JP2000187318A - Positive photosensitive composition for infrared laser beam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive composition for infrared laser beams to be used for directly forming a positive printing plate hardly soluble in unexposed parts even in the case of using a developing solution high in development activity and enhanceable in image discrimination and good in development latitude. SOLUTION: The positive photoresist composition for infrared laser beams is characterized by containing (a) a material absorbing light and generating heat, (b) an aqueous alkali-soluble polymer having phenolic hydroxyl groups, and (c) a polymer of (meth) acrylate monomer having 2 or 3 3-20 C perfluoroalkyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In recent years, lasers have been remarkably developed.
2. Description of the Related Art Semiconductor lasers are easily available in small size with high output. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like.

[0003] Positive type lithographic printing plate materials for infrared lasers are:
An essential component is an alkaline aqueous solution-soluble binder resin and an IR dye or the like that absorbs light and generates heat. The IR dye or the like dissolves in the non-exposed area (image area) by interaction with the binder resin. In the exposed area (non-image area), the generated heat weakens the interaction between the IR dye and the binder resin and dissolves in the alkaline developer to form a lithographic printing plate in the exposed area (non-image area). I do. However, if a developer having a high developer activity is used to increase the solubility of the exposed part (non-image part), there is a problem that even the non-exposed part (image part) is dissolved.

[0004] Such a problem originates in an essential difference in a plate making mechanism between a positive type lithographic printing plate material for infrared laser and a positive type lithographic printing plate material made by UV exposure. That is, in a positive lithographic printing plate material made by UV exposure, a binder resin soluble in an aqueous alkali solution and an onium salt or a quinonediazide compound are essential components, and the onium salt or the quinonediazide compound is used in a non-exposed portion ( In the image area), not only does it act as a dissolution inhibitor due to the interaction with the binder resin, but also in the exposed area (non-image area), it is decomposed by light to generate acid and acts as a dissolution promoter. Things.

On the other hand, IR dyes and the like in a positive type lithographic printing plate material for an infrared laser only act as a dissolution inhibitor in a non-exposed part (image part) and promote dissolution of an exposed part (non-image part). Not something. Therefore, in the positive type lithographic printing plate material for infrared laser, in order to improve the discrimination of the image, that is, to obtain a difference in solubility between the non-exposed portion and the exposed portion, as a binder resin,
A solution having high solubility in an alkali developing solution must be used in advance, and if a developing solution having a strong developing solution activity is used, even the non-exposed area (image area) is dissolved.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, in the present invention, even if a developer having a strong developer activity is used, the unexposed portion (image portion) is hardly dissolved, the discrimination of an image can be improved, and the development latitude is good for direct plate making. An object is to provide a positive photosensitive composition for an infrared laser.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by adding a specific fluorine-containing polymer to a positive-type photosensitive composition for infrared laser, a positive-type photosensitive composition obtained therefrom is obtained. The inventors have found that the photosensitive layer of a lithographic printing plate precursor has excellent solubility in an exposed portion (non-image portion) despite its surface being insoluble in an alkali developing solution, thereby completing the present invention. Reached. The means for solving the above problems are as follows. That is, <1> a positive photosensitive composition for an infrared laser, comprising the following (a) to (c): (A) a substance that absorbs light to generate heat, (b) an alkali aqueous solution-soluble polymer compound having a phenolic hydroxyl group,
(C) A polymer comprising a (meth) acrylate monomer having 2 or 3 perfluoroalkyl groups having 3 to 20 carbon atoms in a molecule as a polymerization component. <2> The positive for infrared laser according to <1>, wherein the polymer in (c) is a copolymer of the polymerization component in (c) and a (meth) acrylate monomer having an OH group. It is a type photosensitive composition. <3> (d) a copolymer containing at least one of the following (1) to (3) as a copolymer component in an amount of 10 mol% or more:
The positive photosensitive composition for an infrared laser according to <1> or <2>, further containing. (1) A monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule. (2) A monomer having an active imino group represented by the following formula in one molecule.

[0008]

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(3) Acrylamide, methacrylamide, acrylate, methacrylate or hydroxystyrene each having a phenolic hydroxyl group.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The positive photosensitive composition for an infrared laser of the present invention (hereinafter sometimes simply referred to as “photosensitive composition”) comprises (a) a substance that absorbs light and generates heat, and (b) a phenolic hydroxyl group. (C) a polymer having a (meth) acrylate monomer having two or three perfluoroalkyl groups having 3 to 20 carbon atoms in a molecule as a polymerization component (hereinafter referred to as “fluorine-containing compound”). (Hereinafter referred to as "polymer"), and, if necessary, other components.

[Fluorine-Containing Polymer] The fluorine-containing polymer is a (meth) acrylate monomer having two or three perfluoroalkyl groups having 3 to 20 carbon atoms in the molecule (hereinafter referred to as “fluorine-containing monomer”). Fluorinated monomer), wherein two or three perfluoroalkyl groups having 3 to 20 carbon atoms are bonded to an acryloyl group or a methacryloyl group by a tetravalent linking group. It is not particularly limited as long as it is a monomer. In the present invention,
In the case of containing only one perfluoroalkyl group or the case where the number of carbon atoms of the perfluoroalkyl group is less than 3, the discrimination of an image may not be improved. If it exceeds, the sensitivity may decrease.

The fluorine-containing polymer has the following general formula (I)
It is preferred that the fluorine-containing monomer represented by General formula (I)

[0013]

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In the general formula (I), R ¹ has 3 to 20 carbon atoms.
Represents a perfluoroalkyl group. R ¹ may represent a perfluoroalkenyl group having 3 to 20 carbon atoms. These may be linear, branched, cyclic, or a combination thereof, and further have an oxygen atom intervening in the main chain, for example, (CF ₃ ) ₂ CFOCF ₂ C
F ₂ -or the like may be used.

Z ¹ is-(CH ₂ ) _n- (where n is 1
Represents an integer of from 6 to 6. ) Or a group represented by the following formula (where R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). Here, in general formula (I), two or three Z ^{1 s} may be different two or three kinds of linking groups, respectively.

[0016]

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Z ² is-(CH ₂ ) _m- (where m is 2
Represents an integer of from 6 to 6. ) Or a group represented by the following formula.

[0018]

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R represents a hydrogen atom, a methyl group, or a halogen atom (Cl, Br, etc.). X represents a divalent linking group represented by the following formula (provided that Y is a divalent linking group having 15 or less carbon atoms and having a weight ratio of 35 to 65% in the X group). Represents a group).

[0020]

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Here, typical examples of the divalent linking group represented by Y include the following.

[0022]

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[0023]

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P and q are integers satisfying p + q = 4 (where p is 2 or 3). A represents a tetravalent linking group represented by the following formula.

[0025]

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The following are specific examples of the fluorine-containing monomer, but the present invention is not limited thereto.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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The above-mentioned fluoropolymer comprises a (meth) acrylate monomer having 2 or 3 perfluoroalkyl groups having 3 to 20 carbon atoms in a molecule, and a hydrocarbon (meth)
It may be a copolymer with an acrylate monomer. The hydrocarbon (meth) acrylate monomer preferably has an OH group. Moreover, you may use together with a hydrocarbon acrylate.

The hydrocarbon-based acrylate has one or two acryloyl groups and is known in the art (for example, Kiyomi Kato, Shoji Nakahara, “U
34, 35 in "Introduction to V-Curing Technology" (Polymer Publishing Association)
Table 10, page 46, table 16, page 46-48, table 20, page 57,
Compounds described in Table 60 and the like on pages 170 to 172) can be appropriately selected.
-8). Among them, B-2 is particularly preferred.

[0039]

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The molecular weight of the fluoropolymer is not particularly limited, but the weight average molecular weight is preferably 3,000 to 3,000.
200,000 are preferred, and 4,000 to 10
More preferably, it is 0000. Further, the addition amount of the fluoropolymer is based on the total solid content of the photosensitive composition.
It is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight.

[Polymer compound soluble in aqueous alkali solution having phenolic hydroxyl group] The polymer compound soluble in aqueous alkaline solution having phenolic hydroxyl group used in the present invention (hereinafter, simply referred to as "polymer having phenolic hydroxyl group"). For example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-
Cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixed)
Novolak resins such as mixed formaldehyde resins are exemplified.

The polymer having a phenolic hydroxyl group has a weight average molecular weight of 500 to 20,000,
Those having a number average molecular weight of 200 to 10,000 are preferred. Further, as described in U.S. Pat. No. 4,123,279, a phenol having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, and formaldehyde are used. May be used in combination. The polymer having a phenolic hydroxyl group,
One type may be used alone, or two or more types may be used in combination.

[Specific Copolymer] In the present invention, the polymer having a phenolic hydroxyl group and (1) one molecule
A monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom (hereinafter, referred to as “(1) monomer”); (2) an active imino group represented by the above formula in one molecule (Hereinafter, referred to as “monomer of (2)”), and (3) acrylamide, methacrylamide, acrylate, methacrylate, or hydroxystyrene each having a phenolic hydroxyl group (hereinafter, “(3) ) Is preferably used in combination with a copolymer containing at least one of the above as a copolymer component in an amount of 10 mol% or more (hereinafter, referred to as a “specific copolymer”). The specific copolymer more preferably contains at least one of the above (1) to (3) as a copolymer component in an amount of 20 mol% or more. If the amount of the copolymer component is less than 10 mol%, the interaction with the polymer having a phenolic hydroxyl group becomes insufficient, and the development latitude may decrease. Further, the specific copolymer may include other copolymer components other than the monomers (1) to (3) (hereinafter, referred to as “other copolymer components”).

The monomer (1) comprises a low molecular compound having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and one or more polymerizable unsaturated bonds in one molecule. Monomer. Among them, a low molecular 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 compounds include compounds represented by the following general formulas (I) to (V).

[0045]

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Where X¹, X^TwoIs -O- or
-NR^{twenty one}Represents-. R^Five, R⁸, R ¹¹, R¹³And R
¹⁷Is a hydrogen atom or -CH_ThreeRepresents R⁶, R
⁹, R¹², R¹⁵And R¹⁹Has a substituent
An alkylene group having 1 to 12 carbon atoms, cycloalkyl
Represents a len group, an arylene group or an aralkylene group.
R⁷, R¹⁶And R^{twenty one}Is a hydrogen atom, each having a substituent
An alkyl group having 1 to 12 carbon atoms which may be
Represents an alkyl group, an aryl group or an aralkyl group. Also,
R^TenAnd R²⁰Is a carbon which may have a substituent
An alkyl group having 1 to 12 primes, a cycloalkyl group, an aryl
And an aralkyl group. R¹⁴And R¹⁸Respectively
1 to 12 carbon atoms which may have a single bond or a substituent
Alkylene group, cycloalkylene group, arylene group or
Represents an aralkylene group. Y¹And Y^TwoAre simply connected
Or -CO-.

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

The monomer (2) is a monomer composed of a low molecular compound having an active imino group represented by the following formula and one or more polymerizable unsaturated bonds in one molecule.

[0049]

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As such a compound, specifically,
N- (p-toluenesulfonyl) methacrylimide, N
-(P-Toluenesulfonyl) acrylimide and the like can be suitably used.

The monomer (3) is a monomer comprising acrylamide, methacrylamide, acrylate, methacrylate or hydroxystyrene each having a phenolic hydroxyl group. As such a compound, specifically, N- (4-hydroxyphenyl) acrylamide, 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 and the like can be suitably used.

As the other copolymer component, for example, the following monomers (4) to (15) can be used. (4) Acrylic esters having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and methacrylic esters. (5) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl Alkyl acrylates such as acrylates; (6) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl Alkyl methacrylates such as methacrylate. (7) acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-
Hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-
Acrylamide or methacrylamide such as phenylacrylamide, N-nitrophenylacrylamide, and N-ethyl-N-phenylacrylamide. (8) 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.

(9) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate. (10) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chloromethylstyrene. (11) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone and phenyl vinyl ketone. (12) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (13) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (14) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide. (15) acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid;

As the specific copolymer, those having a weight average molecular weight of 2,000 or more and a number average molecular weight of 1,000 or more are preferably used. More preferably, the weight average molecular weight is 5,000 to 300,000, and the number average molecular weight is 2,
000 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.

The compounding weight ratio of the polymer having a phenolic hydroxyl group to the specific copolymer is preferably 50:50 to 5:95, and 40:60 to 10:50.
More preferably, it is 90. If the compounding amount of the polymer having a phenolic hydroxyl group is larger than this, the sea-island structure may be reversed and the solvent resistance or the like may not be improved. Conversely, if the amount of the copolymer is more than this, the surface layer of the polymer having the phenolic hydroxyl group may be too thin, and the development latitude may be insufficiently improved.

The alkali-soluble polymer compound comprising the polymer having a phenolic hydroxyl group and the specific copolymer may be used alone or in combination of two or more. 30 in solids
To 99% by weight, preferably 40 to 95% by weight, particularly preferably 50 to 90% by weight. If the amount of the alkali-soluble polymer compound is less than 30% by weight, the durability of the photosensitive layer may be deteriorated.
If the content is more than 10% by weight, both sensitivity and durability are not preferred.

[Substance that Absorbs Light and Generates Heat] In the present invention, as the substance that absorbs light and generates heat, various pigments or dyes can be used. Examples of the pigment include a commercially available pigment and a color index (C.I.).
Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technical Association, 197
7th year), “Latest Pigment Application Technology” (CMC Publishing, 198
6), "Printing Ink Technology", CMC Publishing, 1984).

Examples of the 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 pigments. . 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.

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 (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. No. The above surface treatment methods are described in “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). I have.

The pigment preferably has a particle size of 0.01 to 10 μm, more preferably 0.05 to 1 μm, and particularly preferably 0.1 to 1 μm. When the particle size of the pigment is less than 0.01 μm, the dispersion is not preferred in terms of stability in the photosensitive layer coating solution, and when it exceeds 10 μm, the uniformity of the photosensitive layer is not preferred. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. See “Latest Pigment Application Technology” (CMC
Publishing, 1986).

Examples of the dye include commercially available dyes and literatures (for example, “Dye Handbook” edited by The Society of Synthetic Organic Chemistry, Showa 4
5th edition) can be used. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, and cyanine dyes. In the present invention, among the pigments or dyes, those that absorb infrared light or near-infrared light are particularly preferable because they are suitable for use in lasers that emit infrared light or near-infrared light.

As such a pigment absorbing infrared light or near infrared light, carbon black is preferably used. Further, examples of dyes that absorb infrared light or near infrared light include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829,
Cyanine dyes described in JP-A-60-78787, JP-A-58-173696, JP-A-58-18
1690, methine dyes described in JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59-48187,
JP-A-59-73996, JP-A-60-52940
Naphthoquinone dyes described in JP-A-60-63744, squarylium dyes described in JP-A-58-112792, etc., British Patent 434,875
And the like.

Further, US Pat.
The near-infrared absorption sensitizer described in US Pat. No. 6,938 is also preferably used, and substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 3,881,924; No. 142645 (U.S. Pat. No. 4,327,169)
), A trimethine thiapyrylium salt described in
-181051, 58-22143, 59-
41363, 59-84248, 59-842
No. 49, 59-146063, 59-14606
No. 1;
Cyanine dyes described in U.S. Pat. No. 2,216,146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and JP-B-5-13514 and 5-19702.
Compound disclosed in Japanese Patent Application Publication No.
ght III-178, Epollight III-130,
Epollight III-125 and the like are particularly preferably used.

Another particularly preferred example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993. The pigment or dye is present 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 photosensitive composition.
It can be added to the photosensitive composition in an amount of 10% by weight, particularly preferably 0.5 to 10% by weight for dyes, and particularly preferably 3.1 to 10% by weight for pigments. If the amount of the pigment or dye is less than 0.01% by weight, the sensitivity may be low. If the amount exceeds 50% by weight, the uniformity of the photosensitive layer is lost and the durability of the photosensitive layer deteriorates. Sometimes. The pigment or dye may be added to the same layer as other components, or a separate layer may be provided and added thereto.
In the case of a separate layer, it is preferable to add it to a layer adjacent to a layer containing a substance which is thermally decomposable and substantially reduces the solubility of the binder when not decomposed. The pigment or dye and the binder are preferably in the same layer, but may be in different layers.

[Other Components] The positive photosensitive composition for an infrared laser of the present invention may contain various additives as the other components. For example, a substance which is thermally decomposable, such as onium salts, quinonediazides, aromatic sulfone compounds, and aromatic sulfonate compounds, and which substantially reduces the solubility of the aqueous alkali-soluble polymer compound when not decomposed is used in combination. This is preferable in that the non-exposed portion (image portion) is improved in the dissolution inhibiting property with respect to the developer.

(Onium Salt) As the onium salt,
Diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like.

Suitable onium salts include, for example, SI Schlesinger, Photogr. Sci. Eng.,
18, 387 (1974), TS Bal et al, Polymer, 21, 423
(1980), diazonium salts described in JP-A-5-158230, U.S. Patent Nos. 4,069,055 and 4,069,056
Ammonium salts described in the specification of JP-A-3-140140, DC Necker et al, Macromolecules, 17, 2468 (1
984), CS Wen et al, Teh, Proc. Conf. Rad.
g ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,05
No. 5, the phosphonium salt described in No. 4,069,056, JV
Crivello et al, Macromorecules, 10 (6), 1307 (197
7), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent Nos. 339,049, 410,201.
Iodonium salts described in JP-A-2-150848 and JP-A-2-296514, JV Crivello et al, Polymer J. 17, 7
3 (1985), JV Crivello et al. J. Org. Chem., 43,
3055 (1978), WR Watt et al, J. Polymer Sci., P.
olymer Chem. Ed., 22, 1789 (1984), JV Crivello
et al, Polymer Bull., 14, 279 (1985), JV Criv
ello et al, Macromorecules, 14 (5), 1141 (1981);
V. Crivello et al, J. Polymer Sci., Polymer Chem.
Ed., 17, 2877 (1979), European Patent Nos. 370,693, 23
Nos. 3,567, 297,443 and 297,442, U.S. Pat.
933,377, 3,902,114, 410,201, 339,04
No. 9, 4,760,013, 4,734,444, 2,833,827
Nos. 2,904,626, 3,604,580, 3,60
No. 4,581, sulfonium salt, JV Crivello et
al, Macromorecules, 10 (6), 1307 (1977), JV Criv
ello et al, J. Polymer Sci., Polymer Chem. Ed., 1
7, 1047 (1979), CS Wen et.
al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Toky
o, Oct (1988). Among the onium salts, a diazonium salt is particularly preferred. Particularly preferred diazonium salts include those described in JP-A-5-158230.

(Quinonediazides) Of the above-mentioned quinonediazides, an o-quinonediazide compound is particularly preferred. The o-quinonediazide compound is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and can be a compound having various structures. In other words, 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 fact that o-quinonediazide itself changes to an alkali-soluble substance.

The o-quinonediazide compound includes
For example, J. "Light-Sensitive Systems", Coser (John Wiley & Sons. Inc.) 339-352
The compounds described on page 4 are mentioned, and particularly preferred are sulfonic esters or sulfonic amides of o-quinonediazide reacted with various aromatic polyhydroxy compounds or aromatic amino compounds. Also,
Benzoquinone (1,2) described in 28403
-Diazidosulfonic acid chloride or naphthoquinone-
Esters of (1,2) -diazide-5-sulfonic acid chloride with pyrogallol-acetone resin, U.S. Pat.
Esters of benzoquinone- (1,2) -diazidesulfonic acid chloride or naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride and phenol-formaldehyde resin described in 046,120 and 3,188,210 are also used. Preferred are mentioned.

Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with phenol-formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-
Esters of 4-sulfonic acid chloride and pyrogallol-acetone resin are also preferred. 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, JP-A-48-9657.
5, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, and JP-B-49-17481
No. 2,797,213, U.S. Pat.No. 3,454,400, U.S. Pat.
3,544,323, 3,573,917, 3,674,495,
No. 3,785,825, British Patent No. 1,227,602, No. 1,25
No. 1,345, No. 1,267,005, No. 1,329,888, No.
No. 1,330,932 and German Patent No. 854,890.

The amount of the o-quinonediazide compound added is preferably from 1 to 50 based on the total solids of the photosensitive composition.
%, More preferably 5 to 30% by weight, particularly preferably 10 to 30% by weight. These compounds are
One type may be used alone, or two or more types may be used in combination.

Examples of the counter ion of the onium salt include boric acid tetrafluoride, phosphoric acid hexafluoride, 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.
Of these, particularly preferred are alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid.

The amount of the additives other than the o-quinonediazide compound is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 30% by weight.
It is. It is preferable that the additive and the binder are contained in the same layer.

As the other components, cyclic acid anhydrides, phenols and organic acids can be added for the purpose of improving the sensitivity. (Cyclic anhydride) Examples of the cyclic acid anhydride include phthalic anhydride described in US Pat. No. 4,115,128.
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endooxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride,
Chloromaleic anhydride, α-phenylmaleic anhydride,
And succinic anhydride, pyromellitic anhydride and the like.

(Phenols) Examples of the phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, and 4-hydroxyphenol. Benzophenone, 4,4 ', 4 "-
Trihydroxytriphenylmethane, 4,4 ', 3 ",
4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane and the like.

(Organic acids) Examples of the organic acids include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, and phosphoric acids described in JP-A-60-88942 and JP-A-2-96755. Examples include esters and carboxylic acids. 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,
Examples thereof include 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The proportion of the cyclic acid anhydride, phenols and organic acids in the total solid content of the photosensitive composition is:
0.05-20% by weight is preferred, and 0.1-15% by weight
Is more preferable, and 0.1 to 10% by weight is particularly preferable.

(Surfactant) The photosensitive composition of the present invention is described in JP-A-62-251740 and JP-A-3-208514 in order to widen the stability of processing under development conditions. Nonionic surfactants such as those described in
An amphoteric surfactant as described in JP-A-121044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearic acid, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N- Betaine type (for example, trade name “Amogen K”: manufactured by Daiichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and the amphoteric surfactant in the total solid content of the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

(Print-out agent) In the photosensitive composition of the present invention, a print-out agent for obtaining a visible image immediately after heating by exposure, and a dye or pigment as an image coloring agent can be added. Representative examples of the printing-out agent include a combination of a compound that releases an acid upon exposure to light (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-53-3622
No. 3, 54-74728, 60-3626, 61-143748
And combinations of a trihalomethyl compound and a salt-forming organic dye described in JP-A Nos. 61-151644 and 63-58440. The trihalomethyl compound includes an oxazole-based compound and a triazine-based compound, both of which have excellent stability over time and give clear print-out images.

(Image Coloring Agent) As the image coloring agent,
Other dyes can be used in addition to the salt-forming organic dyes described above. 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 Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000) , Methylene blue (CI5
2015). Dyes described in JP-A-62-293247 are particularly preferred. These dyes can be added to the photosensitive composition at a rate of 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on the total solid content of the photosensitive composition.

(Plasticizer) In the photosensitive composition of the present invention,
Further, if necessary, a plasticizer is added to impart flexibility and the like to the coating film. Specifically, 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.

[Precursor for Lithographic Printing Plate] The positive photosensitive composition for infrared laser of the present invention is preferably used as a material for a lithographic printing plate precursor. Hereinafter, the lithographic printing plate precursor will be described in detail. The lithographic printing plate precursor has a photosensitive layer formed by applying the photosensitive composition on a support,
Further, it has another layer as needed.

(Photosensitive Layer) The photosensitive layer can be usually formed by dissolving the photosensitive composition in a suitable solvent and applying it on a suitable support. Although it does not specifically limit as said solvent, For example, 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-dimethylformamide, tetramethylurea, N-
Examples include methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene and the like. These solvents are used alone or as a mixture. The concentration of the photosensitive composition (total solids including additives) in the solvent is preferably 1 to 50% by weight. The amount of coating (solid content) on the support obtained after coating and drying varies depending on the application, but generally speaking, the photosensitive printing plate is preferably 0.5 to 5.0 g / m ² .

Various methods can be used for coating on the support. For example, bar coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating can be used. And the like. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate. In the photosensitive layer, a surfactant for improving coating properties,
For example, a fluorinated surfactant as described in JP-A-62-170950 can be added. The preferred addition amount is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the photosensitive layer.

(Support) Examples of the support include dimensionally stable plate-like materials, such as paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate ( For example, aluminum, zinc, copper, etc.), plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), the above-mentioned metal-laminated or vapor-deposited paper, or plastic film.

As the support, 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. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is 10% by weight or less. Particularly preferred aluminum in the present invention is
Although it is pure aluminum, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 to 0.6 mm,
0.4 mm is preferable, and 0.2 to 0.3 mm is more preferable.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like is performed to remove the rolling oil on the surface. The surface roughening treatment of the aluminum plate
The method is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. In addition, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte.
Further, as disclosed in JP-A-54-63902, a method in which both are combined can be used. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as required, and then subjected to an anodic oxidation treatment as required to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. 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. In general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., the current density is 5 to 70%. It is appropriate that the range is 60 A / dm ² , the voltage is 1 to 100 V, and the electrolysis time is 10 seconds to 5 minutes. When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient, and the non-image area of the lithographic printing plate precursor is easily damaged, and the ink is applied to the damaged area during printing. So-called "scratch dirt" is likely to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. U.S. Pat.No. 2,714,066 as the hydrophilization treatment
Nos. 3,181,461, 3,280,734 and 3,902,73
No. 4 discloses an alkali metal silicate (for example, sodium silicate aqueous solution) method. In this method, the support is immersed or electrolytically treated with an aqueous solution of sodium silicate. In addition, Japanese Patent Publication No. 36-2206
No. 3,276,868, U.S. Pat.No. 4,153,461, and U.S. Pat.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in JP-A-689,272 is used.

(Other Layers) The lithographic printing plate precursor is as follows:
Although the photosensitive layer is provided on the support, an undercoat layer may be provided between the photosensitive layer and the other layer. As the component for forming the undercoat layer, various organic compounds are used, for example, carboxymethylcellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and may have a substituent. Good organic phosphonic acids such as phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid, naphthylphosphoric acid and alkylphosphoric acid which may have a substituent Organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid, and amino acids such as glycine and β-alanine; Has a hydroxy group such as ethanolamine hydrochloride Hydrochloride salts of amines that. These may be used alone or in combination of two or more.

The undercoat layer can be formed by the following method. That is, a method in which a solution obtained by dissolving the organic compound in water or an organic solvent such as methanol, ethanol, and methyl ethyl ketone or a mixed solvent thereof is coated on an aluminum plate and dried, and a method in which water or methanol, ethanol, methyl ethyl ketone, or the like is provided. In a solution in which the organic compound is dissolved in an organic solvent or a mixed solvent thereof,
The aluminum plate is immersed to adsorb the compound, and then washed and dried with water or the like to form an undercoat layer.

In the former method, 0.0% of the organic compound is used.
A solution having a concentration of 05 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.
The immersion temperature is 20 to 90 ° C., preferably 25 to 5 ° C.
0 ° C. and the immersion time is 0.1 second to 20 minutes, preferably 2 seconds.
Seconds to 1 minute. The solution used for this can be adjusted to pH 1 to 12 with a basic substance such as ammonia, triethylamine, potassium hydroxide or the like, or an acidic substance such as hydrochloric acid or phosphoric acid. Further, a yellow dye may be added for improving the tone reproducibility of the lithographic printing plate precursor. Coverage of the undercoat layer is preferably ^{2~200mg / m 2, 5~100mg / m} 2 is more preferable. If the coating amount is less than 2 mg / m ² , sufficient printing durability may not be obtained. The coating amount is 200 mg / m
^{The same} applies even if it is larger than ² .

[Image Exposure] The lithographic printing plate precursor is usually subjected to image exposure and development processing. 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-ray,
There are ion beams, far infrared rays, and the like. G line, i line, De
Ep-UV light and high density energy beam (laser beam) are also used. Helium laser beam
Examples include a neon laser, an argon laser, a krypton laser, a helium / cadmium laser, a KrF excimer laser, and the like. Among these, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid-state laser,
Semiconductor lasers are particularly preferred.

[Developing Process] As a developing solution and a replenishing solution used in the developing process, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Inorganic alkali salts such as ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also included. These alkali agents may be used alone or in combination of two or more. Among these alkali agents, particularly preferred developers are aqueous silicate solutions such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and concentration of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O which are components of the silicate. An alkali metal silicate described in JP-B-57-7427 is effectively used.

Further, when developing using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is used.
It has been known that a large amount of PS plates can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. Various surfactants and organic solvents may be added to the developing solution and the replenishing solution 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. it can. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, the developing solution and the replenisher may contain, if necessary, a reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as hydroquinone, resorcinol, sulfurous acid, and hydrogen sulfite; an organic carboxylic acid; an antifoaming agent; Agents can also be added. The printing plate that has been developed using the developer 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 of the lithographic printing plate precursor, various combinations of these processes 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 plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a printing plate, each processing solution tank and a spray device, and while pumping the exposed printing plate horizontally, each pumped by a pump. The developing process is performed by spraying a processing liquid from a spray nozzle. 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.

In the case where an unnecessary image portion (for example, a film edge mark of an original film) is present on a lithographic printing plate obtained by image exposure, development, washing and / or rinsing and / or gumming, The unnecessary image portion is erased. Such erasing is preferably carried out by applying an erasing liquid as described in, for example, Japanese Patent Publication No. 2-13293, to an unnecessary image portion, leaving it for a predetermined time, and then rinsing with water. A method described in JP-A-59-174842, in which an actinic ray guided by an optical fiber is applied to an unnecessary image portion and then developed, can also be used.

The planographic printing plate obtained as described above is
After applying the desensitized gum as desired, it can be subjected to a printing process. However, when a lithographic printing plate having a higher printing durability is desired, a burning treatment is performed. When burning a lithographic printing plate, before burning,
Nos. 2518, 55-28062, and JP-A-62-31859, 61
It is preferable to carry out treatment with a surface conditioning liquid as described in each publication of JP-A-159655. As a method, a sponge or absorbent cotton impregnated with a surface-regulating liquid is applied on a lithographic printing plate, or a printing plate is immersed in a vat filled with the surface-regulating liquid, or is applied automatically. Coating by a coater or the like is applied. Further, it is more preferable to make the application amount uniform with a squeegee or a squeegee roller after the application.

The coating amount of the surface conditioning liquid is generally 0.03 to
0.8 g / m ² (dry weight) is suitable. The lithographic printing plate to which the surface conditioning liquid has been applied is dried, if necessary, and then burned (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 preferably in the range of 180 to 300 ° C. and 1 to 20 minutes.

The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming, if necessary. When a liquid is used, so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0099]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1 <Synthesis of Fluoropolymer 1> Stirrer, condenser,
In a glass flask having a temperature property, 30 parts by weight of the fluorine-containing monomer (A-31) shown in the above [Chemical Formula 19], 20 parts by weight of methyl methacrylate, 10 parts by weight of hydroxyethyl methacrylate, and 15 parts by weight of i-butyl methacrylate And 150 parts by weight of methyl isobutyl ketone, and 0.4 parts by weight of azobisisobutyronitrile as a polymerization initiator and 0.3 parts by weight of lauryl mercaptan as a chain transfer agent were added under reflux with nitrogen gas. After that, 7
The mixture was refluxed for an hour to complete the polymerization, whereby a fluoropolymer 1 was synthesized. The molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) was Mn = 10,000.

<Synthesis of Specific Copolymer 1> 31.0 g (0.36 mol) of methacrylic acid and 39.1 g (0.36 mol) of ethyl chloroformate were placed in a 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel. ) And 200 ml of acetonitrile, and the mixture was stirred while being cooled in an ice-water bath. 36.4 g of triethylamine (0.
(36 mol) was dropped by a dropping funnel over about 1 hour. After the addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes.

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

Next, 4.61 g of the obtained N- (p-aminosulfonylphenyl) methacrylamide was placed in a 20 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
(0.0192 mol), 2.94 g of ethyl methacrylate
(0.0258 mol), 0.80 g of acrylonitrile
(0.015 mol) and 20 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. 0.15 g of "V-65" (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the mixture, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. To this reaction mixture was further added a mixture of 4.61 g of N- (p-aminosulfonylphenyl) methacrylamide, 2.94 g of ethyl methacrylate, 0.80 g of acrylonitrile, 0.15 g of N, N-dimethylacetamide and "V-65". Was dropped by a dropping funnel over 2 hours. After dropping, add 2
The resulting mixture was stirred for hours. After the completion of the reaction, 40 g of methanol was added to the mixture, and the mixture was cooled.
This water was added to a liter with stirring, and after stirring the mixture for 30 minutes, the precipitate was taken out by filtration and dried to obtain 15 g of a white solid. By gel permeation chromatography, this particular copolymer 1
Was measured to have a weight average molecular weight (polystyrene standard) of 53,000.

<Preparation of Substrate> An aluminum plate (material 1050) having a thickness of 0.3 mm was washed with trichlorethylene and degreased, and then its surface was grained using a nylon brush and a 400 mesh pumice-water suspension. Washed well with water. This plate was immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds to perform etching.
It was immersed in 0% nitric acid for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . next,
This plate was subjected to a current density of 15 A / dm using 7% sulfuric acid as an electrolyte.
To provide a DC anodic oxide film of 3 g / m ² by ^2, washed with water, dried, further coated with the following undercoat solution, a coating film 90
Dry for 1 minute at ° C. The coating amount of the coating film after drying is 10 mg /
m ² .

Undercoating liquid β-alanine 0.5 g methanol 95 g water・ ・ ・ ・ ・ ・ ・ 5g

Further, the substrate was treated with a 2.5% by weight aqueous solution of sodium silicate at 30 ° C. for 10 seconds, the following undercoating solution was applied, and the coating film was dried at 80 ° C. for 15 seconds to obtain a substrate. The coating amount of the coating film after drying was 15 mg / m ² . Undercoat liquid Compound of the following formula: 0.3 g methanol: 100 g water:・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1g

[0107]

Embedded image

Next, the following photosensitive solution 1 was prepared. Using the obtained substrate as a support, this photosensitive liquid 1 was applied in an amount of 1.8.
g / m ² to form a photosensitive layer to obtain a lithographic printing plate precursor.

Photosensitive solution 1 Fluoropolymer 1 0.01 g Specific copolymer 1 0.75 g m, p-cresol novolak 0.25 g (m, p ratio = 6/4, weight average molecular weight 3,500, unreacted cresol 0.5% by weight 0.003 g Tetrahydrophthalic anhydride 0.03 g Cyanine dye A (structure below) 0.017 g Victoria Pure Blue BOH dye with 1-naphthalenesulfonic acid anion as counter ion・ ・ 0.015g Megafac F-177 ・ ・ ・ ・ ・ ・ 0.05g ( Fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) γ-butyl lactone 10 g methyl ethyl ketone 10 g 1-methoxy-2-propanol 1 g

[0110]

Embedded image

With respect to the obtained lithographic printing plate precursor, the measurement of the sensitivity and the evaluation of the film strength of the photosensitive layer with respect to an alkali developing solution were performed as follows.

(Measurement of Sensitivity) The obtained lithographic printing plate precursor was subjected to an output of 500 mW, a wavelength of 830 nm, and a beam diameter of 17 μm.
m (1 / e ² ) using a semiconductor laser with a main scanning speed of 5 m
/ Sec, and an automatic developing machine (manufactured by Fuji Photo Film Co., Ltd .: “PS” manufactured by Fuji Photo Film Co., Ltd.) containing DP-4, a rinse solution FR-3 (1: 7 dilution). Processor 900VR "). that time,
DP-4 used at a dilution of 1: 6 to 1:10,
The line width of the non-image area obtained with the developing solution was measured, and the irradiation energy of the laser corresponding to the line width was determined, and this was defined as the sensitivity. Table 1 shows the results. The smaller the irradiation energy amount, the higher the sensitivity.
The smaller the difference between the sensitivity at 4 (1: 6 dilution) and the sensitivity at DP-4 (1:10 dilution), the better the development latitude.

(Evaluation of Film Strength of Photosensitive Layer) The obtained lithographic printing plate precursor was not exposed, but was exposed to a developer (manufactured by Fuji Photo Film Co., Ltd.), DP-4, rinse solution FR-3 (1: 7 dilution). ) (Fuji Photo Film Co., Ltd .: "PS
Processor 900VR "). At that time, DP-4 diluted at 1: 6 to 1:10 was used. The reflection density of the obtained solid image is referred to as Macbeth.
RD914 reflection densitometer (Kollmorgen)
Was measured. Table 1 shows the results. The higher the reflection density, the higher the film strength of the photosensitive layer, which means that the surface of the photosensitive layer is not immersed in the developing solution.

Example 2 A lithographic printing plate was prepared in the same manner as in Example 1 except that the photosensitive solution 1 was prepared in the same manner as in Example 1, except that the content of the fluoropolymer 1 was changed from 0.01 g to 0.05 g. A master plate was manufactured and its performance was similarly evaluated. Table 1 shows the results.

Comparative Example 1 A lithographic printing plate precursor was produced in the same manner as in Example 1 except that the photosensitive solution 1 was prepared without containing the fluoropolymer 1 at all. The performance was evaluated. Table 1 shows the results.

[0116]

[Table 1]

From the results shown in Table 1, in Examples 1 and 2, D
Sensitivity at P-4 (1: 6 dilution) and DP-4 (1: 1 dilution)
At 0 dilution), the difference in sensitivity was small, indicating that the development latitude was good. Further, in Examples 1 and 2, even when developed with DP-4 (1: 6 dilution) having high developer activity, the reflection density of a solid image is high and the surface of the photosensitive layer is hardly immersed in the developer (surface (Slightly soluble). On the other hand, in Comparative Example 1, the same sensitivity as in Examples 1 and 2 was obtained, and the development latitude was good. However, when developed with DP-4 (1: 6 dilution) having a high developer activity,
It can be seen that the reflection density of the solid image is low and the film strength of the photosensitive layer is inferior.

[0118]

According to the present invention, even when a developer having a strong developer activity is used, the non-exposed area (image area) is hardly dissolved, the discrimination of the image can be improved, and the development latitude is good. A positive photosensitive composition for an infrared laser for direct plate making can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA04 AB03 AC08 AD03 CB06 CB14 CB15 CB17 CB28 CB41 CB45 CB52 CC11 2H114 AA06 BA01 DA52 DA53 DA59

Claims (3)

[Claims] 1. A positive photosensitive composition for an infrared laser, comprising the following (a) to (c). (A) a substance that absorbs light and generates heat; (b) a polymer compound soluble in an aqueous alkali solution having a phenolic hydroxyl group; and (c) two or three perfluoroalkyl groups having 3 to 20 carbon atoms in the molecule. A polymer containing a (meth) acrylate monomer as a polymerization component. 2. The infrared laser according to claim 1, wherein the polymer in (c) is a copolymer of the polymerization component in (c) and a (meth) acrylate monomer having an OH group. Positive photosensitive composition. 3. The infrared laser according to claim 1, further comprising (d) a copolymer containing at least one of the following (1) to (3) as a copolymer component in an amount of 10 mol% or more. Positive photosensitive composition. (1) A monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule. (2) A monomer having an active imino group represented by the following formula in one molecule: (3) Acrylamide, methacrylamide, acrylate, methacrylate, or hydroxystyrene each having a phenolic hydroxyl group.