JP2001066776A - Image-forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type image forming material capable of recording from digital data of a computer or the like, using IR-emitting solid-state laser and semiconductor laser and having high sensitivity with respect to IR laser light. SOLUTION: Relating to this image-forming material a 1st layer in which a chemical bond is cleaved with an acid generated by the action of light or heat as a catalyst to increase the solubility of the layer in an alkali developing solution is disposed on a substrate and a 2nd layer, in which an acid generating agent is decomposed with an acid generated by the action of light or heat as a catalyst and an acid is propagated, is disposed on the 1st layer to obtain the object image-forming material. The 1st layer and/or the 2nd layer contains an IR absorber.

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 sensitivity to an infrared wavelength region, and more particularly, to a so-called direct plate making positive type lithographic plate capable of making a plate directly from a digital signal of a computer or the like by using an infrared laser. The present invention relates to an image forming material suitable for a printing plate.

[0002]

2. Description of the Related Art In recent years, the development of lasers has been remarkable. In particular, solid-state lasers and semiconductor lasers (hereinafter sometimes referred to as "infrared lasers") which emit infrared light having a wavelength of 760 nm to 1200 nm have high output and small size. Is now readily available. These infrared lasers are very useful as recording light sources when directly making a printing plate using digital data from a computer or the like.
Therefore, there is a growing demand in recent years for an image recording material having high sensitivity to such an infrared recording light source, that is, an image recording material in which a photochemical reaction or the like is caused by irradiation with infrared rays and the solubility in a developing solution is greatly changed. .

Conventionally, an image forming material having a photosensitive layer containing an acid generator and an acid-decomposable compound has been known as a positive photosensitive layer solubilized by irradiation with actinic light. U.S. Pat. No. 3,779,779 discloses a photosensitive composition containing a compound having an orthocarboxylic acid or a carboxylic acid amide acetal group, and Japanese Patent Application Laid-Open No. 53-133429 has an acetal or ketal group in the main chain. The photosensitive composition containing the compound is disclosed in JP-A-60-37.
No. 549 discloses a composition containing a compound having a silyl ether group. However, these are sensitive to ultraviolet light, are alkali-solubilized by exposure to ultraviolet light and become non-image parts, and cannot be used for image exposure with infrared light such as inexpensive and compact semiconductor lasers. That is, since infrared rays have lower energy than ultraviolet rays used as a conventional light source for exposure, exposure to infrared rays causes a photoreaction or the like in a compound such that the solubility of an image recording material in a developing solution is greatly changed. There was a problem that it was difficult to do.

On the other hand, US Pat. No. 5,340,699 discloses a technique capable of exposing an image with infrared rays such as a semiconductor laser.
The specification has a photosensitive layer containing an acid generator, a resole resin, a novolak resin and an infrared absorber, and is used as a negative image by performing a heat treatment before image development and after image exposure. Techniques are disclosed. This material has a problem that a positive type image is not formed unless the above heat treatment is performed, and further, both the negative type and the positive type have low sensitivity. In recent years, JP-A-9-171254 discloses an image forming material having a photosensitive layer containing an acid generator, an acid-decomposable compound and an infrared absorber. In this system, the acid-decomposable compound is decomposed by the acid generated by the irradiation of active light as a catalyst to form a positive image, so that a large amplification effect is obtained chemically. Although the positive effect resulting from the conversion is excellent (development is suppressed in the unexposed area and released or eliminated in the exposed area), the heat generated near the surface does not sufficiently reach the deep part of the material. When a typical aluminum support is used, there is a problem of heat diffusion near the support, and the positive action in the deep part is insufficient. As a result, the discrimination between the non-exposed area and the exposed area is hardly clarified even with alkali development, and further improvement in sensitivity has been desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to enable direct plate making by recording from digital data of a computer or the like using a solid-state laser or a semiconductor laser that emits infrared light. An object of the present invention is to provide a sensitive positive type image forming material.

[0006]

Means for Solving the Problems The present inventors have intensively studied a positive type image forming material capable of directly making a plate by radiating infrared rays. Focusing on the fact that the thermal efficiency deteriorates due to high speed, causing a difference in thermal efficiency between the vicinity of the support and the upper layer of the photosensitive layer. To reduce the difference in thermal efficiency, an acid generator using an acid generated by the action of light or heat as a catalyst to reduce the difference in thermal efficiency Utilizing the properties of a layer that decomposes and proliferates an acid, and as a result of providing this layer on the upper layer side of the photosensitive material, it was found that the above problems could be solved, and the present invention was completed. That is, the present invention provides, on a support, a first layer (hereinafter referred to as a first layer) in which an acid generated by the action of light or heat acts as a catalyst to cleave a chemical bond and increase solubility in an alkali developing solution.
It is called a chemically amplified positive image forming layer. ) And above it,
An image forming material provided with a second layer (hereinafter, referred to as an acid multiplying layer) that decomposes an acid generator by using an acid generated by the action of light or heat as a catalyst to multiply the acid.

In the present invention, when infrared rays are radiated imagewise by an infrared laser or the like, the exposed portion of the image forming material is exposed to the acid propagated in the second layer (acid breeding layer) in the first layer (chemically growing layer). The solubility in an alkaline developer in the amplified positive image forming layer) increases. Therefore, in the exposed portion after the development, both the first layer and the second layer are efficiently dissolved and removed by the developer to obtain a positive plate material for lithographic printing. When producing this positive type lithographic printing plate material, the light transmittance of the photosensitive material decreases from the surface of the photosensitive material toward the support, the light can be used more efficiently on the surface of the photosensitive material, Particularly in the case of heat mode laser type photosensitive materials, there is a problem of thermal diffusion to the support, but by providing an acid multiplying layer on the upper layer, a large amount of acid is generated in the upper layer,
High sensitivity can be realized by diffusing these acids into the lower layer. Also, at this time, the lower layer has a heat insulating effect,
Efficient reaction in the lower layer proceeds by reducing heat diffusion to the support, so that solubility in an alkali solution is improved and high sensitivity can be realized.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. The present invention is characterized in that a chemically amplified positive image forming layer and an acid multiplying layer are sequentially provided on at least a support. These layers may be provided in this order, and may further include known layers such as a surface layer, an intermediate layer, and a back coat layer as long as the effects of the present invention are not impaired.

The chemically amplified positive image forming layer contains a compound (acid-decomposable compound) which cleaves a chemical bond by using an acid generated by the action of light or heat as a catalyst and increases the solubility in an alkali developing solution as an essential component. The compound that generates an acid by the action of light or heat (acid generator) is preferably contained in the chemically amplified positive image forming layer, but is not necessarily contained. When an acid generator is not contained in the chemically amplified positive image forming layer, an acid generator can be contained in the acid breeding layer, and the above-mentioned acid-decomposable compound can be decomposed by an acid diffused from the acid breeding layer. In the chemically amplified positive image forming layer,
Further, a polymer compound which is a binder component for forming this layer may be contained, and the acid-decomposable compound itself may be a polymer compound which functions as a binder component or a precursor thereof.

[Acid-Decomposable Compound] In the present invention, a compound that cleaves a chemical bond by using an acid as a catalyst and increases solubility in an alkali developing solution is a compound having a bonding group that can be decomposed by an acid in a molecule. Can be replaced. Such a compound is disclosed in JP-A-9-171254, "(b) Compound having at least one decomposable bond with acid"
Can be used. The coupling capable of being decomposed by an acid, for _{example, - (CH 2 CH 2 O} ) n -
Preferred examples include a group (n represents an integer of 2 to 5) and the like. Among such compounds, it is preferable to use a compound represented by the following general formula (1) from the viewpoint of sensitivity and developability.

[0011]

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Wherein R, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
Represents an alkoxy group, a sulfo group, a carboxyl group or a hydroxyl group, p, q and r each represent an integer of 1 to 3, and m and n each represent an integer of 1 to 5. ]

In the general formula (1), the alkyl group represented by R, R ¹ and R ² may be linear or branched, for example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl. And a pentyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group,
Examples include a tert-butoxy group and a pentoxy group, and the sulfo group and the carboxyl group include salts thereof. Among the compounds represented by the general formula (1), compounds wherein m and n are 1 or 2 are particularly preferred. The compound represented by the general formula (1) can be synthesized by a known method.

Other acid-decomposable compounds applicable to the present invention include JP-A-48-89603 and JP-A-51-12.
Nos. 0714, 53-133429 and 55-129
No. 95, No. 55-126236, No. 56-17345
Having a C--O--C bond as described in
-37549, 60-114446
Compounds having a -OC bond, JP-A-60-3625
And other acid-decomposable compounds described in JP-A-60-10247.
No. 22246, compounds having a Si--N bond, carbonates described in JP-A-62-251743, orthocarbonates described in JP-A-62-209451, and JP-A-62-209451. Ortho titanate described in JP-A-280841;
Orthosilicate described in JP-A-280842, JP-A-63-010153, JP-A-9-1712
No. 54, No. 10-55067, No. 10-111564
No., 10-87733, 10-153853,
No. 10-228102, No. 10-268507, No. 282648, No. 10-282670, EP-08
Acetals, ketals and orthocarboxylic esters described in 84547 Al, JP-A-62-2440.
Compounds having a CS bond described in No. 38 can be used.

Among the above-mentioned acid-decomposable compounds, in particular, JP-A-53-133429, JP-A-56-17345, and JP-A-60-17345.
No. 112446, No. 60-37549, No. 62-2
09451, 63-010153, JP-A-9-19-1
No. 71254, No. 10-55067, No. 10-111
No. 564, No. 10-87733, No. 10-15385
No. 3, No. 10-228102, No. 10-268507
No., No. 282648, No. 10-282670, EP
0884647Al CO—O— described in each specification
Compounds having a C bond, compounds having a Si-OC bond, orthocarbonates, acetals, ketals, and silyl ethers are preferred. Among these acid-decomposable compounds, a polymer compound having a repeating acetal or ketal portion in the main chain and increasing its solubility in an alkaline developer by the generated acid is preferably used.

These acid-decomposable compounds are used in an amount of 5 to 70% by weight, preferably 10 to 50% by weight, more preferably 15 to 35% by weight based on the total solids of the chemically amplified positive-working image forming layer.
In the layer. If the addition amount is less than 5% by weight, stains on the non-image area are likely to occur, and the addition amount is 7%.
If it exceeds 0% by weight, the film strength of the image area is insufficient, and both are not preferred.

As the precursor of the acid-decomposable compound, an enol ether type crosslinking agent described in JP-A-8-220755 can be used. This compound is a compound having at least two enol ether groups represented by the following general formula (2) in the molecule, and contains this compound and a general-purpose alkaline water-soluble resin having an acid group in the molecule. By forming a coating solution to be formed and drying by heating to form a layer, the compound having an enol ether group and the alkali water-soluble polymer having an acid group are thermally crosslinked at the time of heating, and a layer insoluble in an alkali developing solution. Is formed, but by irradiating this with a laser beam imagewise, only the exposed portion is hydrolyzed by the generated acid and becomes soluble in an alkali developing solution.

[0018]

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In the formula, R ¹ , R ² and R ³ represent hydrogen, an alkyl group or an aryl group, which may be the same or different. Also, two of them may combine to form a saturated or olefinically unsaturated ring.

Examples of the compound having two or more enol ether groups which can be used in the present invention include the compounds described in JP-A-8-2
No. 20752, paragraph numbers [0030] to [005]
1]. Further, as the alkali water-soluble polymer used in combination with this compound in the layer formation, an alkali water-soluble polymer described in detail in the positive recording layer described later can be suitably used.

The compound having two or more enol ether groups, which is a precursor of the acid-decomposable compound, is contained in an amount of 1 to 80% by weight, preferably 3 to 80% by weight based on the total solid content of the chemically amplified positive image forming layer.
５０50% by weight, more preferably 5-30% by weight is added to the layer. When the addition amount is less than 1% by weight, the film strength is insufficient, and when the addition amount exceeds 80% by weight, stains on the image area occur, which is not preferable.

[Acid Generator] In the present invention, the compound capable of generating an acid by light or heat (acid generator) refers to a compound capable of generating an acid when decomposed by irradiation with infrared rays or heating at 100 ° C. or more. The generated acid is preferably a strong acid having a pKa of 2 or less, such as sulfonic acid and hydrochloric acid. The acid generated from the acid generator functions as a catalyst, the chemical bond in the acid-decomposable compound is cleaved, and this layer becomes soluble in an alkaline developer.

The acid generator preferably used in the present invention includes onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and the like.
Specifically, US Pat. No. 4,708,925 and JP-A-7-2
No. 0629. Particularly, an iodonium salt, a sulfonium salt, and a diazonium salt having a sulfonate ion as a counter ion are preferable.
As diazonium salts, US Pat. No. 3,867,14
7, the diazonium compound described in US Pat.
Also preferred are diazonium compounds described in 2,703 and diazo resins described in JP-A-1-102456 and JP-A-1-102457. Also, US Pat. No. 5,135,838 and US Pat.
Benzyl sulfonates described in U.S. Pat. No. 0,544 are also preferred. Further, active sulfonic acid esters and disulfonyl compounds described in JP-A Nos. 2-100054, 2-100055 and 8-9444 are also preferable. Besides, haloalkyl-substituted S-triazines described in JP-A-7-271029 are also preferable. Further, Japanese Unexamined Patent Application Publication No. Hei.
In JP-A-9-171254, compounds described as "acid precursors" or as "(a) compounds capable of generating an acid upon irradiation with actinic rays" in JP-A-9-171254 Can also be applied as the acid generator of the present invention.

When these acid generators are incorporated in the chemically amplified positive image forming layer, the acid generator is contained in an amount of 0.01 to 50% by weight, preferably 0.1 to 50% by weight, based on the total solid content of the chemically amplified positive image forming layer.
It is added to the layer in a proportion of 1 to 40% by weight, more preferably 0.5 to 30% by weight. When the amount is less than 0.01% by weight, it is difficult to obtain an image. On the other hand, if the amount exceeds 50% by weight, non-image areas are stained during printing.

These compounds may be used alone,
Also, two or more kinds may be used in combination. Since the acid generators listed here can be decomposed by irradiation with ultraviolet rays, the image recording material of the present invention can record images not only with infrared rays but also with irradiation with ultraviolet rays.

In the present invention, the solubility of the chemically amplified positive image forming layer in an alkali developing solution is increased by light or heat. The chemically amplified positive image forming layer contains a water-insoluble and alkali-water-soluble polymer (alkali-soluble polymer) as a binder polymer. The alkaline water-soluble polymer in the present invention is a homopolymer containing an acidic group in a main chain and / or a side chain in the polymer,
These copolymers or mixtures thereof are included. Therefore, the image forming material of the present invention forms a positive image and can be developed with an alkaline developer. Among them, those having an acidic group described in the following (1) to (6) in the main chain and / or side chain of the polymer are preferable in terms of solubility in an alkaline developer and expression of a dissolution inhibiting ability.

(1) Phenol group (—Ar—OH) (2) Sulfonamide group (—SO ₂ NH—R) (3) Substituted sulfonamide acid group (hereinafter referred to as “active imide group”) _{SO 2 NHCOR, -SO 2 NHSO 2} R, -CONHSO 2 R ] (4) carboxylic acid group (-CO ₂ H) (5) sulfonic acid group (-SO ₃ H) (6), a phosphoric acid 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. . The above (1)
Among the alkaline water-soluble polymers having an acidic group selected from (6) to (6), an alkaline water-soluble polymer having (1) a phenol group, (2) a sulfonamide group, and (3) an active imide group is preferable. Alkaline water-soluble polymers having (1) a phenol group or (2) a sulfonamide group are most preferred from the viewpoint of ensuring sufficient solubility in an alkaline developer, development latitude, and film strength.

Examples of the alkali water-soluble polymer having an acidic group selected from the above (1) to (6) include the following. (1) Examples of the alkaline water-soluble polymer having a phenol group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde, a condensation polymer of p-cresol and formaldehyde,
Condensed polymer of m- / p-mixed cresol and formaldehyde, phenol and cresol (m-, p- or m
-/ P- mixture) and a novolak resin such as a condensation polymer of formaldehyde, and a condensation polymer of pyrogallol and acetone. further,
Copolymers obtained by copolymerizing a compound having a phenol group in the 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.

Weight average molecular weight of alkaline water soluble polymer
Is 5.0 × 10^Two~ 2.0 × 10^Four And the number average molecular weight is
2.0 × 10^Two~ 1.0 × 10^FourWhat is image forming
It is preferred in terms of. In addition, these polymers are used alone
Not only can you use two or more kinds in combination
No. If combined, see US Pat. No. 4,123,279.
T-butyl phenol as described in US Pat.
And octylpheno
Number of carbon atoms, such as polycondensates of
A phenol having 3 to 8 alkyl groups as substituents;
A condensation polymer with formaldehyde may be used in combination.

(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 at least one polymerizable unsaturated group 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.

[0034]

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[Where X is¹, X^TwoAre independently-
O- or -NR²⁷Represents-. R^{twenty one}, R^{twenty four}Respectively
Independently a hydrogen atom or -CH_ThreeRepresents R^{twenty two}, R^{twenty five}, R
²⁹, R ³²And R³⁶Each independently has a substituent
An alkylene group having 1 to 12 carbon atoms, cycloalkyl
Represents a len group, an arylene group or an aralkylene group. R
^{twenty three}, R²⁷And R³³Are each independently a hydrogen atom, a substituent
An alkyl group having 1 to 12 carbon atoms which may have
Represents a loalkyl group, an aryl group or an aralkyl group.
Also, R²⁶, R³⁷Each independently has a substituent
C1-C12 alkyl group, cycloalkyl
Represents an aryl group or an aralkyl group. R ²⁸, R³⁰as well as
R³⁴Is independently a hydrogen atom or -CH_ThreeThe table
You. R³¹, R ³⁵Are each independently a single bond or substituted
An alkylene group having 1 to 12 carbon atoms which may have a group,
Cycloalkylene, arylene or aralkylene
Represents a group. Y^Three, Y^FourAre each independently a single bond,
Represents -CO-. ]

Among the compounds represented by the general formulas 1 to 5, in the positive lithographic printing material of the present invention, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (P-Aminosulfonylphenyl) acrylamide and the like can be suitably used.

(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. As the above compound, an active imide group, a polymerizable unsaturated group,
In the molecule.

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 at least one carboxylic acid group and at least one polymerizable unsaturated group in the molecule. Examples of the polymer may be a main component.

(5) Examples of the alkali-soluble polymer having a sulfonic acid group include, for example, a minimum structural unit derived from a compound having at least one sulfonic acid group and at least one polymerizable unsaturated group in the molecule. Examples of the polymer include a structural unit.

(6) The alkaline water-soluble polymer having a phosphate group includes, for example, a minimum structural unit derived from a compound having at least one phosphate group and at least one polymerizable unsaturated group in the molecule. Examples of the polymer may be a main component.

Among the above-mentioned alkali water-soluble polymers, (1) an alkali water-soluble polymer having a phenolic hydroxyl group, since strong interaction with the polyfunctional amine compound can be obtained. Is preferred.

The above-mentioned (1) to (10), which constitute the alkali water-soluble polymer used in the material for a positive planographic printing plate of the present invention.
The minimum structural unit having an acidic group selected from (6) does not need to be only one kind, and two or more types of the minimum structural units having the same acidic group or two or more types of the minimum structural units having different acidic groups may be used. Those copolymerized by more than one kind can also be used.

As the method of copolymerization, conventionally known methods such as graft copolymerization, block copolymerization, and random copolymerization can be used.

The above 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 having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and methacrylic esters. (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 used in the image forming material of the present invention has a weight average molecular weight of 1.0 × 10 ^{3 to} 2.0 × 1 regardless of whether it is a homopolymer or a copolymer.
0 ⁵ and the number average molecular weight is from 5.0 × 10 ^{2 to} 1.0 × 10 ²
Those having a range of ⁵ are preferable in terms of sensitivity and development latitude, and those having a polydispersity (weight average molecular weight / number average molecular weight) of 1.1 to 10 are preferable.

In the case where a copolymer is used in the present invention, the above-mentioned (1) to (10) which constitute the main chain and / or side chain thereof are used.
(6) The minimum constitutional unit derived from a compound having an acidic group selected from (6), and the other minimum constitutions (1) to (6), which do not contain an acidic group, constitute a part of a main chain and / or a side chain. The unit and the compounding weight ratio are, from the viewpoint of development latitude,
Those in the range of 50:50 to 5:95 are preferable, and
Those in the range of 0:60 to 10:90 are more preferred.

The alkali water-soluble polymer may be used alone or in combination of two or more, and may be used in combination with the total solid content of the material constituting the recording layer in the image forming material. , 30 to 99% by weight, more preferably 40 to 95% by weight, even more preferably 50 to 90% by weight. If the amount of the alkali water-soluble polymer is less than 30% by weight, the durability of the recording layer tends to deteriorate, and if it exceeds 99% by weight, the sensitivity and durability decrease. Each is not preferable because of the tendency.

Solvents that can be used in the synthesis of the alkali water-soluble polymer used in the present invention include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, 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.

(Acid Propagating Layer) In the present invention, an acid propagating layer is provided on the above-mentioned chemically amplified positive image forming layer.
The acid breeding layer contains at least an acid breeding agent that decomposes the acid generator using the acid generated by light and heat as a catalyst and multiplies the acid. That is, the acid multiplying layer contains at least an acid multiplying agent, and the acid generator is preferably contained in the acid multiplying layer, but is not contained in the acid multiplying layer but contained in the chemically amplified positive image forming layer. And both layers may contain an acid generator. When the acid generator is contained only in the chemically amplified positive image forming layer, the acid generated by the decomposition of the acid generator in the chemically amplified positive image forming layer diffuses into the acid multiplying layer, and the acid multiplying agent is removed. Via which the acid is multiplied.

(Acid multiplying agent) The acid multiplying agent in the present invention is a compound substituted by a relatively strong acid residue, and is easily desorbed in the presence of an acid catalyst to generate a new acid. Compound. That is, it is decomposed by an acid-catalyzed reaction and generates an acid (hereinafter, referred to as ZOH in the general formula) again. One or more acids are increased in one reaction, and the acid concentration increases rapidly with the progress of the reaction, so that the photosensitive speed is dramatically improved. The generated acid has an acid dissociation constant (pKa) of 3 or less, and more preferably 2 or less. If the acid is weaker than this, an acid-catalyzed elimination reaction cannot be caused.

Acid proliferating agents are described in WO95 / 29968, W.
No. O98 / 24000, JP-A-8-305262, JP-A-9-34106, JP-A-8-248561, JP-T-8-503082, U.S. Pat. No. 5,445,91
7, U.S. Pat. No. 5,503,083, U.S. Pat.
No. 4,393, US Pat. No. 5,395,736, US Pat. No. 5,741,630, US Pat.
No. 489, U.S. Patent No. 5,582,956, U.S. Patent No. 5,578,424, U.S. Patent No. 5,453,34.
No. 5, U.S. Pat. No. 5,445,917, European Patent No. 6
65,960; EP 757,628; EP 665,961; US Pat. No. 5,667,943.
And the acid proliferating agent described in JP-A-10-1598, etc.
Species can be used, or two or more can be used in combination.

The following compounds may be mentioned as specific examples of the acid multiplying agent in the present invention.

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These acid proliferating agents are contained in the acid proliferating layer at a concentration of 0.0
1-20% by weight, preferably 0.01-10% by weight, more preferably 0.1-5% by weight can be added.
When the addition amount of the acid multiplying agent is less than 0.01% by weight, the effect of the acid multiplying is small and does not contribute to the improvement of the photosensitivity. Also,
If the amount of the acid proliferating agent exceeds 20% by weight, adverse effects such as insufficient film strength in the image area occur, which is not preferable.

As a component other than the acid generator and the acid multiplying agent in the acid multiplying layer, it is desirable to contain a binder in the chemically amplified positive image forming layer. The acid generator used in the acid amplification layer may be the acid generator in the chemically amplified positive image forming layer.

(Infrared absorber) In the present invention,
It is preferable to add an infrared absorber to the chemically amplified positive image forming layer and / or the acid breeding layer from the viewpoint of photosensitivity,
In particular, it is preferable to add an infrared absorber to the acid breeding layer. Addition of the infrared absorber increases the generation of acid and the proliferation of acid due to the generated acid, the solubility of the chemically amplified positive-type image forming layer in the alkali developing solution by the acid increases, and the sensitivity is improved.

The infrared absorber usable in the present invention is not particularly limited as long as it has a function of generating heat by irradiation with an infrared laser. It is preferable to use a compound having an onium salt type structure, since it is necessary to exert the effect of being suppressed or being released or eliminated in the exposed portion and becoming soluble in alkaline water. Specifically, a cyanine dye,
Dyes such as pyrylium salts can be suitably used.

Preferred dyes described above include, for example, JP-A-58-125246, JP-A-59-84356,
JP-A-59-202829, JP-A-60-78787
Cyanine dyes described in US Pat.
No. 875, and the like.

Further, a near-infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and further, a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is used. Pyrylium salt, JP-A-57-14264
No. 5 (U.S. Pat. No. 4,327,169), a trimethinethiapyrylium salt described in JP-A-58-181051,
No. 58-220143, No. 59-41363, No. 5
Nos. 9-84248, 59-84249, 59-1
Pyrrilium compounds described in JP-A-46063 and JP-A-59-146061, cyanine dyes described in JP-A-59-216146, pentamethinethiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fairness 5-1
Pyrylium compounds disclosed in Nos. 3514 and 5-19702 are also preferably used.

Further, near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 can also be mentioned as preferable dyes. Furthermore, 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 but has an anionic structure in a mother nucleus of a dye that absorbs infrared light. For example, (c1) an anionic metal complex, (c1)
2) Anionic carbon black; (c3) anionic phthalocyanine; and (c4) a compound represented by the following general formula 6. The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.

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[0078] [Ga ^- represents an anionic substituent, Gb
Represents a neutral substituent. Xm ⁺ is 1 to m
And m represents an integer of 1 to 6. ]

Here, the (c1) anionic metal complex refers to an anion in which the central metal and the ligand in 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.

The anionic infrared absorber obtained by ionic bonding of an onium salt as a counter cation to the anionic group of the anionic carbon black is suitably used in the present invention. Is not included in the anionic infrared absorber suitably used in the present invention, and the effect of the present invention cannot be obtained with a mere adsorbate.

(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 to form an anion as a whole.

Next, the compound (c4) represented by the general formula 6 will be described in detail. In the general formula 6, M represents a conjugated chain, and the conjugated chain M may have a substituent or a ring structure. The conjugated chain M can be represented by the following formula.

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[Wherein 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. ]

Among the anionic infrared absorbers represented by the above general formula 6, the following A-1 to A-19 are preferably used.

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The following are examples of the infrared absorber having an onium salt structure, which is a preferred example of the infrared absorber used in the present invention. Specific examples (A-1 to A-56) of such an infrared absorbent are shown, but the present invention is not limited to these.

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[0109] In the structural formulas of A-1~A-56, T ^- A,
Represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a Lewis acid anion (B
F ₄ ⁻ , PF ₆ ⁻ , SbCl ₆ ⁻ , ClO ₄ ⁻ ), an alkyl sulfonate anion and an aryl sulfonate anion.
The alkyl herein refers to a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group,
Examples thereof include a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among them, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

[0110] The term "aryl" as used herein means one consisting of one benzene ring, two or three benzene rings forming a condensed ring, and benzene ring and a 5-membered unsaturated ring forming a condensed ring. Phenyl group,
Examples include a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

The dye as an infrared absorbing agent is contained in the material constituting the chemically amplified positive-type image forming layer and / or the acid propagation layer in an amount of 0.01 to 50% by weight, preferably 0.1 to 50% by weight, based on the total solid content. To 10% by weight, particularly preferably 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 material constituting the chemically amplified positive-type image forming layer or the acid multiplying layer in the image forming material of the present invention includes:
Further, for the purpose of improving sensitivity and development latitude, other dyes, pigments and the like can be contained. As other dyes, commercially available dyes and known dyes described in literatures such as "Dye Handbook" (edited by The Society of Synthetic Organic Chemistry, Japan, 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes,
Dyes such as a carbonium dye, a quinone imine dye, a methine dye, a diimmonium dye, an aminium dye, a squarylium dye, and a metal thiolate complex are exemplified.

Other pigments include commercially available pigment and color index (CI) handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, 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 above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

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

As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

The addition amount of these pigments to the total solid content of the material constituting the chemically amplified positive image forming layer / acid breeding layer in the image forming material is preferably 0.01 to 50% by weight, more preferably 0.1 to 50% by weight. 10% by weight is preferred. If the amount of the pigment is less than 0.01% by weight, the effect of improving the sensitivity is not sufficient, and if it exceeds 50% by weight, the non-image area may be stained during printing or may cause scratches. There is.

These dyes or pigments may be added to the same layer as other components, or a separate layer may be provided and added thereto. 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 additives can be added to the material constituting the chemically amplified positive-type image forming layer / acid-propagating layer in the image forming material of the present invention. For example, the chemically amplified positive image forming layer preferably contains a polyfunctional amine compound. When the polyfunctional amine compound is present together with the alkali water-soluble polymer, the polyfunctional amine compound strongly interacts with an alkali-soluble group in the polymer and has an action of stabilizing the film structure of the recording layer (crosslinking action). . Such a polyfunctional amine compound refers to an amine compound having at least two functional groups. If the number of functional groups is one, the effect of addition cannot be obtained because no crosslinking effect occurs. The lower limit of the number of functional groups is preferably 3 or more because a stronger network can be formed, and the upper limit of the number of functional groups is preferably a viewpoint of production suitability and an insoluble complex due to a strong interaction between polyfunctional groups. 10 to avoid formation
It is preferably at most 6, more preferably at most 6.

The polyfunctional amine compound as an additive is preferably water-soluble or water-dispersible. If so-called neutral water has sufficient water solubility or water dispersibility, during alkaline development described below, the developer sufficiently penetrates into the lithographic printing material to reduce discrimination of the image. It can be excellent in developability without loss. In the present invention, the ability of "water-soluble" includes:
It is preferable to dissolve 0.5 g / liter or more in water. In addition, the ability of “water dispersibility” is 0.
Preferably, the dispersion is 5 g / liter or more.

The polyfunctional amine compound used in the present invention preferably does not have an onium structure from the viewpoint of developability. Examples of the polyfunctional amine compound suitably used in the present invention include a compound obtained by adding an amine compound to a commercially available polyfunctional polymerizable monomer. The polyfunctional amine compound used in the present invention may be used alone or as a mixture of two or more.

In the present invention, when the polyfunctional amine compound is added to the chemically amplified positive-working image forming layer, the addition amount is preferably 3% by weight based on the alkali water-soluble polymer.
The range is preferably from 50 to 50% by weight, and more preferably from 10 to 20% by weight. If the amount is less than 3% by weight, the effect of the present invention is not sufficiently exerted, so that it is not preferable.

Further, for example, other onium salts, aromatic sulfone compounds, aromatic sulfonate compounds and the like act as a thermally decomposable substance. This is preferable because the blocking property 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).

The counter ions of the above onium salts 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 addition amount of the onium salt to the total solid content of the material constituting the chemically amplified positive image forming layer / acid breeding layer in the lithographic printing material is preferably 1 to 50% by weight, more preferably 5 to 30% by weight. And particularly preferably 10 to 30
% By weight.

A dye having a large absorption in the visible light region can be used as a colorant for an image. 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 addition of these dyes is preferable because the distinction between the image area and the non-image area after image formation becomes clear. The addition amount is preferably in the range of 0.01 to 10% by weight based on the total solids of the material constituting the recording layer in the lithographic printing material.

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-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used.

As phenols, 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-60-8894.
2, sulfonic acids, sulfinic acids, alkyl sulfates described in JP-A-2-96755 and the like;
Examples include phosphonic acids, phosphoric esters and carboxylic acids, and specifically, p-toluenesulfonic 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.

The ratio of the above-mentioned cyclic acid anhydride, phenols and organic acids to the total solid content of the material constituting the chemically amplified positive-working image forming layer / acid-propagating layer in the lithographic printing plate material is 0.05 to 20. % By weight, more preferably 0.1 to 15% by weight, particularly preferably 0.1 to 10% by weight.

In the lithographic printing material of the present invention, the material constituting the chemically amplified positive-working image forming layer / acid-propagating layer is used in order to improve the stability of processing under development conditions.
JP-A-62-251740 and JP-A-3-208514.
Non-ionic surfactants as described in JP-A-59-121044 and JP-A-4-13149 can be added.

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

Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, and N-tetradecyl-N , N-betaine type (for example,
(Trade name: Amogen K, manufactured by Dai-ichi Kogyo Co., Ltd.).

The proportion of the above nonionic surfactant and amphoteric surfactant in the total solids of the material constituting the recording layer in the lithographic printing material is preferably 0.05 to 15% by weight, more preferably 0.1 to 15% by weight. 1 to 5% by weight.

In the material constituting the chemically amplified positive image forming layer / acid breeding layer in the image forming material of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure,
Dyes and pigments as image colorants can be added.
Representative examples of the printing-out agent include 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. In particular,
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53-36223, 54-74728, 6
No. 0-3626, No. 61-143748, No. 61-1
Combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-51644 and JP-A-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 terms of storage stability.

Further, a plasticizer may be added to the material constituting the chemically amplified positive-type image forming layer / acid-propagating layer in order to impart flexibility to the coating film, if necessary. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate,
Dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid, and the like can be preferably used.

Further, a surfactant for improving coating properties, for example, a fluorine-based surfactant as described in JP-A-62-170950 can be added. The preferred amount of addition is 0.01 to
1% by weight, more preferably 0.05 to 0.5% by weight.

Using the image forming material of the present invention, a positive planographic printing plate can be manufactured by the following general method for manufacturing a planographic printing plate. The lithographic printing plate is usually prepared by dissolving the material constituting the chemically amplified positive image forming layer in the image forming material of the present invention comprising the above components in a solvent and coating the solution on a suitable support. It is manufactured by dissolving the constituent materials in a solvent and applying the solution on a chemically amplified positive image forming layer. Here, as a solvent used for coating each layer, 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 can be mentioned, but it is not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. The coating amount (solid content) of the chemically amplified positive image forming layer on the support obtained after coating and drying varies depending on the use, but when used as a photosensitive printing plate, it is generally 0.5 to 5%. 0.0g
/ 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 each film deteriorate.

The support is a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper). Etc.), plastic films (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and metals such as those described above. Can be used, or a laminated paper or a vapor-deposited paper or a plastic film.

As the support used in the present invention, a polyester film or an aluminum plate is preferable. Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The different elements contained in aluminum alloys include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth,
Nickel, titanium and the like. 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, but completely pure aluminum is difficult to produce due to refining technology,
It may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used.

The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably about 0.1 mm to 0.6 mm.
15 mm to 0.4 mm, particularly preferably 0.2 mm to
0.3 mm.

The aluminum plate is used after being roughened, but before the surface is roughened, if necessary, a degreasing treatment with a surfactant, an organic solvent or an alkaline aqueous solution or the like for removing rolling oil on the surface can be performed. . 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, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. 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. Also, Japanese Patent Application Laid-Open
As disclosed in JP-A-63902, a method combining the two can also be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to an anodic oxidation treatment, if necessary, in order to increase the water retention and abrasion resistance of the surface. You. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes 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 anodizing treatment conditions vary depending on the electrolyte used, and thus cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C.
Current density 5 to 60 A / dm ^2, voltage 1 to 100 V, which is an electrolyzing time of 10 seconds to 5 minutes. When the amount of the anodic oxide coating is less than 1.0 g / m ² , the printing durability is insufficient or the non-image portion of the lithographic printing plate is easily damaged, and the ink adheres to the damaged portion during printing. So-called "scratch dirt" tends to occur.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. The hydrophilic treatment used in the present invention is described in U.S. Pat.
No. 66, No. 3,181,461, No. 3,280,7
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in No. 34 and 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689,272 are disclosed. A method of treating with polyvinyl phosphonic acid as described above is used.

An undercoat layer may be provided between the support and the chemically amplified positive image forming layer, if necessary.
As the undercoat layer component, various organic compounds are used, for example, carboxymethyl cellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid; phenylphosphoric acid which may have a substituent; naphthylphosphoric acid; Organic phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloride of triethanolamine Such as hydro -Alanine, and hydrochlorides of amines having a sheet group may be used in combination of two or more.

In the present invention, the polyfunctional amine compound can be added to the undercoat layer as described above. In this case, the undercoat layer may be formed together with the other organic compound, or the undercoat layer may be formed using only the polyfunctional amine compound.

The undercoat layer can be provided by the following method. A method in which a solution obtained by dissolving the above organic compound and / or polyfunctional amine compound in water or an organic solvent such as methanol, ethanol and methyl ethyl ketone or a mixed solvent thereof is applied to an aluminum plate, and dried to form an undercoat layer; An aluminum plate is immersed in a solution in which the above organic compound and / or polyfunctional amine compound is dissolved in water or an organic solvent such as methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof to adsorb the above compound, and then water etc. Washing and drying to form an undercoat layer. In the former method, a solution of the above organic compound and / or polyfunctional amine compound having a concentration of 0.005 to 10% by weight can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, and the immersion temperature is 20 to 90 ° C, preferably 25 to 90%.
50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The pH of the solution used for this is adjusted to pH 1 to 12 by a basic substance such as ammonia, triethylamine, potassium hydroxide, or an acidic substance such as hydrochloric acid or phosphoric acid.
It can also be adjusted to the range. Further, a yellow dye may be added for improving the tone reproducibility of the lithographic printing material.

The coating amount of the undercoat layer is 2 to 200 mg / m
² is suitable, and preferably 5 to 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability may not be obtained. In addition, 200mg /
greater than m ² is the same.

The lithographic printing plate manufactured is usually subjected to image exposure,
A development process is performed to form an image. 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. As radiation, electron beam, X
There are lines, ion beams, far infrared rays, and the like. G line, i
Lines, Deep-UV light, high density energy beams (laser beams) are also used. Examples of the laser beam include a helium / neon laser, an argon laser, a krypton laser, a helium / cadmium laser, a KrF excimer laser, a solid laser, and a semiconductor laser. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser and a semiconductor laser are particularly preferable.

As a developer and a replenisher used for developing the image forming material of the present invention, conventionally known aqueous alkali solutions can be used. These include, using an alkali silicate, containing silicon dioxide, a so-called "silicate developer", a non-reducing sugar, and a base, and a "non-silicate developer" substantially free of silicon dioxide. is there.
Here, “substantially” means that the presence of trace amounts of silicon dioxide as unavoidable impurities and by-products is allowed. In the developing step of the image forming material of the present invention, any of the above-mentioned developing solutions can be applied, but from the viewpoint of the effect of suppressing the generation of scratches, it is preferable to use a non-silicate developing solution. As the aqueous alkaline solution, particularly p
H12.5 to 13.5 are preferred.

First, the "silicate developer" will be described. The alkali silicate exhibits alkalinity when dissolved in water, and examples thereof include alkali metal silicates such as sodium silicate, potassium silicate, and lithium silicate, and ammonium silicate. The alkali silicate may be used alone or in combination of two or more. The aqueous alkali solution contains silicon oxide SiO _{2 as} a component of silicate and alkali oxide M ₂ O (M
Represents an alkali metal or ammonium group. ) Can be easily adjusted by adjusting the mixing ratio and the concentration, for example, an alkali metal described in JP-A-54-62004 and JP-B-57-7427. Silicates are used effectively. Among the alkali aqueous solutions, those having a mixing ratio (SiO ₂ / M ₂ O: molar ratio) of the silicon oxide SiO ₂ and the alkali oxide M ₂ O of 0.5 to 3.0 are preferable, and 1.0 to 3.0. 2.
0 is more preferred. When the SiO ₂ / M ₂ O is 0.
If it is less than 5, the alkali strength increases,
When a general-purpose aluminum plate or the like is etched as a support for a lithographic printing original plate, a bad effect may occur, and when it exceeds 3.0, developability may be reduced.

The concentration of the alkali silicate in the developer is 1 to 10% by weight based on the weight of the aqueous alkali solution.
Is preferably 3 to 8% by weight, and most preferably 4 to 7% by weight. If the concentration is less than 1% by weight, the developability and the processing capacity may be reduced. If the concentration is more than 10% by weight, precipitates and crystals are easily formed. And it may interfere with waste liquid treatment.

Next, the “non-silicate developer” will be described. As described above, this developer is composed of a non-reducing sugar and a base, and the non-reducing sugar does not have a reducing property because it has no free aldehyde group or ketone group. It means a saccharide, and is classified into a trehalose-type oligosaccharide in which reducing groups are bonded to each other, a glycoside in which a reducing group of a saccharide is bonded to a non-saccharide, and a sugar alcohol reduced by hydrogenating a saccharide. In the present invention, any of these can be suitably used.

The trehalose-type oligosaccharides include, for example, saccharose and trehalose, and the glycosides include, for example, alkyl glycosides, phenol glycosides, and mustard oil glycosides. Examples of the sugar alcohol include D, L-arabit, ribit, xylit, D, L-sorbit, D, L-annit,
D, L-idit, D, L-talit, zuricit, allozurcit and the like. Further, maltitol obtained by hydrogenation of a disaccharide, a reductant (reduced starch syrup) obtained by hydrogenation of an oligosaccharide, and the like can also be preferably mentioned.

Among the non-reducing sugars, sugar alcohols and saccharose are preferable, and D-sorbitol, saccharose and reduced starch syrup are more preferable, since they have a buffering action in an appropriate pH range. These non-reducing sugars may be used alone or in combination of two or more, and the ratio in the developer is preferably 0.1 to 30% by weight,
1-20% by weight is more preferred.

The alkali silicate or the non-reducing sugar can be combined with an alkali agent as a base by appropriately selecting from those conventionally known. Examples of the alkaline agent include sodium hydroxide, potassium hydroxide,
Lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate And inorganic alkali agents such as ammonium bicarbonate, sodium borate, potassium borate and ammonium borate, potassium citrate, tripotassium citrate and sodium citrate. In addition, monomethylamine, dimethylamine, trimethylamine,
Monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine,
Organic alkali agents such as triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanol amici, ethyleneimine, ethylenediamine, and pyridine can also be suitably mentioned. These alkaline agents may be used alone or in combination of two or more.

Among them, sodium hydroxide and potassium hydroxide are preferred. The reason is that adjusting the amount of addition to the non-reducing sugar enables pH adjustment in a wide pH range. Also, trisodium phosphate,
Tripotassium phosphate, sodium carbonate, potassium carbonate, and the like are also preferable because they themselves have a buffering action.

Further, when developing using an 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 a lithographic printing plate can be processed without replacing the developing solution in the developing tank for a long time by adding the lithographic printing plate to the developing solution. This replenishment system is also preferably applied in the present invention. 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, the developer and replenisher may be hydroquinone, resorcin, sulfurous acid,
A reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as bisulfite, an organic carboxylic acid, an antifoaming agent, and a water softener can also be added.

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

In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize plate making operations. A lithographic printing plate using the lithographic printing material of the present invention can also be processed by this automatic developing machine. This automatic developing machine generally consists of a developing section and a post-processing section, and consists of a device for transporting the printing plate, each processing solution tank and a spray device, and each processing solution pumped up by the pump while transporting the exposed printing plate horizontally. Is sprayed from a spray nozzle to perform development processing. Recently, a method has been known in which a printing plate is immersed and conveyed by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid to perform processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

After image exposure, development, washing with water, and / or rinsing and / or gumming, if there is an unnecessary image portion on the lithographic printing plate (for example, a film edge mark of the original film), A measure for erasing the unnecessary image portion can be taken. As a method for erasing, for example, a method described in Japanese Patent Publication No. 2-1293, in which an erasing liquid is applied to an unnecessary image portion, left as it is for a predetermined time, and then washed with water, is preferable.
The method of irradiating an unnecessary image portion with an actinic ray guided by an optical fiber and developing the same as described in JP-A-174842 can also be used.

The lithographic printing plate that has been subjected to the above treatment can be subjected to a printing step after applying a desensitized gum as required. Burning treatment may be performed for the purpose of improving printing durability. When the lithographic printing plate is to be subjected to a burning process, the lithographic printing plate must be burned before the burning process.
No. 8, No. 55-28062, JP-A-62-31859.
And JP-A-61-159655. As a method, with a sponge or absorbent cotton impregnated with the surface conditioning liquid,
A method in which the lithographic printing plate is applied on the lithographic printing plate, or immersed in a vat filled with a surface-regulating liquid to apply the lithographic printing plate, or an automatic coater is used. 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 0.1.
An appropriate amount is from 03 to 0.8 g / m ² (dry weight).

After drying the lithographic printing plate coated with the surface conditioning liquid, a burning processor (for example, a burning processor sold by Fuji Photo Film Co., Ltd.):
"BP-1300") or the like. The heating temperature and time in this case depend on the type of the component forming the image, but are in the range of 180 to 300 ° C. and 1 to 20 ° C.
A range of minutes is preferred.

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

The 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.

[0172]

The present invention will be described below in detail with reference to examples.
However, the present invention is not limited to these. What
Unless otherwise specified, “parts” means “parts by weight”
You. <Preparation of support> Aluminum plate having a thickness of 0.30 mm
(Material 1050) is washed with trichlorethylene and degreased
Nylon brush and 400 mesh pamistone-
Use a water suspension to grain the surface, wash well with water
Was. Put this plate in a 25% aqueous solution of sodium hydroxide at 45 ° C.
After dipping for 9 seconds, etching and washing with water, further 2% H
NO _ThreeFor 20 seconds and washed with water. Graining at this time
The amount of etching on the surface is about 3 g / m^TwoMet. Then this
7% H_TwoSO_FourCurrent density 15A / dm
^Two3g / m^TwoWas provided. Then 7
After immersing in a 2.5% aqueous solution of sodium silicate at 0 ° C for 1 minute, washing with water
Dried.

Next, an undercoat solution having the following composition was applied to the aluminum plate, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 20 mg / m ² . (Coating solution for undercoating liquid) ・ Dibutylnaphthalenesulfonic acid 0.1 g of condensate of 4-diazodiphenylamine and phenoxyacetic acid with formaldehyde ・ 100 g of methanol The plate material having the undercoating layer is treated as follows. Examples 1 to 6 and Comparative Examples 1 to 3
Was prepared.

(Example 1) A coating liquid (a) for a chemically amplified positive type image forming layer was applied to the above-mentioned primed aluminum plate and dried at 100 ° C for 2 minutes to have a chemically amplified positive type image forming layer. A plate material of 1 g / m ² was obtained. (A) Coating solution for chemically amplified positive image forming layer ・ Binder A (the following compound) 60 parts ・ Acid decomposable compound A (the following compound) 20 parts ・ Photoacid generator A (the following compound) 5 parts ・ Infrared absorbing agent IR -1 (the following compound) 2 parts ・ Propylene glycol monomethyl ether 700 parts ・ Toluene 300 parts

[0175]

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[0176]

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The solution (a) for an acid breeding layer having the following composition was applied on the above-mentioned plate material, dried at 100 ° C. for 1 minute, and 1.8 g
/ M ² of a lithographic printing plate (image forming material).

(A) Coating solution for acid breeding layer: 50 parts of phenol formaldehyde novolak (Mw 3000) Acid breeding agent: 5-methyl-2- (p-toluenesulfonyloxy) -3-ketobutane tert-butyl ester 5 parts Diphenyl (p-phenylthiophenyl) sulfonium hexafluoroantimonate 5 parts ・ Infrared absorber IR-1 2 parts ・ Methanol 400 parts ・ γ-butyrolactone 400 parts ・ Water 80 parts

(Example 2) 1.8 g of Example 1 was repeated in the same manner as in Example 1 except that the following (b) solution for acid breeding layer was used instead of (a) the coating solution for acid breeding layer. / M ² of a lithographic printing plate (image forming material). (B) Solution for acid breeding layer ・ 50 parts of phenol formaldehyde novolak (Mw3500) ・ 4- (pN, N-bis (ethoxycarbonylmethyl) aminophenyl) -2,6-bis (trichloromethyl) -s-triazine 5 parts ・ Acid multiplying agent: cis-1-methyl-1-hydroxy-2- (p-toluenesulfonyloxy) hexane 5 parts ・ Infrared absorber IR-1 2 parts ・ Methanol 400 parts ・ γ-butyrolactone 400 parts ・ Water 80 copies

Example 3 The following (c) chemically amplified positive image forming layer was used in place of (a) the chemically amplified positive image forming layer coating solution and (a) the acid multiplying layer coating solution in Example 1. Example 1 except that a coating solution for use and (c) a solution for an acid multiplication layer were used.
In the same manner as in the above, a lithographic printing plate (image forming material) of 1.8 g / m ² was obtained. (C) Coating solution for chemically amplified positive-type image forming layer Binder A (the above compound) 10 parts Phenol / m, p-cresol novolak resin 60 parts (phenol / m-cresol / p-cresol ratio = 20/48) / 32, number average molecular weight 500, weight average molecular weight 2500) 3 parts of photoacid generator A (the above compound) 25 parts of acid decomposable compound B (the following compound) 25 parts of infrared absorber IR-1 2 parts of propylene glycol monomethyl ether 700 parts ・ Toluene 300 parts

[0181]

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(C) Coating solution for acid breeding layer 50 parts of polyhydroxystyrene (Mw 20,000) 5 parts of bis (3-bromo-2,3-dimethyl-2-butyl) squarate 5 (4-octyloxyphenyl) phenyl 5 parts of iodonium hexafluoroantimonate ・ 2 parts of infrared absorbent IR-1 ・ 1 part of Megafac F-177 (a fluorosurfactant manufactured by Dainippon Ink and Chemicals, Inc.) 1 part ・ 400 parts of methanol ・ 400 gamma-butyrolactone Part ・ Water 80 parts

Example 4 1.8 g of Example 3 was repeated in the same manner as in Example 3 except that the following solution (d) was used instead of the coating solution (c). / M ² of a lithographic printing plate (image forming material). (D) Acid breeding layer-50 parts of phenol formaldehyde novolak (Mw3500)-5 parts of acid generator A (the above compound)-5 parts of p-methoxyoxalate-2 parts of infrared absorber IR-1-2 parts of Megafac F-177 ( 0.5 parts ・ Coloring agent (VPB-Naps: manufactured by Hodogaya Chemical Co., Ltd.) 0.1 part ・ Methanol 400 parts ・ γ-butyrolactone 400 parts ・80 parts of water

(Example 5) The following (e) chemically amplified positive-type image forming layer was used in place of (a) the chemically amplified positive-type image forming layer coating solution and (a) the acid-propagating layer coating solution in Example 1. Example 1 except that a coating solution for use and a solution for (e) an acid breeding layer were used.
In the same manner as in the above, a lithographic printing plate (image forming material) of 1.8 g / m ² was obtained. (E) Coating solution for chemically amplified positive-type image forming layer Binder A (the above compound) 10 parts Phenol / m, p-cresol novolak resin 60 parts (phenol / m-cresol / p-cresol ratio = 20/48) / 32, number average molecular weight 500, weight average molecular weight 2500)-3 parts of photoacid generator A (the above compound)-25 parts of acid decomposable compound C (the following compound)-2 parts of infrared absorber IR-1-2 parts of propylene glycol monomethyl ether 700 parts ・ Toluene 300 parts

[0185]

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(E) Coating solution for acid multiplication layer ・ Phenol formaldehyde novolak 50 parts ・ Acid multiplication agent: 1,2-epoxy-2-methyl-3- (p-toluenesulfonyloxy) propane 5 parts ・ Acid generator A (The above compound) 5 parts ・ Infrared absorbing agent IR-1 2 parts ・ Megafac F-177 (Dainippon Ink & Chemicals, Inc., fluorine-based surfactant) 0.1 part ・ Colorant (VPB-naps: Hodogaya Chemical Co., Ltd.) 0.1 parts ・ Methanol 400 parts ・ γ-butyrolactone 400 parts ・ Water 80 parts

Example 6 1.8 g of Example 5 was repeated in the same manner as in Example 5 except that the following solution (f) was used instead of the coating solution (e) for the acid breeding layer. / M ² of a lithographic printing plate (image forming material). (F) Coating solution for acid breeding layer ・ Novolak resin (m / p = 6/4, Mw = 10,000) 40 parts ・ Resol resin 20 parts (weight average molecular weight obtained from bisphenol A and formaldehyde: 2,000, number average) (Molecular weight: 1000) ・ Diphenyliodonium hexafluorophosphate 5 parts ・ Acid multiplying agent: 1- (p-toluenesulfonyloxy) -3-phenyl-3,3-ethylenedioxypropane 5 parts ・ Infrared absorber IR-1 2 parts

(Comparative Examples 1 to 3) Coating solutions for (a) a chemically amplified positive image forming layer, (c) a chemically amplified positive image forming layer,
(E) A 1.8 g / m ² lithographic printing plate (image forming material) (Comparative Example 1, Comparative Example 2, Comparative Example 3) was obtained by applying only the coating liquid for the chemically amplified positive image forming layer.

The lithographic printing plates of Examples 1 to 6 and Comparative Examples 1 to 3 produced as described above were evaluated for performance based on the following criteria.

<Evaluation of Image Formability and Sensitivity> Examples 1 to 6
The lithographic printing plates of Comparative Examples 1 to 3 were exposed using a semiconductor laser having a wavelength of 840 nm. After exposure, an automatic developing machine (“PS Processor 900”) was charged with a developing solution having the following composition.
VR ", manufactured by Fuji Photo Film Co., Ltd.).

(Composition of developer) 1 K potassium silicate 3.0 parts by weight Potassium hydroxide 1.5 parts by weight C ₁₂ H ₂₅ -C ₆ H ₄ -OC ₆ H ₄ -SO ₃ Na 0 0.3 parts by weight ・ Water 95.2 parts by weight

The line width of the non-image portion of each lithographic printing plate obtained with the developer was measured, the irradiation energy of the laser corresponding to the line width was determined, and the sensitivity index (mJ / cm) was obtained.
² ) The smaller the measured value (mJ / cm ² ), the higher the sensitivity of the lithographic printing plate. Table 1 shows the results of the above evaluations.

[0193]

[Table 1]

From the above results, it was found that the lithographic printing plates of Examples 1 to 6 had higher sensitivity to the infrared laser in any combination than the lithographic printing plates of Comparative Examples 1 to 3. On the other hand, it was confirmed that the lithographic printing plate of the comparative example using only the chemically amplified positive image forming layer as the recording layer was insufficient in sensitivity.

[0195]

According to the present invention, plate making can be performed directly from digital data of a computer or the like by using a solid-state laser and a semiconductor laser that irradiate infrared rays, and a positive-type image forming apparatus having high sensitivity to the infrared lasers described above. Material can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA01 AB03 AC08 AD03 BE00 BE10 BG00 CB41 CB52 CC11 CC20 DA13 FA10 FA17 2H096 AA06 BA11 EA04 EA23 GA08 KA03 KA06 2H114 AA04 AA15 BA01 BA05 FA15 GA05

Claims (2)

[Claims] 1. A first layer on a support, in which an acid generated by the action of light or heat acts as a catalyst to cleave a chemical bond to increase the solubility in an alkali developing solution, and a first layer formed thereon by the action of light or heat An image forming material, comprising: a second layer that decomposes an acid generator using the generated acid as a catalyst to multiply the acid. 2. The image forming material according to claim 1, wherein the first layer and / or the second layer contains an infrared absorber.