layer of the present invention in order to improve the oil sensitivity of the image forming layer.

Examples of the lipophilic resin include a condensate of a phenol substituted with an alkyl group having 3 to 15 carbon atoms and an aldehyde, for example, t-butylphenol, as described in JP-A-50-125806. Formaldehyde resin and the like can be used.

The image-forming material of the present invention can be produced by dissolving the components for forming the image-forming layer in a solvent, coating the solution on a suitable support surface, and drying to provide the image-forming layer. .

Solvents that can be used include, for example, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether,
Diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, ethyl formate, Propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, methyl ethyl ketone, cyclohexanone, methyl Cyclohexanone, diacetone Alcohol, acetylacetone,
γ-butyrolactone and the like. These solvents are
They can be used alone or in combination of two or more.

The coating method used for coating the photosensitive composition on the surface of the support may be a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, static spraying. Methods such as electric air spray coating, roll coating, blade coating, and curtain coating are used. At this time, the coating amount varies depending on the application, but for example, 0.05 to 5.0 g / solid content.
An application amount of m ² is preferred.

For processing the image forming material of the present invention, a conventional method is applied. That is, by exposing through a transparent original image having a line image, a halftone dot image, and the like, and then developing with an aqueous developer, a negative relief image can be obtained for the original image. Examples of a light source of active light suitable for exposure include a carbon arc lamp, a mercury lamp, a xenon lamp, a metal halide lamp, a strobe, a laser beam, and the like.The photosensitive composition of the present invention includes a visible light laser such as an argon ion laser. It has a sufficient sensitivity to, and is preferably used for performing scanning exposure based on digitized information using a visible light laser such as an argon ion laser.

When an array type light source such as a light emitting diode array is used, or when a light source such as a halogen lamp, a metal halide lamp, or a tungsten lamp is controlled to be exposed by an optical shutter material such as a liquid crystal or PLZT, an image signal is used. It is possible to perform a corresponding digital exposure. In this case, writing can be performed directly without using a mask material.

In the case of a laser, light can be focused in a beam form and scanning exposure can be performed in accordance with image data. Therefore, it is suitable for directly writing without using a mask material. When a laser is used as a light source, the exposure area can be easily reduced to a minute size, and high-resolution image formation can be performed.

The laser light source used in the present invention is generally well-known as long as it has an oscillation wavelength in the visible light region, a solid-state laser such as a YAG laser, a second harmonic of the YAG laser, a glass laser, or the like. He-Ne
Laser, CO ₂ laser, Ar ion laser, Kr
Gas lasers such as ion lasers and He-Cd lasers, other discharge-excited molecular lasers, excimer lasers, chemical lasers, dye lasers, and semiconductor lasers can be used. Among them, the second harmonic of YAG laser, He-Ne laser, semiconductor laser,
Ar ion lasers are preferred.

Among the semiconductor lasers, at the focal point without significantly lowering the optical efficiency, 1 / e ² several μm in diameter
It is preferable to use a so-called single mode laser diode as it is easy to narrow down to m to several tens μm. Light sources other than lasers include light emitting diodes (LE
D). LEDs and semiconductor lasers that are easy to use as an array in which a plurality of light-emitting elements are integrated are LEDs and semiconductor lasers.

When a light source having a wavelength of about 400 to 550 nm is required, a semiconductor laser or YA
It is also possible to convert to a half wavelength by combining a G laser with an element having a nonlinear optical effect.

As a laser scanning method, there are a cylinder outer surface scan, a cylinder inner surface scan, and a plane scan. In the cylinder outer surface scanning, laser exposure is performed while rotating a drum around which a recording material is wound around the outer surface, and rotation of the drum is main scanning and movement of laser light is sub scanning. In the cylinder inner surface scanning, a recording material is fixed on the drum inner surface, a laser beam is irradiated from the inside, and a part or all of the optical system is rotated to perform a main scanning in the circumferential direction, and a part of the optical system or Sub-scanning is performed in the axial direction by moving the whole linearly in parallel with the axis of the drum. In the planar scanning, the main scanning of the laser beam is performed by combining a polygon mirror or a galvanometer mirror with an Fθ lens or the like, and the sub-scanning is performed by moving the recording medium. Scanning of the outer surface of the cylinder and scanning of the inner surface of the cylinder are easier to improve the accuracy of the optical system, and are suitable for high-density recording. In the case of scanning the outer surface of the cylinder, it is easy to increase the scanning speed by increasing the rotation speed of the drum. However, the increase in the rotation speed tends to cause charging of the recording material, thereby attracting dust and causing image defects. In the case of so-called multi-channel exposure in which a plurality of light emitting elements are used at the same time, scanning of the outer surface of a cylinder is most suitable.

The developer used for developing the image-forming material of the present invention may be any of known ones.
It is preferable to use a liquid containing a specific organic solvent, an alkali agent and water as essential components. Here, the specific organic solvent is capable of dissolving or swelling the non-exposed portion (non-image portion) of the above-mentioned photosensitive composition layer when it is contained in a developer, and at normal temperature (20 ° C.) An organic solvent having a solubility in water of 10% by mass or less. Such an organic solvent only has to have the above-mentioned properties, and is not limited to the following. However, examples thereof include ethyl acetate, propyl acetate, and butyl acetate. Carboxylic acid esters such as amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, and butyl replate; ketones such as ethyl butyl ketone, methyl isobutyl ketone and cyclohexanone; ethylene glycol monobutyl ether; ethylene glycol benzyl ether; ethylene Glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, alcohols such as n-amyl alcohol, methyl amyl alcohol, alkyl-substituted aromatic hydrocarbons such as xylene, methylene dichloride, ethylene Chloride, and the like halogenated hydrocarbons monochlorobenzene and the like. One or more of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. The content of these organic solvents in the developer is generally from 0.001 to 20% by mass, and particularly preferably from 0.01 to 10% by mass.

On the other hand, examples of the alkaline agent contained in the developer include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium or ammonium salt of secondary or tertiary phosphoric acid, Sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine,
Examples include diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneamine, and ethylenediamine.

Preferred are potassium silicate, sodium silicate, dibasic sodium phosphate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, monoethanolamine, diethanolamine and triethanolamine. The alkali agents may be used alone or in combination of two or more. The content of these alkali agents in the developer is usually 0.05 to 8% by mass, preferably 0.5 to 6% by mass.
% By mass.

In order to further improve the storage stability, printing durability and the like, it is preferable to add a water-soluble sulfite to the developer as required. As such a water-soluble sulfite, an alkali or alkaline earth metal sulfite is preferable, and examples thereof include sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite.
The content of these sulfites in the developer composition is usually 0.05 to 4% by mass, and preferably 0.1 to 1% by mass.

Further, a certain solubilizing agent may be contained to assist the dissolution of the above-mentioned specific organic solvent in water. As such a solubilizing agent, it is preferable to use low molecular weight alcohols and ketones which are more water-soluble than the specific organic solvent used. Further, an anionic surfactant, an amphoteric surfactant and the like can also be used. Examples of such alcohols and ketones include methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol,
Ethoxybutanol, 4-methoxymethylbutanol,
It is preferable to use N-methylpyrrolidone or the like. As the surfactant, for example, sodium isopropylnaphthalenesulfonate, sodium n-butylnaphthalenesulfonate, sodium N-methyl-N-pentadecylaminoacetate, sodium lauryl sulfate, and the like are preferable. The amount of these solubilizers such as alcohols and ketones is not particularly limited, but is generally preferably about 30% by mass or less based on the whole developer.

[0127]

EXAMPLE 1 "Preparation of Support" An aluminum plate (material: 1050, tempered H16) having a thickness of 0.3 mm was degreased with a 5% aqueous sodium hydroxide solution maintained at 65 ° C. for 1 minute. After the cleaning, it was washed with water, immersed in a 10% aqueous sulfuric acid solution kept at 25 ° C. for 1 minute, neutralized, and further washed with water. This aluminum plate was placed in a 1.0% by mass aqueous nitric acid solution at a temperature of 25 ° C
Electrolytic surface roughening was performed with an alternating current under the conditions of a current density of 10 A / dm ² and a processing time of 60 seconds.

Next, in a 5% aqueous sodium hydroxide solution,
A desmut treatment is performed at a temperature of 60 ° C. for 10 seconds, and then in a 20% sulfuric acid solution at a temperature of 20 ° C. and a current density of 3 A / dm.
^2. Anodizing treatment was performed under the condition of a treatment time of 1 minute. Then, it was immersed in a 1% aqueous solution of ammonium acetate kept at 80 ° C. for 30 seconds, washed with water and dried at 80 ° C. for 3 minutes. Furthermore, carboxymethylcellulose (C
MC (hereinafter abbreviated as below)
After immersion for 2 seconds, it was dried at 80 ° C. for 5 minutes to prepare a support.

<Production Example 1> Novolak resin A 300 ml separable flask was charged with phenol 3.4.
8 g, meta-cresol 45.84 g, para-cresol 3
0.56 g, formalin (37% aqueous solution) 32.1 g,
Oxalic acid (0.16 g) was charged, and the mixture was heated and stirred in a 110 ° C. oil bath for 3 hours to react. The product was dried under reduced pressure to obtain a novolak resin. The weight average molecular weight of the resin thus obtained was 3,700.

<Production Example 2> Acid-decomposable compound 58 g of 1,1-dimethoxycyclohexane, 85 g of diethylene glycol, 194 mg of p-toluenesulfonic acid
And 200 ml of toluene were mixed and reacted at 120 ° C. for 11 hours while stirring. After completion of the reaction, methanol and reaction solvent generated by the reaction were removed, and 200
After washing with water (ml), the solution was washed with 400 ml of a 1% aqueous sodium hydroxide solution, and then washed with saturated saline until neutral. The obtained compound was dehydrated with anhydrous potassium carbonate and then distilled under reduced pressure to obtain a target acid-decomposed compound.

(Photosensitive composition) Infrared absorber (IR25) 1 part by mass Acid generator ((III) -1) 3 parts by mass Acid-decomposable compound (Production Example 2) 20 parts by mass Novolak resin (Production Example 1) 73 3 parts by mass of compound C1 700 parts by mass of propylene glycol monomethyl ether 300 parts by mass of methyl ethyl ketone 300 parts by mass of the photosensitive solution having the above composition was dried
2.0 g / m dry mass ^TwoPaint with a wire bar
Cloth and dried in a 95 ° C. atmosphere for 90 seconds to form an image forming material.
Obtained.

The obtained photosensitive lithographic printing plate was subjected to image exposure using a semiconductor laser (absorption wavelength: 830 nm, output: 500 mW). The laser radius is 1 / the intensity at the peak
It was 13μm in e ^2. The resolution was 2000 dpi in both the scanning direction and the sub-scanning direction (dpi represents the number of dots per inch, that is, 2.54 cm). After the image exposure, the film was immersed in a Konica PS plate developer SDR-1 (manufactured by Konica Corporation) diluted to a predetermined concentration with water at 30 ° C. for 30 minutes, developed, washed with water and dried.

Evaluation of Sensitivity Under the above conditions, evaluation was made with exposure energy (mj / cm ² ) necessary for developing the exposed part.

Chemical Resistance The image obtained from the sensitivity evaluation image was immersed in a stock solution of Ultraplate Cleaner (manufactured by Dainichi Seika Co., Ltd.), washed with water, and visually compared with the image portion before immersion. Was evaluated. The image portion was slightly eroded, and the time during which the grain of the support under the image forming layer was slightly exposed was measured.

Erasability An image part having a width of 0.5 cm and a length of 10 cm was erased with an erasing solution RP-
Erased with 1S (manufactured by FUJIFILM Corporation) and washed with water.
Thereafter, a surface-regulating liquid was applied to the plate surface, heated at 250 ° C. for 6 minutes, washed again with water, and a developing ink SPO-1 (manufactured by Konica Corporation) was applied to the plate surface. At this time, it was confirmed whether or not stains with ink were observed around the trace of the erasing liquid.

：: No stain is observed. Δ: No stain is observed visually, but when a loupe is used, stain is observed. X: Stain is visually observed. Examples 2 to 22 Compound C1 in photosensitive composition Was replaced with C2 to C22, and the same evaluation as in Example 1 was performed.

Comparative Example 1 The same evaluation as in Example 1 was performed, except that Compound C1 in the photosensitive composition was replaced with R1.

Comparative Example 2 A photosensitive composition was replaced with the following.
The same evaluation as in Example 1 was performed.

Infrared absorber (IR25) 1 part by mass Acid generator ((III) -1) 3 parts by mass Acid-decomposable compound (Production Example 2) 20 parts by mass Novolak resin (Production Example 1) 61 parts by mass Compound R1 15 parts by mass Part Propylene glycol monomethyl ether 700 parts by weight Methyl ethyl ketone 300 parts by weight Comparative Example 3 The same evaluation as in Example 1 was carried out except that the photosensitive composition was changed to the following.

Infrared absorber (IR25) 1 part by mass Acid generator ((III) -1) 3 parts by mass Acid-decomposable compound (Production Example 2) 20 parts by mass Novolak resin (Production Example 1) 76 parts by mass propylene glycol monomethyl ether 700 parts by mass Methyl ethyl ketone 300 parts by mass

[0141]

[Table 5]

From Table 5, it can be seen that Examples 1 to 22, ie, the sample of the present invention, are superior to the comparative sample in chemical resistance and erasability.

[0143]

According to the present invention, elution and peeling of an image area due to a cleaner wiping operation at the time of a printing operation using a photosensitive lithographic printing plate, and furthermore, an erase fringe stain caused by using a correction liquid can be improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/40 511 G03F 7/40 511

Claims (8)

[Claims] An image forming layer on a support, wherein the image forming layer contains a novolak resin, an infrared absorber and a compound containing a repeating unit represented by the following general formula (1),
An image forming material, which forms an image by laser exposure. Embedded image (Wherein, A represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, X represents an alkylene, and Y represents a group substituted by a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a phosphonoxy group, a dialkyl Represents a phosphonoxy group, a trialkoxysilyl group, or an alkyldialkoxysilyl group.) 2. An image forming layer on a support, wherein the image forming layer is composed of a novolak resin, an infrared absorber, a group in which Y in the general formula (1) is substituted by a carboxyl group, a sulfo group, and a phosphonoxy group. Contains at least one selected compound containing a repeating unit represented by the general formula (1) and at least one compound selected from organic amine compounds, organic aniline compounds, alkali metal hydroxides and alkali metal salts, and forms an image by laser exposure. An image forming material comprising: 3. An image forming layer on a support, wherein the image forming layer contains a novolak resin, an infrared absorbent and a compound containing a repeating unit represented by the following general formula (2):
An image forming material, which forms an image by laser exposure. Embedded image (Wherein, R _{1 to} R ₅ are the same or different and are each a group selected from a hydrogen atom, a halogen atom, an alkyl, an alkoxy, an alkoxycarbonyl, an acyl, an aryloxy, an aralkyl, a hydroxyl, a cyano, an amide, a nitro and an amino group. Provided that at least one is a hydroxyl group.) 4. The image forming material according to claim 1, wherein the solubility of the exposed portion in an alkaline aqueous developer is changed by laser exposure. 5. The image forming material according to claim 1, wherein the image forming layer contains a compound that generates an acid by decomposing in the image forming layer and a compound that decomposes in the presence of the acid. 6. The image-forming material according to claim 1, wherein the image-forming layer contains a compound that generates an acid by being decomposed in the image-forming layer and a compound that is cross-linked by the presence of the acid. 7. A coating solution obtained by adding a novolak resin, an infrared absorbing agent, and a compound containing a repeating unit selected from the general formula (1) or (2) to a support. A method for producing an image forming material. 8. A support represented by the general formula (1) selected from a novolak resin, an infrared absorber, a group in which Y of the general formula (1) is substituted by a carboxyl group, a sulfo group, and a phosphonoxy group on a support. At least one compound selected from a compound containing a unit, an organic amine compound, an organic aniline compound, an alkali metal hydroxide and an alkali metal salt.
A method for producing an image forming material, comprising applying a coating liquid obtained by adding a seed.