JP2003149799A - Planographic printing plate for infrared laser - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a planographic printing plate for an infrared laser excellent in age stability of a flaw. SOLUTION: The planographic printing plate is obtained by disposing a heat sensitive layer comprising (A) a material which absorbs light and generates heat, (B) a resin soluble in an aqueous alkali solution and having phenolic hydroxyl groups and (C) a compound having 2-12 groups of the formula -R<1> -Y- CO-X-R<2> (where X is O, S or NR<3> ; Y is NR<3> or a single bond; R<1> is a 1-32C alkylene or arylene; and R<2> and R<3> are each H or a 1-18C alkyl, alkenyl or aryl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material that can be used as an offset printing master, and particularly for a planographic printing plate for an infrared laser mainly used for so-called direct plate making which can be made directly from digital signals of a computer or the like. Regarding the original edition.

[0002]

2. Description of the Related Art The development of lasers in recent years has been remarkable, especially solid-state lasers having a light emitting region from the near infrared to the infrared.
As for the semiconductor laser, a high-power and small-sized laser oscillator is easily available. Direct exposure such as CTP (Computer Toe Plate) method, in which an original of digital data processed by a computer is recorded as an image on a printing original plate using the exposure light source of these lasers, and the plate making process is omitted. Simplified printing / printing is a very useful printing method because it shortens the process from original preparation to printing and simplifies the operation.

A printing original plate suitable for this direct plate making method is a positive type lithographic printing plate material for infrared laser,
This material contains a binder resin that is soluble in an alkaline aqueous solution and a photothermal conversion infrared dye (hereinafter also referred to as IR dye) that absorbs light and generates heat, and the like. Part) acts as a dissolution inhibitor that substantially reduces the solubility of the binder resin due to the interaction with the binder resin, and in the exposed part (non-image part), the IR dye etc. and the binder resin interact with each other due to the heat generated. The action is weakened and dissolved in an alkali developing solution to form a lithographic printing plate.

Further, in order to improve the surface slipperiness of the lithographic printing plate precursor for infrared laser and to have a scratch suppressing effect, that is, scratch resistance, in the image forming layer of the lithographic printing plate precursor for infrared laser. The addition of a WAX agent is under consideration. However, when the printing plate precursor having a WAX agent in the image forming layer is stored for a long period of time, there is a problem that the scratch resistance decreases with time.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to overcome the above-mentioned drawbacks of the prior art, and an object thereof is to provide a lithographic printing plate for infrared laser, which is excellent in the stability of scratches over time. To do.

[0006]

As a result of intensive studies, the present inventors have found that the above object can be achieved by adding a specific WAX agent to the heat-sensitive layer, and complete the present invention. Came to. That is, the present invention is achieved by the following configurations.

(1) (A) a substance that absorbs light to generate heat, (B) an alkaline aqueous solution-soluble resin having a phenolic hydroxyl group, (C) a group represented by the following general formula (I):
A lithographic printing plate for infrared laser, which is provided with a heat-sensitive layer containing a compound having 12 to 12.

—R ¹ —Y—CO—X—R ² General formula (I)

(Wherein X represents O, S or NR ³ ,
Y represents NR ³ or a single bond, R ¹ represents an alkylene group having ¹ to 32 carbon atoms or an arylene group, R ² and R ³ are hydrogen atoms, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, Alternatively, it represents an aryl group. )

(2) The heat-sensitive layer is provided on the support (A).
Infrared ray according to (1) above, which has a second heat-sensitive layer on the first heat-sensitive layer containing a substance that absorbs light and generates heat and (B) an alkali aqueous solution-soluble resin. Planographic printing plate for laser.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Heat-sensitive layer] First, the heat-sensitive layer will be described. As described above, the heat-sensitive layer is represented by (A) a substance that absorbs light to generate heat, (B) an alkaline aqueous solution-soluble resin having a phenolic hydroxyl group, and (C) represented by the general formula (I). Although it contains a compound having 2 to 12 groups, the component (C), which is a characteristic component of the present invention, will be described first.

(C) The group represented by the above general formula (I) is 2
Compound having 12 to 12 (also referred to as component (C) or compound of (C)) The compound having 2 to 12 groups represented by the general formula (I) of the present invention has a large number of carbon atoms called so-called wax. It is a fatty acid derivative or an alcohol derivative having a large number of carbon atoms.

In the formula, R ¹ represents an alkylene group having ¹ to 32 carbon atoms or an arylene group. The alkylene group or the arylene group may have a branch, and examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-hexene group. Linear alkylene groups such as heptylene group, n-octylene group, n-nonylene group, n-decylene group, and n-undecylene group, 14-methylpentadecylene group, 16
Examples include branched alkylene groups such as a methylheptadecylene group. Further, examples of the arylene group include a phenylene group, a biphenylene group, a 1,3′-dimethylbiphenylene group and the like. Among these, an alkylene group having 25 or less carbon atoms and an arylene group are preferable from the viewpoint of solubility in the coating solvent.

R ² and R ³ are hydrogen atoms or have 1 carbon atom.
To 18 alkyl groups, alkenyl groups, or aryl groups. The alkyl group and alkenyl group may have a branch or may have a substituent. Examples of such an alkyl group include a methyl group, an ethyl group, an n-hexyl group, an n-nonyl group, a benzyl group and a cyclohexylmethyl group, and an alkenyl group includes a propylenyl group, a 1-butenyl group and a 1-butenyl group. Examples thereof include isobutenyl group, 1-pentenyl group, 3-methyl-1-butenyl group, 1-hexenyl group, 1-octenyl group and the like. The aryl group may have a substituent, and as the aryl group,
Examples thereof include a phenyl group, a 4-hydroxyphenyl group and a cyclohexylphenyl group. X is O, S, or NR
³ , Y represents NR ³ or a single bond.

That is, the compound (C) contains a compound containing a plurality of ester groups in the molecule, a compound containing a plurality of thioester groups, a compound containing a plurality of amide groups, and a plurality of urethane groups. Indicates a compound or the like.

Specific examples of the compound (C) will be given below.
As the diester compound, dienanthic acid, dicaprylic acid, dipelargonic acid, dicapric acid, diundecyl acid,
Dilauric acid, ditridecylic acid, dimyristic acid, dipentadecyl acid, dipalmitic acid, diheptadecyl acid, distearic acid, dinonadecanoic acid, diarachidic acid, dibehenic acid, dilignoceric acid, diserotic acid, diheptacosanoic acid, dimontanic acid, dimericinic acid, dilaccelic acid, Diundecylenic acid, dioleic acid, dielaidic acid, dicetrainic acid, dierucic acid, dibrassidic acid, thiodipropionic acid, thiodibutanoic acid and other methyl esters, ethyl esters, propyl esters, butyl esters, dodecyl esters, phenyl esters, naphthyl esters, etc. Can be mentioned.

Examples of the dithioester compound include methylthioester, butylthioester and benzylthioester of these fatty acids. Examples of triester compounds include esters of trihydric alcohols such as glycerin with fatty acids and esters of tricarboxylic acids with alcohols. Similarly, as a tetraester compound,
Examples thereof include esters of tetravalent alcohol and fatty acid and esters of tetravalent fatty acid and alcohol. Furthermore, polyvalent esters of monosaccharides and disaccharides and fatty acids can be mentioned. Examples of the polyvalent amide compound include amides of the above fatty acids, and examples of the polyvalent urethane compound include a condensation product of a polyhydric alcohol and an isocyanate and a condensation product of a polyvalent isocyanate and an alcohol.

The component (C) of the present invention may be any compound having 2 to 12 groups represented by the general formula (I), and is represented by the general formula (I). A compound having 2 to 6 groups represented by the general formula (I)
Compounds having 2 to 4 groups represented by are more preferable.

The compounds (C) may be used alone or in combination of two or more.
The compound of the formula (I) may have different R ² components of the group represented by the general formula (I) in the same molecule. When the compound (C) contains compounds having different R ² components of the group represented by the general formula (I) in the same molecule, weeping or crystallization of the compound in the heat-sensitive layer Is preferable because it can be effectively prevented. Also,
The above (C) is usually 0.02-1 in the total solid content of the printing plate material.
It is used in an amount of 0% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 5% by weight. (C)
If the addition amount of the compound is less than 0.02% by weight, the development stability against external damage becomes insufficient, and conversely, if it is added in an amount of 10% by weight or more, a problem that dust is generated in the developer occurs.

(B) Alkaline Aqueous Solution Soluble Resin Having Phenolic Hydroxyl Group Examples of the alkaline aqueous solution soluble resin having a phenolic hydroxyl group (hereinafter referred to as "resin having a phenolic hydroxyl group") used in the present invention include, for example, phenol formaldehyde resin. , M-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-
Mention may be made of novolak resins such as mixed cresol formaldehyde resins, phenol / cresol (m-, p-, or m- / p-mixed) mixed formaldehyde resins.

The resin having a phenolic hydroxyl group preferably has a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000. Further, as described in U.S. Pat. No. 4,123,279, a condensate of formaldehyde with a phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin. You may use together. The resin having such a phenolic hydroxyl group may be one type or two types.
You may use it in combination of 2 or more types.

In the present invention, a copolymer containing the above-mentioned resin having a phenolic hydroxyl group and 10 mol% or more of at least one of the following (a) to (c) as a copolymerization component (hereinafter referred to as "specific copolymer It is preferable to use together with ".

(A) Monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule (b) Monomer having an active imino group represented by the following formula in one molecule

[0024]

[Chemical 1]

(C) Acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, or hydroxystyrene each having a phenolic hydroxyl group.

The specific copolymer of the present invention comprises at least one of (a) to (c) as a copolymer component.
It is necessary that the content is 20 mol% or more, more preferably 20 mol% or more. If it is less than 10 mol%,
The interaction with the resin having a phenolic hydroxyl group becomes insufficient, and the development latitude decreases. In addition, the above (a)
From (c) to (c) may be included.

The monomer corresponding to (a) is a low molecular weight compound having at least one sulfonamide group having at least one hydrogen atom bonded to a nitrogen atom and at least one polymerizable unsaturated bond in one molecule. It is a monomer consisting of.
Among them, a low molecular weight compound having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group is preferable. Examples of such a compound include compounds represented by the following general formulas (I) to (V).

[0028]

[Chemical 2]

In the formula, X ¹ and X ² are each --O-- or-
NR ¹⁰ − is shown. R ^4, R ⁷ each is a hydrogen atom or a -C
Represents H ₃ . R ⁵ , R ⁸ , R ¹² , R ¹⁵ , and R ¹⁹ each represent an alkylene group having 1 to 12 carbon atoms, which may have a substituent, a cycloalkylene group, an arylene group, or an aralkylene group. R ⁶ , R ¹⁰ and R ¹⁶ are each a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms,
A cycloalkyl group, an aryl group or an aralkyl group is shown. R ⁹ and R ²⁰ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group which may have a substituent. R ¹¹ , R ¹³ , R
¹⁷ represents a hydrogen atom or -CH _3. R ¹⁴ and R ¹⁸ are each a single bond or a carbon atom which may have a substituent.
Represents an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group. Y ^1, Y ² each represent a single bond or -CO-.

Specifically, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide and the like can be preferably used.

The monomer corresponding to (b) is a monomer composed of a low molecular weight compound having one or more active imino groups represented by the above formula and one or more polymerizable unsaturated bonds in one molecule. As such a compound, specifically, N- (p-toluenesulfonyl) methacrylimide, N- (p-toluenesulfonyl) acrylimide, or the like can be preferably used.

The monomer corresponding to (c) is a monomer composed of acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, or hydroxystyrene each having a phenolic hydroxyl group. Specific examples of such a compound include N- (4
-Hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, p-hydroxy Phenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like can be preferably used.

As the other copolymerization component, for example, the following monomers (1) to (12) can be used. (1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl Alkyl acrylate such as acrylate. (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl. Alkyl methacrylate such as methacrylate. (4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-
Hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-
Acrylamide or methacrylamide such as phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide. (5) 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.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate. (7) Styrenes such as styrene, α-methylstyrene, methylstyrene and chloromethylstyrene. (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide. (12) acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid.

The specific copolymer of the present invention preferably has a weight average molecular weight of 2000 or more and a number average molecular weight of 1000 or more. More preferably, the weight average molecular weight is 5,000 to 300,000 and the number average molecular weight is 200.
It is 0 to 250,000 and the degree of dispersion (weight average molecular weight / number average molecular weight) is 1.1 to 10.

The specific copolymer may be used alone or in combination of two or more kinds.

The compounding weight ratio of the resin having a phenolic hydroxyl group to the specific copolymer is 50:50 to 5: 5.
Preferably in the range of 95, 40:60 to 1
More preferably, it is in the range of 0:90. When the compounding amount of the resin having a phenolic hydroxyl group is larger than this, the sea-island structure is reversed and it becomes difficult to improve the solvent resistance and the like. On the contrary, when the amount of the copolymer added is larger than this, the surface layer of the resin having the phenolic hydroxyl group becomes too thin, and the development latitude is insufficiently improved.

These alkali-soluble polymer compounds composed of a resin having a phenolic hydroxyl group and a specific copolymer may be used either individually or in combination of two or more, and they may be used in the total solid content of the printing plate material. , 30-99
It is used in an amount of 50% by weight, preferably 40 to 95% by weight, particularly preferably 50 to 90% by weight. When the amount of the alkali-soluble polymer compound added is less than 30% by weight, the durability of the recording layer deteriorates, and when it exceeds 99% by weight, both the sensitivity and the durability are unfavorable.

(A) Substance that Absorbs Light and Generates Heat (also referred to as Photothermal Converter) In the present invention, various pigments or dyes can be used as the substance that absorbs light and generates heat. As the pigment, commercially available pigments and color indexes (C.I.
I. ) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association,
1977), "Latest pigment application technology" (CMC Publishing,
1986), "Printing Ink Technology", CMC Publishing, 19
The pigments described in 1984) can be used.

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer bound dyes may be mentioned. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments,
Quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black and the like can be used.

These pigments may be used without surface treatment or may be used after surface treatment. The surface treatment method includes a method of surface-coating a resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment method is described in "Characteristics and Applications of Metal Soap" (Koushobo), "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 198).
6 years).

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 0.1 μm to 1 μm.
It is preferably in the range of. Particle size of pigment is 0.01μ
When it is less than m, it is not preferable from the viewpoint of stability of the dispersion in the coating liquid for the photosensitive layer, and when it exceeds 10 μm, it is not preferable from the viewpoint of uniformity of the photosensitive layer. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production or the like can be used. As the disperser, ultrasonic disperser, sand mill, attritor, pearl mill, super mill,
A ball mill, an impeller, a despather, a KD mill, a colloid mill, a dynatron, a three roll mill, a pressure kneader and the like can be mentioned. For details, see "Latest Pigment Application Technology."
(CMC Publishing, published in 1986).

As the dye, commercially available dyes and known dyes described in the literature (for example, "Dye Handbook" edited by the Society of Organic Synthetic Chemistry, published in 1945) can be used. Specific examples include dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes. In the present invention, among these pigments or dyes, those that absorb infrared light or near infrared light are particularly preferable because they are suitable for use in a laser that emits infrared light or near infrared light.

Carbon black is preferably used as a pigment that absorbs such infrared light or near infrared light. Examples of dyes that absorb infrared light or near infrared light include JP-A-58-125246 and JP-A-59.
-84356, JP-A-59-202829, JP-A-60-78787 and the like,
JP-A-58-173696, JP-A-58-18169
No. 0, methine dyes described in JP-A-58-194595, JP-A-58-112793, and JP-A-58.
-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744 and the like, and JP-A-58-112792. Examples thereof include squarylium dyes and cyanine dyes described in British Patent 434,875.

Further, as a dye, US Pat. No. 5,156,
The near-infrared absorption sensitizer described in US Pat. No. 938 is also preferably used, and the substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, JP-A-57-1.
No. 42645 (US Pat. No. 4,327,169), a trimethine thiapyrylium salt, JP-A-58-1810.
No. 51, No. 58-220143, No. 59-41363.
No. 59-84248, No. 59-84249, No. 59-146063, No. 59-146061, and the pyrylium compounds described in JP-A-59-2161.
Cyanine dye described in US Pat. No. 4,283,4
No. 75, pentamethine thiopyrylium salt, etc., and the pyrylium compounds disclosed in Japanese Examined Patent Publication Nos. 5-13514 and 5-19702, Epolight III-1.
78, Epolight III-130, Epolight
t III-125 and the like are particularly preferably used.

Further, as another particularly preferable example of the dye, there can be mentioned near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993. These pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 10% by weight, in the case of pigments, based on the total solid content of the printing plate material. Particularly preferably 3.1
It can be added to the printing plate material in a proportion of from 10 to 10% by weight. If the amount of the pigment or dye added is less than 0.01% by weight, the sensitivity will be low, and if it exceeds 50% by weight, the uniformity of the photosensitive layer will be lost and the durability of the recording layer will be poor. These dyes or pigments may be added to the same layer as other components, or may be added to another layer provided separately. When it is formed as a separate layer, it is desirable to add it to a layer adjacent to a layer containing a substance which is to be described later and is a substance which substantially decomposes the solubility of the binder in the state of being thermally decomposable and not decomposed. The dye or pigment and the binder resin are preferably in the same layer, but may be in different layers.

[Other Components] In forming the heat-sensitive layer, various additives may be added, if necessary, in addition to the components described above, as long as the effects of the present invention are not impaired. . For example, an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, an aromatic sulfonic acid ester compound, or the like, which is thermally decomposable, is used in combination with a substance that substantially reduces the solubility of the alkaline water-soluble polymer compound when not decomposed. Doing so is preferable from the viewpoint of improving the dissolution inhibiting property of the image area in the developing solution. Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like.

Suitable onium salts used in the present invention are, for example, SI Schlesinger,
Photogr. Sci. Eng., 18, 387 (1974), TS Bal et a
l, Polymer, 21, 423 (1980), JP-A-5-158230
Diazonium salt described in U.S. Pat. No. 4,069,055
No. 4,069,056, ammonium salts described in JP-A-3-140140, DC Necker et al, Macromolecul
es, 17, 2468 (1984), CS Wen et al, Teh, Proc. Co
nf.Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31.
(1988), European Patent 104,143, U.S. Patent 339,049.
No. 410,201, JP-A No. 2-150848, and JP-A No. 2-2965.
Iodonium salt described in No. 14, JVCrivello et al, P
olymer J. 17, 73 (1985), JV Crivello et al. J.
Org. Chem., 43, 3055 (1978), WR Watt et al, J. P.
olymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JV Crivello et al, Polymer Bull., 14, 279 (198
5), JV Crivello et al, Macromorecules, 14 (5),
1141 (1981), JV Crivello et al, J. Polymer Sci.,
Polymer Chem. Ed., 17, 2877 (1979), European Patent 37
0,693, 233,567, 297,443, 297,442
U.S. Pat.Nos. 4,933,377, 3,902,114, 410,
No. 201, No. 339,049, No. 4,760,013, No. 4,734,444
No. 2,833,827, German Patent Nos. 2,904,626, 3,60
Sulfonium salts described in 4,580 and 3,604,581, J.
V. Crivello et al, Macromorecules, 10 (6), 1307 (19
77), JV Crivello et al, J. Polymer Sci., Polyme
r Chem. Ed., 17, 1047 (1979), selenonium salt, CS Wen et al, Teh, Proc.Conf. Rad. Curing AS
Examples include arsonium salts described in IA, p478 Tokyo, Oct (1988). Among the onium salts, the diazonium salt is particularly preferable. Further, particularly preferable diazonium salts include those described in JP-A-5-158230.

As the counter ion of the onium salt, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5
-Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic 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- Examples thereof include benzoyl-benzenesulfonic acid and paratoluenesulfonic acid. Among these, alkylaromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable.

Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and compounds having various structures can be used. That is, o-quinonediazide assists the solubility of the light-sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder by thermal decomposition and the effect of changing o-quinonediazide itself into an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include those described in J. The compounds described on pages 339 to 352 of "Light-Sensitive Systems" (John Wiley & Sons. Inc.) by Coser can be used, but in particular, they have been reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. -Sulfonic acid esters or sulfonic acid amides of quinonediazide are preferred. Further, benzoquinone (1,2) -diazide sulfonic acid chloride or naphthoquinone- (1,3) as described in JP-B-43-28403.
2) -Diazido-5-sulfonic acid chloride ester with pyrogallol-acetone resin, US Pat. No. 3,046,12
0 and benzoquinone- (1,2) -diazide sulfonic acid chlorides or naphthoquinone- (1,2) -diazide-5-sulfonic acid chlorides and esters of phenol-formaldehyde resins described in No. 3,188,210 It is preferably used.

Further, an ester of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride and a phenol formaldehyde resin or a cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-
Esters of 4-sulfonic acid chloride and pyrogallol-acetone resin are likewise preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, and JP-A-48-96.
575, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481
U.S. Pat.Nos. 2,797,213, 3,454,400, 3,544,323, 3,573,917, 3,674,495.
No. 3,785,825, British Patent No. 1,227,602, No.
1,251,345, 1,267,005, 1,329,888,
Examples thereof include those described in each specification such as the above-mentioned 1,330,932 and German Patent No. 854,890.

The amount of the o-quinonediazide compound added is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 3% by mass based on the total solid content of the printing plate material.
It is in the range of 0 mass%. These compounds can be used alone, but may be used as a mixture of several kinds.

Further, cyclic acid anhydrides, phenols and organic acids may be used in combination for the purpose of further improving the sensitivity. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, and anhydride described in U.S. Pat. No. 4,115,128. Maleic acid, chloromaleic anhydride,
α-Phenyl maleic anhydride, succinic anhydride, pyromellitic dianhydride, etc. 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. Further, as organic acids, sulfonic acids, sulfinic acids, alkylsulfates, phosphonic acids, phosphoric acid esters, carboxylic acids and the like described in JP-A-60-88942 and JP-A-2-96755 are mentioned. Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethylsulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, Adipic acid, p-
Toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid,
Examples thereof include terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid and ascorbic acid. The proportion of the above cyclic acid anhydride, phenols and organic acids in the printing plate material is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 0.1% by mass. It is 10% by mass.

Further, in the printing plate material according to the present invention, in order to broaden the stability of processing under developing conditions, JP-A-62-62 is used.
Nonionic surfactants such as those described in JP-A-251740 and JP-A-3-208514;
Amphoteric surfactants as described in JP-A-9-121044 and JP-A-4-13149, EP9505.
17, a siloxane-based compound as described in
A fluorine-containing monomer copolymer as described in JP-A No. 11-288093 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride and polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric activator include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine. Examples include molds (for example, trade name “Amorgen K”: manufactured by Daiichi Kogyo Co., Ltd.). As the siloxane compound, a block copolymer of dimethylsiloxane and polyalkylene oxide is preferable, and specific examples thereof include DBE-224 and DBE-6 manufactured by Chisso Corporation.
21, DBE-712, DBP-732, DBP-53
4. Polyalkylene oxide-modified silicone such as Tego Glide 100 manufactured by Tego, Germany can be mentioned. The proportion of the nonionic surfactant and amphoteric surfactant in the printing plate material is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

In the printing plate material of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure and a dye or pigment as an image colorant can be added. A typical example of the print-out agent is a combination of a compound that releases an acid when heated by exposure (photo-acid releasing agent) and an organic dye capable of forming a salt. Specifically, a combination of an o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53 / 1983. -36223, 54-74728, 60
-3626, 61-143748, 61-15
Examples thereof include combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A Nos. 1644 and 63-58440. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent stability over time and give a clear printout image.

As the image colorant, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic 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 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl. Violet (CI42535), ethyl violet, Rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201).
5) etc. can be mentioned. In addition, JP-A-62-2
The dyes described in Japanese Patent No. 93247 are particularly preferable. These dyes are added in an amount of 0.
It can be added to the printing plate material in a proportion of 01 to 10% by mass, preferably 0.1 to 3% by mass. Further, a plasticizer is added to the printing plate material of the present invention, if necessary, in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid. Oligomers and polymers are used.

In the lithographic printing plate precursor of the invention, the heat-sensitive layer composition of a plate material containing the above components is usually dissolved in a solvent to prepare a lithographic printing plate precursor,
It can be produced by coating on a suitable support. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2.
-Propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N,
N-dimethylformamide, tetramethylurea, N-
Examples thereof include methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and toluene, but are not limited thereto. These solvents may be used alone or as a mixture. In selecting the coating solvent, for those having a two-layer structure of the upper recording layer and the lower recording layer, in order to prevent mutual compatibility at the interface between the layers when they are provided adjacent to each other, the coating solvent for the upper recording layer It is preferable to select a material that does not substantially dissolve the lower recording layer. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by mass.

Various methods can be used for coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. You can As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate. In the photosensitive layer according to the present invention, a surfactant for improving the coatability, for example, a fluorine-based surfactant as described in JP-A-62-170950 can be added. The preferable addition amount is 0.01 in the total solid content of the recording layer.
~ 1 mass%, more preferably 0.05-0.5 mass%
Is.

The heat-sensitive layer of the plate material of the present invention may have a two-layer structure. In that case, it is preferable that a first heat-sensitive layer containing a photothermal conversion agent and an alkali aqueous solution-soluble resin is provided on a support, and a heat-sensitive layer having the above-mentioned composition is provided thereon as a second heat-sensitive layer.

[Support] The support used in the present invention includes a dimensionally stable plate-like material having necessary strength and durability, and examples thereof include paper and plastic (eg, polyethylene, Paper laminated with polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate) , Polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal and the like), paper laminated with the above metal or vapor-deposited, or a plastic film.

As the support used in the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. The preferred aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a slight amount of a foreign element, and may be a plastic film in which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of foreign elements in the alloy is at most 10% by mass. Aluminum which is particularly preferred in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in terms of refining technology, and thus may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly known aluminum plates can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if desired, a degreasing treatment for removing the rolling oil on the surface is carried out, for example, with a surfactant, an organic solvent or an alkaline aqueous solution. Roughening treatment of the surface of the aluminum plate,
Various methods are used, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface. As the mechanical method, known methods such as a ball polishing method, a brush polishing method, a blast polishing method and a buff polishing method can be used. Further, as an electrochemical graining method, there is a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution.
Further, as disclosed in Japanese Patent Laid-Open No. 54-63902, a method in which both are combined can be used. The thus roughened aluminum plate is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to anodizing treatment if desired to enhance the water retention and abrasion resistance of the surface. As the electrolyte used for the anodizing 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 electrolyte.

The treatment conditions for anodic oxidation cannot be unconditionally specified because they vary depending on the electrolyte used, but generally, the concentration of the electrolyte is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C.
A current density of 5 to 60 A / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are suitable. If the amount of the anodized film is less than 1.0 g / m ² , printing durability is insufficient, or the non-image area of the planographic printing plate is easily scratched, and ink adheres to the scratched portion during printing. So-called "scratch stains" tend to occur. After being subjected to anodizing treatment, the aluminum surface is optionally subjected to hydrophilic treatment. Examples of the hydrophilic treatment used in the present invention include US Pat.
No. 714,066, No. 3,181,461, No. 3,
There are alkali metal silicate (eg sodium silicate aqueous solution) processes such as those disclosed in 280,734 and 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolyzed. In addition, potassium fluorozirconate disclosed in JP-B-36-22063 and U.S. Pat. Nos. 3,276,868 and 4,153,461,
For example, the method of treating with polyvinylphosphonic acid as disclosed in the above-mentioned No. 4,689,272 is used.

In the lithographic printing plate precursor according to the invention, the heat-sensitive layer is provided on the support in a single layer or in a laminate of two or more layers. In this case, an undercoat layer can be provided between the lower heat-sensitive layer). Various organic compounds are used as the undercoat layer component,
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, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid Organic phosphonic acid such as acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, organic phosphoric acid such as alkylphosphoric acid and glycerophosphoric acid, phenylphosphinic acid which may have a substituent, naphthylphosphinic acid, It is selected from organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxy group such as triethanolamine hydrochloride. You may use it.

This organic undercoat layer can be provided by the following method. That is, water or methanol, ethanol,
A method in which the above organic compound is dissolved in an organic solvent such as methyl ethyl ketone or a mixed solvent thereof is applied onto an aluminum plate and dried, and an organic solvent such as water or methanol, ethanol, methyl ethyl ketone or a mixed solvent thereof is applied. Is a method in which an aluminum plate is immersed in a solution in which the above organic compound is dissolved to adsorb the above compound, followed by washing with water or the like and drying to provide an organic undercoat layer. In the former method, a solution having a concentration of 0.005 to 10 mass% of the above organic compound can be applied by various methods. In the latter method, the concentration of the solution is 0.01 to 20% by mass, preferably 0.05 to 5% by mass.
And the immersion temperature is 20 to 90 ° C., preferably 25 to 5
The temperature is 0 ° C., and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds to 1 minute. The solution used for this is ammonia,
The pH can be adjusted within the range of 1 to 12 by using a basic substance such as triethylamine and potassium hydroxide, or an acidic substance such as hydrochloric acid and phosphoric acid. Further, a yellow dye may be added to improve the tone reproducibility of the image recording material. The coating amount of the organic undercoat layer is appropriately ² to 200 mg / m ² , and preferably 5 to 100 mg / m ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same applies when the amount is larger than 200 mg / m ² .

[Plate making / printing] The lithographic printing plate precursor prepared as described above is usually subjected to image exposure and development. As a light source of actinic rays used for image exposure, 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 preferable. As the emission wavelength,
760 to 1080 nm is preferable.

As the developer and replenisher for the planographic printing plate for infrared laser of the present invention, a conventionally known alkaline aqueous solution may be used. Examples of the alkaline compound used in the known alkaline aqueous solution applicable to the method of the present invention include sodium silicate, potassium potassium, sodium triphosphate, potassium phosphate, ammonium phosphate, dibasic sodium phosphate, potassium phosphate, and the like. Same ammonium, sodium carbonate, same potassium, same ammonium, sodium hydrogencarbonate, same potassium, same ammonium, sodium borate, same potassium, same ammonium, sodium hydroxide,
Examples thereof include inorganic alkali salts such as ammonium, potassium and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine,
Organic alkaline agents such as diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine are also used. To be These alkaline agents may be used alone or 2
Used in combination of two or more species. Among these alkaline agents, a particularly preferable developer is an aqueous silicate solution such as sodium silicate or potassium silicate. The reason is that the developability can be adjusted by the ratio and concentration of silicon oxide SiO ₂ which is a component of silicate and alkali metal oxide M ₂ O. For example, JP-A-54-62004, An alkali metal silicate as described in JP-B-57-7427 is effectively used.

Further, when developing using an automatic processor, an aqueous solution (replenisher) having a higher alkali strength than the developer.
It is known that a large amount of lithographic printing plate can be processed without changing the developing solution in the developing tank for a long time by adding the above-mentioned to the developing solution. Also in the present invention, this replenishment system is preferably applied. Various surfactants and organic solvents can be added to the developing solution and the replenishing solution, if necessary, for the purpose of promoting or suppressing the developing property, dispersing the development residue and enhancing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, in the developing solution and the replenishing solution, if necessary, a reducing agent such as hydroquinone, resorcin, sodium salt or potassium salt of an inorganic acid such as sulfurous acid or bisulfite, an organic carboxylic acid, a defoaming agent, and a water softening agent. It can also be added.

The printing plate developed using the above-mentioned developing solution and replenishing solution is post-treated with washing water, a rinse solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As the post-treatment when the image recording material of the present invention is used as a printing plate, various combinations of these treatments can be used.

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 the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate, each processing liquid tank and a spraying device, which conveys an exposed printing plate horizontally while pumping it up with each pump. The processing liquid is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid for processing. In such automatic processing, it is possible to perform processing while supplementing each processing solution with a replenishing solution according to the processing amount, operating time, and the like. Further, a so-called disposable processing method of processing with a substantially unused processing liquid can be applied.

In the lithographic printing plate precursor of the present invention, an unnecessary image portion (for example, of an original image film) obtained by image exposure, development, washing with water and / or rinsing and / or gumming is obtained. If there is a film edge mark or the like), the unnecessary image portion is erased. Such erasing is preferably performed, for example, by applying an erasing liquid as described in Japanese Patent Publication No. 2-13293 to the unnecessary image portion, leaving it as it is for a predetermined time, and then rinsing with water. It is also possible to use a method described in Japanese Patent Laid-Open No. 59-174842, in which an actinic ray guided by an optical fiber is applied to an unnecessary image portion and then developed.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitizing gum, if desired, but when a lithographic printing plate having higher printing durability is desired. Is subjected to a burning process. When burning a lithographic printing plate, before printing
No. 2518, No. 55-28062, JP-A-62-3
It is preferable to treat with a surface-adjusting solution as described in JP-A-1859 and JP-A-61-159655. As the method, with a sponge or absorbent cotton soaked with the surface-adjusting solution, it is applied on the lithographic printing plate, or by immersing the printing plate in a vat filled with the surface-adjusting solution, Application by an automatic coater is applied. Further, making the coating amount uniform with a squeegee or a squeegee roller after coating gives more preferable results.

The amount of the surface conditioning solution applied is generally 0.03 to 0.8.
g / m ² (dry weight) is suitable. The planographic printing plate coated with the surface-adjusting solution is dried if necessary, and then a burning processor (for example, a burning processor sold by Fuji Photo Film Co., Ltd .: “BP-130”).
0 ") and so on. The heating temperature and time in this case depend on the types of components forming the image,
The range of 180 to 300 ° C. and the range of 1 to 20 minutes are preferable.

The lithographic printing plate which has been subjected to the burning treatment can be subjected to conventional treatments such as washing with water and gumming, if necessary, but a surface-adjusting solution containing a water-soluble polymer compound or the like. When is used, so-called desensitizing treatment such as gumming can be omitted. The planographic printing plate obtained by such treatment is applied to an offset printing machine or the like and used for printing a large number of sheets.

[0075]

EXAMPLES The present invention will be described below with reference to examples.
The scope of the invention is not limited to these examples.

[Production of Alkali-Soluble Polymer Compound A]
A 500 ml three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel was charged with 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 200 ml of acetonitrile, while cooling with an ice-water bath. The mixture was stirred. To this mixture, 36.4 g (0.36 mol) of triethylamine was added dropwise with a dropping funnel over about 1 hour. After the dropping was completed, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes. In this reaction mixture,
51.7 g of p-aminobenzenesulfonamide (0.3
0 mol) was added, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, this mixture was put into 1 liter of water while stirring the water, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to remove the precipitate, which was slurried with 500 ml of water, and the slurry was filtered, and the obtained solid was dried to obtain N-.
A white solid of (p-aminosulfonylphenyl) methacrylamide was obtained (yield 46.9 g).

Next, in a 100 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel, 5.04 g (0.0) of N- (p-aminosulfonylphenyl) methacrylamide was obtained.
210 mol), 2.05 g of ethyl methacrylate (0.0
180 mol), acrylonitrile 1.11 g (0.02
1 mol) and 20 g of N, N-dimethylacetamide were added, and the mixture was stirred while heating to 65 ° C. in a hot water bath. Add "V-65" to this mixture (manufactured by Wako Pure Chemical Industries, Ltd.)
0.15 g was added and the mixture was stirred under a nitrogen stream for 2 hours while maintaining the temperature at 65 ° C. The reaction mixture was further charged with N- (p-aminosulfonylphenyl) methacrylamide 5.04.
g, 2.05 g of ethyl methacrylate, 1.11 g of acrylonitrile, 20 g of N, N-dimethylacetamide and 0.15 g of "V-65" were added dropwise by a dropping funnel over 2 hours. After the dropping was completed, the obtained mixture was further stirred at 65 ° C. for 2 hours. After the reaction, 40g of methanol
Was added to the mixture, the mixture was cooled, and the resulting mixture was added to 2 liters of water while stirring this water, the mixture was stirred for 30 minutes, and the precipitate was taken out by filtration and dried to obtain 15 g of a white solid. Obtained. When the weight average molecular weight was measured, it was 53,000. Weight average molecular weight (M
w) was measured by gel permeation chromatography (polystyrene standard).

[Production of Substrate] Aluminum having a thickness of 0.3 mm
Wash the aluminum plate (material 1050) with trichlorethylene.
After degreasing with a nylon brush and 400 mesh
Grain this surface with a water-suspension and wash it thoroughly with water.
Clean 25% sodium hydroxide aqueous solution at 45 ℃
Immerse in the liquid for 9 seconds to perform etching, wash with water, and then
It was immersed in 20% nitric acid for 20 seconds and washed with water. The grain at this time
The amount of etching on the vertical surface is about 3g / m ²Met. next
This plate has a current density of 15 A / dm with 7% sulfuric acid as an electrolyte.
²At 3 g / m²After providing the DC anodized film of, washed with water,
Dried and then with a 2.5% by weight aqueous solution of sodium silicate
Treat at 30 ° C for 10 seconds, apply the following undercoat liquid, and apply the coating film
A substrate was obtained by drying at 80 ° C. for 15 seconds. Covering the coating after drying
Coverage is 15 mg / m²Met.

[0079] Undercoat liquid   0.3 g of the following compound   100 g of methanol   1 g water

[0080]

[Chemical 3]

Example 1 The substrate 1 obtained as described above was coated with the following photosensitive solution 1 so that the coating amount after drying was 1.0 g / m ^2, and then PERFECT OVEN PH200 manufactured by TABAI.
The Wind Control was set to 7 and dried at 140 ° C. for 50 seconds to obtain a lithographic printing plate 1.

[0082] Photosensitive liquid 1   m, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight 5000 ) 0.474g   Alkali-soluble polymer compound A 2.37 g   Cyanine dye A (the following structure) 0.155 g   2-methoxy-4- (N-phenylamino) benzene   Diazonium hexafluorophosphate 0.03g   Tetrahydrophthalic anhydride 0.19g   The counter ion of ethyl violet was 6-hydroxy-β-   Naphthalene sulfonic acid 0.11g   Fluorine-based surfactant (MegaFac F177,   Dainippon Ink and Chemicals Co., Ltd.) 0.02g   Fluorosurfactant (MegaFac MCF-312,   Dainippon Ink and Chemicals Co., Ltd.) 0.05g   Paratoluenesulfonic acid 0.008g   Bis-p-hydroxyphenyl sulfone 0.13g   WAX agent (listed in Table 1) 0.06 g   γ-Butyl lactone 13g   Methyl ethyl ketone 24g   1-methoxy-2-propanol 11g

[0083]

[Chemical 4]

Examples 2 to 7 Lithographic printing plates 2 to 7 were obtained in the same manner as in Example 1 except that the WAX agent used in the photosensitive solution 1 of Example 1 was replaced by the one shown in Table 1. .

Comparative Example 1 A comparative printing plate 1 was obtained by the same procedure as in Example 1 except that the WAX agent used in the photosensitive solution 1 of Example 1 was not added.

Comparative Example 2 Instead of the WAX agent used in the photosensitive solution 1 of Example 1, Table 1 was used.
Comparative printing plate 2 was obtained in the same manner as in Example 1 except that the one described in 1 was used.

Example 8 A substrate was coated with the following photosensitive solution 2 at a coating amount of 0.85 g /
After coating so that it becomes m ² , PERFEC manufactured by Tabai
Wind Control was set to 7 in TOVEN PH200 and dried at 140 ° C. for 50 seconds. Subsequently, the photosensitive solution 3 was applied so that the applied amount after drying would be 0.15 g / m ^2, and was winded with PERFECT OVEN PH200 manufactured by Tabai.
Control was set to 7 and dried at 120 ° C. for 60 seconds to obtain a lithographic printing plate 8.

[0088] Photosensitive liquid 2   m, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight 5000 ) 0.237g   Alkali-soluble polymer compound A 2.37 g   Cyanine dye A (the above structure) 0.10 g   2-methoxy-4- (N-phenylamino) benzene   Diazonium hexafluorophosphate 0.01 g   Tetrahydrophthalic anhydride 0.19 g   The counter ion of ethyl violet was 6-hydroxy-β-   Compound made into naphthalene sulfonic acid 0.11 g   Fluorine-based surfactant (MegaFac F177,   Dainippon Ink and Chemicals Co., Ltd. 0.02 g   Fluorosurfactant (MegaFac MCF-312,   Dainippon Ink and Chemicals Co., Ltd.) 0.05 g   p-toluenesulfonic acid 0.008 g   Bis-p-hydroxyphenyl sulfone 0.10 g   γ-butyl lactone 13 g   Methyl ethyl ketone 24 g   1-methoxy-2-propanol 11 g

[0089] Photosensitive liquid 3   m, p-cresol novolac (m / p ratio = 6/4, weight average molecular weight 5000 ) 0.237g   Cyanine dye A (above structure) 0.025 g   2-methoxy-4- (N-phenylamino) benzene   Diazonium hexafluorophosphate 0.01 g   Fluorine-based surfactant (MegaFac F177,   Dainippon Ink and Chemicals Co., Ltd. 0.02 g   Fluorosurfactant (MegaFac MCF-312,   Dainippon Ink and Chemicals Co., Ltd.) 0.05 g   Bis-p-hydroxyphenyl sulfone 0.003 g   Methyl ethyl ketone 15 g   1-methoxy-2-propanol 8 g   WAX agent (described in Table 1) 0.06 g

Comparative Example 3 Instead of the WAX agent used in the photosensitive solution 3 of Example 8, Table 1 was used.
Comparative printing plate 3 was obtained in the same manner as in Example 8 except that the one described in 1 was used.

Examples 9 to 11 Instead of the WAX agent used in the photosensitive solution 1 of Example 1, Table 1 was used.
Lithographic printing plates 9 to 11 were obtained in the same manner as in Example 1 except that the one described in 1 was used. here,

[Evaluation of Scratch Performance] The obtained lithographic printing plate was subjected to rotary ablation tester (TOYOSEIK).
(Manufactured by I Co., Ltd.), and was abraded 50 times with Abraser Felt CS5 under a load of 250 g. Then, Fuji Photo Film Co., Ltd. developer DT-1 (diluted with tap water at 1: 8) was charged into Fuji Photo Film PS processor 900H and developed at a liquid temperature of 30 ° C. for a development time of 12 seconds. FP-2W (diluted with tap water at 1: 1) was used as the gum solution. Observing the obtained lithographic printing plate, ○ that the optical density of the photosensitive film of the worn portion did not change compared to the non-wearing part ○, the optical density of the photosensitive film of the worn part compared to the non-wearing part Those that were significantly reduced were marked with x.

[Evaluation of stability over time] The lithographic printing plate thus obtained was assumed to have poor storage conditions, and the room temperature was 35 ° C. and the relative humidity was 85.
%, And stored for 2 weeks in a state of being bonded to the interleaving paper. After that, the scratch performance was evaluated, and the optical density of the photosensitive film in the worn part did not change compared to the non-wearing part. ○, the optical density of the photosensitive film in the worn part was significantly larger than that in the non-wearing part. Those that fell to x were marked with x. The results are shown in Table 1.

[0093]

[Table 1]

The WAX agent used in Table 1 has the following structure.

[0095]

[Chemical 5]

As is clear from Table 1, the addition of the specific WAX agent of the present invention makes it possible to obtain an infrared laser lithographic printing plate which is excellent in scratch stability over time and is also excellent in scratch resistance. Further, it is understood that even if the lithographic printing plate for infrared laser of the present invention has a heat-sensitive layer having a multilayer structure, excellent effects can be obtained.

[0097]

INDUSTRIAL APPLICABILITY The present invention can provide a lithographic printing plate for infrared laser which is excellent in stability of scratches over time.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Noriaki Watanabe             Fuji-Sha, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture             Shin Film Co., Ltd. F term (reference) 2H025 AA11 AA13 AB03 AC08 AD03                       CB13 CB29 CB42 CC05 CC11                       CC20 DA13 FA17                 2H096 AA06 BA09 EA04 EA23 GA08

Claims (2)

[Claims] 1. (A) A substance that absorbs light and generates heat,
(B) an alkaline aqueous solution-soluble resin having a phenolic hydroxyl group, (C) a group represented by the following general formula (I),
A lithographic printing plate for infrared laser, comprising a heat-sensitive layer containing a compound having two compounds. ^{-R 1 -Y-CO-X-} R 2 Formula (I) (wherein, X represents O, and S or NR ^3, Y represents NR ³ or a single bond, R ¹ is 1 to 32 carbon atoms Represents an alkylene group or an arylene group, and R ² and R ³ represent a hydrogen atom, or an alkyl group, an alkenyl group, or an aryl group having 1 to 18 carbon atoms.) 2. A heat-sensitive layer formed on a support, the first heat-sensitive layer containing (A) a substance that absorbs light to generate heat and (B) an alkali aqueous solution-soluble resin, and a second heat-sensitive layer. The lithographic printing plate for infrared laser according to claim 1, which has a heat-sensitive layer.