JP2003012746A - Image recording material and polymer compound used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both an image recording material capable of forming a high-sensitivity image by an infrared laser and an image having excellent stain prevention of non-image part and scratch resistance of image part and a high image quality, and a new polymer compound having infrared absorption ability used therefor. SOLUTION: The image recording material is characterized in that the material comprises a polymer compound having (A) a structural unit containing an alkali-soluble functional group, (B) a structural unit having a surface orientation functional group and (C) a structural unit having infrared absorption ability, and solubility in an alkali development solution is changed by infrared ray irradiation. A fluorine atom-containing group such as a perfluoroalkenyl group, a polysiloxane group, a >=5C straight or branched chain alkyl group, or the like, may be cited as the surface orientation functional group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type or negative-type image recording material capable of recording an image by exposure to an infrared laser and changing the solubility of the recording layer in the exposed portion, and a polymer compound used therein. An image recording material for an infrared laser, which is writable by exposure in a near infrared region such as an infrared laser, and is particularly suitable for a lithographic printing plate precursor for so-called direct plate making, which can directly make a plate from a digital signal of a computer or the like, and The present invention relates to a polymer compound that can be preferably used.

[0002]

2. Description of the Related Art In recent years, with the development of solid-state lasers and semiconductor lasers having a light emitting region from near infrared to infrared, as a system for directly making a plate from computer digital data,
The thing using these infrared lasers attracts attention. A positive type lithographic printing plate material for infrared laser for direct plate making is disclosed in JP-A-7-285275. The present invention is an image recording material in which a substance that absorbs light and generates heat and a positive photosensitive compound such as quinonediazide compounds are added to an alkali aqueous solution soluble resin, and a positive photosensitive compound is used in the image area. However, it acts as a dissolution inhibitor that substantially reduces the solubility of the alkali aqueous solution soluble resin, and in the non-image area it is decomposed by heat so that it does not develop the dissolution inhibiting ability, and it can be removed by development, and the image is Form.

On the other hand, it is known that onium salts and compounds capable of forming a hydrogen bond network with low alkali solubility have an alkali dissolution inhibiting action on alkali-soluble polymers.
As an infrared laser compatible image recording material, a composition using a cationic infrared absorbing dye as a dissolution inhibitor of an alkaline water-soluble polymer exhibits a positive action.
It is described in. This positive action is a function in which the infrared absorbing dye absorbs the laser light and the generated heat eliminates the dissolution inhibiting effect of the polymer film in the irradiated portion to form an image.
Further, as a negative type image forming method, a recording method of forming an image part by curing a recording layer in an exposed part by causing a condensation crosslinking reaction by a heat treatment after exposure using an acid generated by light or heat as a catalyst As a printing plate having such an acid-catalyzed cross-linking recording layer, JP-A-7-2710 is known.
A technique described in Japanese Patent Publication No. 29 is known. Further, there is a recording method in which a polymerization reaction is caused by using a radical generated by light or heat as an initiator to cure the recording layer in the exposed area to form an image area. As the printing plate having layers,
Techniques using a photopolymerizable or thermopolymerizable composition as described in JP-A-8-108621 and JP-A-9-34110 as a photosensitive layer are known.

The image forming properties of the above various recording materials will be described. Although the laser irradiation surface of the light-sensitive material can obtain sufficient energy for the image forming reaction, thermal diffusion, especially,
When a general-purpose aluminum support is used as the support,
Since the thermal conductivity is good, the heat diffusion to the support is remarkable, the energy is not fully utilized for image formation, and the sensitivity is low. The effect of accelerating the curing reaction cannot be obtained due to
The positive type is liable to cause non-image stains due to the residual film, and the negative type has a problem that sufficient image strength cannot be obtained and the scratch resistance is poor. For the purpose of easily achieving the film strength (image strength) when used as an image forming material, for example, US6
No. 124425 describes an example of an alkali-soluble resin having an infrared absorbing functional group in its side chain. That is, it is intended to improve the film strength by introducing a partial structure having a photothermal conversion function into the alkali-soluble resin to reduce the components in the material. However, since this alkali-soluble resin is a high molecular weight compound having a molecular weight of 5000 or more, its adhesion to the base material becomes great and its solubility in the processing agent at the time of development becomes insufficient. When used as an image forming material, the solubility of the non-image area is low, the recording layer to be removed is not sufficiently removed by the development process, and a residual film is liable to cause stains on the non-image area. Had.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to form an image with high sensitivity by an infrared laser,
An object of the present invention is to provide an image recording material capable of forming a high-quality image with excellent stain resistance in the non-image area and scratch resistance in the image area, and a novel polymer compound having an infrared absorbing ability which can be suitably used for the image recording material.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventor for the purpose of improving the sensitivity and image forming property of image recording materials, as a result, a structural unit having an infrared absorbing ability in an alkali-soluble resin, The present invention has been completed by finding that the above object can be achieved by using a polymer compound into which a structural unit having surface orientation is introduced. That is, the image recording material of the present invention comprises (A) a structural unit having an alkali-soluble functional group, (B) a structural unit having a surface-orienting functional group,
And (C) a polymer compound having a structural unit having an infrared absorbing ability, which is characterized in that its solubility in an alkali developing solution is changed by infrared irradiation. Further, the polymer compound of the present invention according to claim 2 is (A) a structural unit having an alkali-soluble functional group, (B) a structural unit having a surface-oriented functional group, and (C) an infrared absorbing ability. And a structural unit having

Although the action of the present invention is not clear, since the polymer compound used in the image recording material of the present invention has (B) a structural unit having a surface orientation, it is used in a recording layer such as a lithographic printing plate precursor. , Tends to be localized in the vicinity of the surface of the recording layer and is less likely to be adsorbed to the interface between the support and the substrate. Therefore, (C) while maintaining high sensitivity and image strength due to the structural unit having infrared absorbing ability, It is considered that only the stain resistance of the non-image area is improved. Further, (B) the surface-oriented structural unit in the alkali-soluble resin has a relatively low surface energy and effectively prevents scratches due to rubbing, and at the same time the dissolution inhibiting ability is maintained, the penetration of the developer is effective. It is considered that excellent scratch resistance can be achieved because the scratch resistance can be suppressed.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
First, the specific alkali-soluble polymer compound used in the image recording material of the present invention will be described. [(A) a structural unit having an alkali-soluble functional group,
(B) a structural unit having a surface-oriented functional group, and
(C) Polymer Compound Comprising Structural Unit Having Infrared Absorption Ability] (A) Structural Unit Having Alkali-Soluble Functional Group, (B) Structural Unit Having Surface-Orienting Functional Group, and , (C) a polymer compound having a structural unit having infrared absorbing ability (hereinafter, appropriately referred to as a surface orientation type infrared absorbing alkali-soluble resin) is a conventionally known water-insoluble and soluble in an alkaline aqueous solution. Any polymer may be used as long as at least one substituent having surface orientation and at least one substituent (structural unit) having infrared absorbing ability are introduced into the structure of a polymer compound.

The base water-insoluble and alkali-water-soluble polymer compound (hereinafter, appropriately referred to as alkali-soluble polymer) includes (1) phenolic hydroxyl group and (2)
A polymer compound having a functional group of either a sulfonamide group or (3) an active imide group in the molecule is preferable, and a polymer compound having (1) a phenolic hydroxyl group in the molecule is particularly preferable. However, it is not limited to this. Examples of such an alkali-soluble polymer include compounds described in JP-A 2000-338651 as (c) alkali-soluble polymer.

The surface alignment type infrared absorbing alkali-soluble resin is specifically (b) a surface alignment group in one molecule,
And a polymerizable monomer composed of a low molecular weight compound having at least one polymerizable unsaturated bond (hereinafter, referred to as “(b) surface alignment type monomer unit”), (c) an infrared absorbing group in one molecule, and A polymerizable monomer composed of a low molecular weight compound having at least one polymerizable unsaturated bond group (hereinafter referred to as “(c) infrared absorbing monomer unit”) and a preferred polymerization component of an alkali-soluble polymer compound ( a-1) Copolymerization with at least one of a polymerizable monomer having a phenolic hydroxyl group, (a-2) a polymerizable monomer having a sulfonamide group, and (a-3) a polymerizable monomer having an active imide group. Examples thereof include a combination or a copolymer of these three kinds of monomers and another polymerizable monomer. Further, as the surface-aligned infrared absorbing alkali-soluble resin having a phenolic hydroxyl group as an alkali-soluble group, a resin obtained by condensing a phenol compound such as novolak resin and aldehydes such as formaldehyde can be mentioned. A structural unit having a surface-orienting substituent and an infrared-absorbing substituent in either or both of the compound and the aldehyde, and consequently (A) an alkali-soluble functional group in one molecule, (B ) All of the structural units having a surface-orienting functional group and (C) the structural units having an infrared absorbing ability are included.

The surface-aligned infrared-absorbing alkali-soluble resin according to the present invention may have a specific monomer unit having each function as a constituent unit, as exemplified below. In order to obtain such a surface-aligned infrared absorbing alkali-soluble resin of the present invention, a method of synthesizing each of the following specific monomer units as a starting material can also be used. From the surface-aligning functional group and the monomer excluding the substituent having infrared-absorbing property was synthesized, and then homopolymerized or copolymerized to obtain a polymer compound. It is also possible to adopt a method in which a specific alkaline water-soluble polymer having the following specific monomer unit as a constitutional unit is eventually obtained by introducing a substituent having a property by a polymer reaction.

As the polymer reaction for introducing a substituent having surface orientation and infrared absorption ability, a method of electrophilically or nucleophilically substituting an aromatic ring in an alkali-soluble polymer, or an alkali-soluble polymer is used. Examples thereof include a method of modifying a substituent such as a hydroxyl group or an amino group therein with an ester bond, an ether bond, a (thio) urethane bond, an ester bond, a (thio) urea bond or an amide bond. Among them, the method of modification with a bond such as an amide bond is preferable, and the method of modification with an ether bond, an ester bond, or a (thio) urethane bond is particularly preferable from the viewpoint of ease of synthesis and availability of raw materials.

As the substituent having surface orientation introduced into the surface orientation type infrared absorbing alkali-soluble resin according to the present invention, a recording layer coating solution containing an image recording material is prepared,
When the recording layer is formed by coating and drying it, the surface-aligned infrared absorbing alkali-soluble resin shifts to the vicinity of the surface and has a function of being localized.
Substituents having so-called surface orientation are preferred.

The following are suitable examples of the substituent having such surface orientation. (a) Fluorine atom, (b) trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, (c) −
_{(CF 2) n CF 3,} -CF 2 (CF 2) m H ( wherein, n represents an integer of 3 to 20, m is an integer of 0 to 19) perfluoroalkyl group represented by, (d ) Fluorine-substituted aryl groups such as pentafluorophenyl group and tetrafluorophenyl group, (e) —C (CF ₂ CF ₃ ) ═C (CF ₃ ) ₂ , —C
_{(CF 3) = C [CF} (CF 3) 2], - C [CF (C
_{F 3) 2] = C (} CF 3) CF 2 CF 2 CF 3, -C (C
F ₃ ) = C (CF ₃ ) C (CF ₃ ) (CF ₂ CF ₃ ) ₂ and other perfluoroalkenyl groups, (f) a plurality of —Si—O—S
A polysiloxane group having an i-bond, (g) a linear or branched alkyl group having 5 or more carbon atoms, and the like.

Specific examples of these (b) specific monomer units having surface orientation will be shown below by specifically listing their general structures and functional groups to be introduced. It is not limited to.

[0016]

[Chemical 1]

[0017]

[Chemical 2]

[0018]

[Chemical 3]

[0019]

[Chemical 4]

[0020]

[Chemical 5]

[0021]

[Chemical 6]

Next, the infrared absorbing monomer unit (c) will be described. The unit having infrared absorbing ability to be bonded to the infrared absorbing monomer unit used in the present invention has a functional group capable of forming a bond with the above alkali-soluble polymer, and is a compound that absorbs infrared light and generates heat. There is no particular limitation so long as it is an organic material such as a polymethine dye such as a cyanine dye, a (thio) pyrylium dye, an oxonol dye, or a phthalocyanine dye, from the viewpoint of image forming property and solvent solubility when used as a positive image recording material. A unit having a dye skeleton is preferable, and a particularly preferable polymethine dye unit is a dye having a structure of the following general formula (1).

[0023]

[Chemical 7]

In the general formula (1), R ¹ and R ² each independently represents an alkyl group having 1 to 12 carbon atoms, and on the alkyl group, an alkoxy group, an aryl group, an amide group, an alkoxycarbonyl group, a hydroxyl group. It may have a substituent selected from a sulfo group and a carboxyl group. Y ¹ and Y ² are each independently oxygen, sulfur, selenium, a dialkylmethylene group or -C.
Represents H = CH-. Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group or a heterocyclic group, and are an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an alkyl (oxy) sulfonyl group, an aryl (oxy) sulfonyl group, a halogen-substituted group. A hydrocarbon group having a naphthalene skeleton is preferable, which may have a substituent selected from an alkyl group, and an aromatic ring may be condensed with two consecutive carbon atoms adjacent to Y ¹ and Y ² . X represents a counter ion necessary for neutralizing the charge, and is not always necessary when the dye cation portion has an anionic substituent. Q represents a trimethine group, a pentamethine group, a heptamethine group, a nonamethine group or an undecamethine group, which is preferably substituted on any carbon atom with a chlorine atom, and a cyclohexene ring or cyclopentene ring containing three consecutive methine chains. Having a ring is preferable from the viewpoint of stability.

Specific examples of these specific monomer units having infrared absorbing ability are shown below by specifically listing their general structures and functional groups to be introduced.
The present invention is not limited to these.

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

Next, typical examples of the polymerization component of the alkaline water-soluble polymer compound into which these surface orientation unit and infrared absorbing unit are introduced will be described. Examples of the polymerizable monomer (a-1) having a phenolic hydroxyl group include a polymerizable monomer composed of a phenolic hydroxyl group and a low molecular weight compound having at least one polymerizable unsaturated bond, and examples thereof include phenolic compounds. Examples thereof include acrylamide having a hydroxyl group, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene.

Specifically, for example, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl).
Methacrylamide, N- (3-hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate,
m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate, p
-Hydroxyphenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (2-hydroxyphenyl) ethyl acrylate, 2- (3-hydroxyphenyl) ethyl acrylate, 2- (4-hydroxyphenyl) Examples thereof include ethyl acrylate, 2- (2-hydroxyphenyl) ethyl methacrylate, 2- (3-hydroxyphenyl) ethyl methacrylate and 2- (4-hydroxyphenyl) ethyl methacrylate. Two or more kinds of these monomers having a phenolic hydroxyl group may be used in combination.

(A-2) Polymerization having a sulfonamide group
As the volatile monomer, at least one nitrogen atom is present in one molecule.
Sulfonamide group (-NH-
SO ₂-) And at least one polymerizable unsaturated bond
The polymerizable monomer composed of the above low molecular weight compound
, For example, an acryloyl group, an allyl group, or vinylo
An oxy group and a substituted or monosubstituted aminosulfonyl group or
Low molecular weight compounds having a substituted sulfonylimino group are preferred.
Good Examples of such a compound include, for example, JP-A-8-
Represented by the general formulas (I) to (V) described in No. 123029.
Compounds. (A-2) a polymerizable monomer having a sulfonamide group
Specifically, m-aminosulfonylphenylmethac
Relate, N- (p-aminosulfonylphenyl) meta
Chrylamide, N- (p-aminosulfonylphenyl)
Acrylamide and the like can be preferably used.

As the polymerizable monomer (a-3) having an active imide group, those having an active imide group described in JP-A No. 11-84657 in the molecule are preferable, and an active imide group is contained in one molecule. Examples of the polymerizable monomer include a low molecular weight compound having one or more polymerizable unsaturated bonds. As the polymerizable monomer having (a-3) an active imide group, specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be preferably used. .

Examples of the other polymerizable monomer that constitutes the alkali-soluble polymer include the following (a-4) to (a-
The monomers listed in 15) can be used, but the monomers are not limited to these. (A-4) 2-hydroxyethyl acrylate or 2-
Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as hydroxyethyl methacrylate. (A-5) Alkyl such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, etc. Acrylate. (A-6) Methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2
-Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, etc. (A-7) acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide,
N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide,
Acrylamide or methacrylamide such as N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide.

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

The alkaline water-soluble polymer compound having (b) the surface aligning unit and (c) the infrared absorbing unit is excellent in image formability upon exposure with an infrared laser or the like, and thus the surface aligning unit and the infrared ray A polymer having a phenolic hydroxyl group in the structure of a polymer compound, such as a polymer of a polymerizable monomer having an absorptive unit and a polymerizable monomer having a phenolic hydroxyl group, is preferable. It is also possible to use a polymer unit and an infrared absorbing unit introduced into an alkaline water-soluble polymer compound having a phenolic hydroxyl group. Examples of such an alkaline water-soluble polymer compound having a phenolic hydroxyl group include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin,
Examples thereof include novolak resins such as m- / p-mixed cresol formaldehyde resin and phenol / cresol (m-, p-, or m- / p-mixed) mixed formaldehyde resin, and pyrogallolacetone resin.

As the alkaline water-soluble polymer compound having a phenolic hydroxyl group, further, as described in US Pat. No. 4,123,279,
Carbon number 3 ~, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin
Examples thereof include a condensation polymer of phenol and formaldehyde having the alkyl group of 8 as a substituent. As a method of copolymerizing the alkaline water-soluble polymer compound having a surface orientation unit and an infrared absorbing unit, a conventionally known method such as a graft copolymerization method, a block copolymerization method, or a random copolymerization method may be used. it can.

In the surface alignment type infrared absorbing alkali-soluble resin of the present invention, (A) a structural unit having an alkali-soluble functional group, (B) a structural unit having a surface-aligning functional group, and (C) an infrared absorbing Regarding the content of each structural unit of the structural unit having a function, (b) a polymerizable monomer having a surface alignment unit and (c) a polymerizable monomer having an infrared absorbing unit, which are the basis of the structural unit, (A) Blending molar ratio with other polymerizable monomer (total of polymerizable monomer having surface orientation unit and polymerizable monomer having infrared absorbing unit: other polymerizable monomer, [(b) + ( c)]:
(A)) is preferably 1:99 to 75:25, more preferably 5:95 to 65:35, and most preferably 5:95 to 50:50. Further, the blending molar ratio of the monomer unit (b) having surface orientation in the polymer compound is preferably in the range of 1 to 60%. When the blending ratio is small, the surface of the positive type lithographic printing plate material is locally dispersed. Difficult to form a localized outermost layer, the development latitude, the effect of improving scratch resistance tends to be small, and conversely, if it is too large, the image forming property and the solubility in a coating liquid tend to decrease, and both Not preferable. Further, the blending molar ratio of the infrared absorbing monomer unit (c) is preferably in the range of 1 to 40% in the polymer compound. When the blending ratio is small, the sensitivity to infrared rays is lowered and the image forming property is lowered. If it is too large, on the other hand, the developability and the solubility in the coating solution tend to decrease, and both are not preferable.

The surface-aligned infrared absorbing alkali-soluble resin of the present invention preferably has a weight average molecular weight of 500 or more, more preferably 1,000 to 700,000. The number average molecular weight is preferably 500 or more, more preferably 750 to 650,000. The dispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.

The surface-aligned infrared absorbing alkali-soluble resin may be used alone or in combination of two or more kinds,
The total content is 1 to 9 in the total solid content of the image recording material.
0 wt% is preferable, 2-80 wt% is more preferable,
2-75% by weight is particularly preferred. When the content is less than 1% by weight, durability tends to deteriorate, and
When it exceeds 90% by weight, the sensitivity and the image forming property tend to be deteriorated, which is not preferable. Hereinafter, typical compounds of the surface-aligned infrared-absorbing alkali-soluble resin will be exemplified together with the maximum weight-average molecular weight absorption wavelength and the m / p ratio in the alkali-soluble resin structural unit as the main component, but the present invention is not limited thereto. .

[0043]

[Chemical 14]

[0044]

[Chemical 15]

[0045]

[Chemical 16]

[0046]

[Chemical 17]

[0047]

[Chemical 18]

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23]

[Other Components] 1. Alkali-Soluble Resin In the image recording material of the present invention, a conventionally known alkali water-soluble polymer compound may be used in combination with the surface-aligned infrared absorbing alkali-soluble resin as long as the effect of the present invention is not impaired. it can. The conventionally known alkali water-soluble polymer compound is mentioned as the polymerization component of the alkali water-soluble polymer compound into which the surface alignment unit and the infrared absorbing unit are introduced (a).
Examples thereof include a homopolymer of a polymerization component monomer of an alkaline water-soluble polymer compound, a copolymer obtained by combining a plurality of kinds, and a copolymer of the monomer (a) with another polymerizable component. The content of this general alkali-soluble resin is 0 to 95% by weight with respect to the surface alignment type infrared absorbing alkali-soluble resin according to the present invention, preferably 5
It is 0 to 95% by weight, and more preferably 70 to 90% by weight.

2. Infrared absorbing agent In the image recording material of the present invention, a conventionally known infrared absorbing agent can be used in combination with the surface-aligned infrared absorbing alkali-soluble resin as long as the effect of the present invention is not impaired. The infrared absorbent that can be used in the present invention can be used without any limitation in the absorption wavelength range as long as it is a substance that absorbs the light energy radiation used for recording and generates heat. Wavelength 760nm to 1200nm from the viewpoint of compatibility with output lasers
Infrared absorbing dyes or pigments having maximum absorption are preferably mentioned.

As the dye, commercially available dyes and known dyes described in documents such as "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, oxonol dyes. , Dyes such as diimonium dyes, aminium dyes, and croconium dyes.

Preferred dyes are, for example, JP-A-5
Cyanine dyes described in JP-A No. 8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and JP-A-58-1736.
96, JP-A-58-181690, JP-A-58-1
Methine dyes described in Japanese Patent Application No. 94595, JP-A-Sho 5
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940, JP-A-60-63744 and the like, JP-A-58-1
Squarylium dyes described in No. 12792,
Examples thereof include cyanine dyes described in British Patent 434,875.

The near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and the substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also used. Pyrylium salt, JP-A-57-142645
Trimethine thiapyrylium salt described in U.S. Pat. No. 4,327,169, JP-A Nos. 58-181051, 58-220143, 59-41363 and 59-11363.
-84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranium compounds described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fair 5-13
The pyrylium compounds disclosed in Nos. 514 and 5-19702 are also preferably used.

Another preferred example of the dye is represented by the formula (I) in US Pat. No. 4,756,993:
The near infrared absorbing dye described as (II) can be mentioned.

Of these dyes, particularly preferred are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Further, the dyes represented by the following general formulas (a) to (e) are preferable because they are excellent in light-heat conversion efficiency, and particularly, the cyanine dye represented by the following general formula (a) is used in the polymerizable composition of the present invention. This is most preferable because it gives high polymerization activity, and is excellent in stability and economy.

[0060]

[Chemical formula 24]

In the general formula (a), X ¹ represents a hydrogen atom, a halogen atom, -NPh ₂ , X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom or a sulfur atom, and L ¹
Represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, and a hydrocarbon group having 1 to 12 carbon atoms containing a hetero atom. Here, the hetero atom means N,
S, O, a halogen atom and Se are shown.

[0062]

[Chemical 25]

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the photosensitive layer coating solution, R ¹ and R ² are preferably a hydrocarbon group having 2 or more carbon atoms, and R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable to form a 6-membered ring.

Ar ¹ and Ar ^{2, which} may be the same or different, each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a hydrocarbon group having 12 or less carbon atoms,
Examples thereof include a halogen atom and an alkoxy group having 12 or less carbon atoms. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ^{4, which} may be the same or different, each represents a hydrocarbon group having 20 or less carbon atoms, which may have a substituent. Preferred substituents include an alkoxy group having 12 or less carbon atoms, a carboxyl group and a sulfo group. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, hydrogen atom is preferable. In addition, Za ^-
Represents a counter anion. However, when any of R ^{1 to} R ⁸ is substituted with a sulfo group, Za ⁻ is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion from the storage stability of the photosensitive layer coating solution, and a perchlorate ion is particularly preferred,
Hexafluorophosphate ion and aryl sulfonate ion.

In the present invention, specific examples of the cyanine dye represented by the general formula (a) which can be preferably used include those shown below and Japanese Patent Application No. 11-31062.
Paragraph numbers [0017] to [0019] of the specification No. 3 and paragraph number [001] of the specification of Japanese Patent Application No. 2000-224031.
2] to [0038], and those described in paragraph Nos. [0012] to [0023] of Japanese Patent Application No. 2000-211147.

[0066]

[Chemical formula 26]

[0067]

[Chemical 27]

[0068]

[Chemical 28]

[0069]

[Chemical 29]

[0070]

[Chemical 30]

In the general formula (b), L represents a methine chain having a conjugated carbon atom number of 7 or more, and the methine chain may have a substituent, and the substituents are bonded to each other to form a ring structure. You may have. Zb ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Ni ⁺ , K ⁺ , Li ⁺ ) and the like. R ⁹ ~ R
¹⁴ and R ^{15 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. Represents a substituent selected from the above, or a substituent in which two or three of them are combined, and may be bonded to each other to form a ring structure. Here, in the general formula (b), L represents a methine chain having 7 conjugated carbon atoms, and R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ all represent hydrogen atoms, which are easily available. It is preferable from the viewpoint of the effect.

In the present invention, specific examples of the dye represented by formula (b) which can be preferably used include the followings.

[0073]

[Chemical 31]

[0074]

[Chemical 32]

In the general formula (c), Y ³ and Y ⁴ each represent an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. M represents a methine chain having a conjugated carbon number of 5 or more.
R ^{21 to} R ²⁴ and R ^{25 to} R ²⁸ may be the same or different and each is a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group or a thiol group. Represents a group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. Also, in the formula Z
a ^- represents a counter anion, Za in the general formula (a) ^-
Is synonymous with.

In the present invention, specific examples of the dye represented by formula (c) which can be preferably used include the followings.

[0077]

[Chemical 33]

[0078]

[Chemical 34]

In the general formula (d), R²⁹Through R³¹Is each
Independently represent a hydrogen atom, an alkyl group, or an aryl group.
You R³³And R³⁴Are each independently an alkyl group or a substituted
Represents a hydrogen atom or a halogen atom. n and m are independent of each other
An integer of 0 to 4 is shown. R ²⁹And R³⁰, Or R³¹And R³²
Each may combine with each other to form a ring, and R²⁹as well as
/ Or R³⁰Is R³³And again R³¹And / or R³²Is R³⁴When
May combine with each other to form a ring, and further, R³³Or R³⁴
If there are multiple³³Each other or R³⁴One another
They may be bonded to each other to form a ring. X¹And X²Each is German
By the way, a hydrogen atom, an alkyl group, or an aryl group,
X¹And X²At least one of is a hydrogen atom or an alkyl group
Indicates. Q is a trimethine group which may have a substituent or
Is a pentamethine group and has a ring structure together with a divalent organic group.
May be formed. Zc^-Represents a counter anion, and
Za in formula (a)^-Is synonymous with.

In the present invention, specific examples of the dye represented by formula (d) which can be preferably used include the followings.

[0081]

[Chemical 35]

[0082]

[Chemical 36]

In the general formula (e), R ^{35 to} R ⁵⁰ are each independently a hydrogen atom which may have a substituent, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, A hydroxyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, an amino group, and an onium salt structure are shown. M represents two hydrogen atoms or a metal atom, a halometal group or an oxymetal group, and the metal atom contained therein is IA, IIA or II in the periodic table.
IB, IVB group atoms, first, second and third period transition metals,
Examples of the lanthanoid element include copper, magnesium, iron, zinc, cobalt, aluminum, titanium and vanadium.

Specific examples of the dye represented by the general formula (e) which can be preferably used in the invention include the followings.

[0085]

[Chemical 37]

As the pigment used as the infrared absorber in the present invention, commercially available pigments and color index (CI) handbook, "Latest pigment handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment" Applied Technology "(CMC
Published in 1986), "Printing Ink Technology" published by CMC, published in 1984).

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 pigment, nitroso pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic pigment, carbon black and the like can be used.
Preferred among these pigments is carbon black.

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 surface treatment method is "property and application of metal soap" (Koushobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably 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 image-sensitive layer, and when it exceeds 10 μm, it is not preferable from the viewpoint of uniformity of the image-sensitive layer.

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

When these pigments or dyes are used in combination, 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on the total solids constituting the recording layer, and particularly preferably 0.1 to 10% by weight in the case of dyes. ˜5 wt%, and particularly preferably 0.2 to 10 wt% in the case of a pigment.
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 30% by weight, the uniformity of the photosensitive layer will be lost and the durability of the recording layer will be deteriorated.

As the other components of the image recording material of the present invention, various known components of image recording materials which can be recorded by infrared rays can be appropriately selected and used. The image recording material of the present invention forms a recording layer whose solubility in an alkaline aqueous solution is changed by exposure to infrared rays. Such a recording layer has a developability contrary to the negative type in which the alkali developability is lowered by the exposure to infrared rays. Can be divided into two types, positive type.

Examples of the negative type recording layer include known negative type polarity conversion material type (change from hydrophilic to hydrophobic), radical polymerization type and acid catalyst cross-linking type (including cationic polymerization) recording layers. Of these, the radical polymerization system and the acid catalyst crosslinking system are particularly preferable in terms of printing durability. In these, radicals or acids generated by light irradiation or heating serve as initiators or catalysts,
The compound constituting the recording layer undergoes a polymerization reaction and a crosslinking reaction to cure and form an image portion.

Examples of the positive type recording layer include known positive type polarity conversion material type (change from hydrophobic to hydrophilic) type, acid catalyst decomposition type and interaction releasing type (thermosensitive positive type) recording layer. Among these, a positive polarity conversion material system obtained by thermally decomposing a sulfonic acid ester, an acid catalyst decomposing system, and an interaction releasing system are particularly preferable from the viewpoint of image quality. These are soluble in water or alkaline water due to the action of releasing the bond of the polymer compound forming the layer by the acid generated by light irradiation or heating or the thermal energy itself, and are removed by development to be non-soluble. The image portion is formed. Hereinafter, each recording layer will be described in detail.

<Radical Polymerization Layer> When the image recording material of the present invention is used as a radical polymerization layer of a lithographic printing plate precursor,
Contains a compound that generates a radical by light or heat (hereinafter referred to as a radical generator) and a compound capable of radical polymerization (referred to as a polymerizable compound), and generates a radical in an exposed area by irradiation with an infrared laser, for example. Radicals are generated from the agent, which serves as an initiator, and the polymerizable compound is cured by a radical polymerization reaction to form an image area. The combination of the radical generator and the polymerizable compound used here can be appropriately selected and used from known ones as long as the strength of the film formed by radical polymerization satisfies the requirements for the recording layer. . Further, in order to improve the reactivity of the radical generator, an accelerator such as an onium salt or a reducing agent may be used in combination. Examples of components that can be used in the radical polymerization layer include, for example, JP-A-8-1086.
Compounds described as constituent components of the thermopolymerizable recording layer in JP-A No. 21-21, and compounds described as constituent components of the recording layer in JP-A No. 9-34110 can also be preferably used.

(Radical Generator) As the radical generator used in the radical polymerization layer, known radical polymerization initiators generally used in polymer synthesis reaction by radical polymerization can be used without particular limitation. 2'-azobisisobutyronitrile, 2,2'-azobispropionitrile and other azobisnitrile compounds, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, perbenzoic acid-t
-Butyl, α-cumylhydroperoxide, di-t-butylperoxide, diisopropylperoxydicarbonate, t-butylperoxyisopropylcarbonate, peracids, alkylperoxycarbamates, nitrosoarylacylamines, etc. Peroxides, inorganic peroxides such as potassium persulfate, ammonium persulfate and potassium perchlorate, azo or diazo compounds such as diazoaminobenzene, p-nitrobenzenediazonium, azobis-substituted alkanes, diazothioethers and arylazosulfones Compounds, nitrosophenyl urea, tetraalkyl thiuram disulfides such as tetramethyl thiuram disulfide, diaryl disulfides such as dibenzoyl disulfide, dialkylxanthogenic acid disulfides, arylsulfinic acid , Arylalkyl sulfones include a 1-alkanoic sulfinic acids and the like.

When the image recording material of the present invention is recorded by an infrared laser, the ultimate temperature of the exposed surface becomes 600 ° C. or more, though it depends on the energy of the laser, and therefore a radical generator having a large activation energy is also sufficient. Sensitivity can be obtained. The activation energy for radical generation of the radical generator is preferably 30 Kcal / mol or more, and examples thereof include azobisnitrile compounds and organic peroxides. Among them, compounds that are excellent in stability at room temperature, have a high decomposition rate when overheated, and become colorless upon decomposition are preferable, and examples thereof include benzoyl peroxide and 2,2′-azobisisobutyronitrile. The above radical generators may be used alone or in combination of two or more, and are used in an amount of about 0.5 to 30% by weight, preferably 2 to 10% by weight, based on the total solid content of the radical polymerization layer.

Further, a compound which generates a radical by the interaction with an onium salt described later can also be preferably used. Specifically, halides (α-haloacetophenones, trichloromethyltriazines, etc.), azo compounds, aromatic carbonyl compounds (benzoin esters, ketals, acetophenones, o-acyloxyimino ketones, acylphosphine oxides) etc),
Hexaarylbisimidazole compounds, peroxides and the like can be mentioned, but preferably, the above-mentioned JP-A-9-3411.
Examples of the bisimidazole derivatives disclosed as (A-1) to (A-4) on page 16 of JP-A-No. The latter radical generator achieves high sensitivity by interaction with an onium salt. Examples of onium salts that can be used in combination with this radical generator include paragraphs [0022] to
Examples thereof include phosphonium salt, sulfonium salt, iodonium salt, and ammonium salt compounds described in [0049]. The addition amount of the onium salt varies depending on the type and usage of the onium salt, but is preferably 0.05 to 50% by weight based on the total solid content of the recording layer.

Onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts, which can be preferably used as the (acid generator) in the below-mentioned <acid crosslinking agent>, are not used together with the radical generator. However, it can be used alone as a radical generator, and its addition amount is preferably 0.05 to 50% by weight with respect to the total solid content of the recording layer, although it varies depending on the type and usage form.

(Polymerizable Compound) As the polymerizable polymer compound which is polymerized and cured by radicals generated from the radical generator, known monomers having a polymerizable group can be used without particular limitation. Specific examples of such a monomer include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-ethylhexyl acrylate.
Monofunctional acrylic acid esters such as hydroxypropyl acrylate and their derivatives or compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, etc .; polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A diacrylate, hydroxypivalic acid neo Bifunctional acrylic acid esters such as diacrylates of ε-caprolactone adduct of pentyl glycol and their derivatives or compounds in which these acrylates are replaced with methacrylates in the same manner as described above; or trimethylolpropane tri (meth) acrylate, dipentaerythritol Polyfunctional acrylics such as pentaacrylate, dipentaerythritol hexaacrylate, and pyrogallol triacrylate Compounds ester and their derivatives or their acrylate is replaced with methacrylate, and the like. Further, a so-called prepolymer in which acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to impart photopolymerization property can also be suitably used.

In addition to this, JP-A-58-212994,
61-6649, 62-46688, 62-
48589, 62-173295, 62-18.
7092, 63-67189, JP-A-1-244.
Compounds described in No. 891 and the like can be mentioned, and further, “11290 chemical products”, Chemical Industry Daily, 286-
The compounds described on page 294, the compounds described on pages 11 to 65 of "UV / EB curing handbook (raw material edition)", Kobunshi Kogyo Kai, etc. can also be preferably used.

Of these, compounds having two or more acryl groups or methacryl groups in the molecule are preferable in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are desirable. In the present invention, the polymerizable compound is a monomer having a polymerizable group, including those exemplified above, or a prepolymer, and if there is no problem with one kind or compatibility or compatibility depending on the purpose,
Two or more kinds can be used in combination. The compound having an ethylenically unsaturated group, as a solid content in the radical polymerization layer, is preferably 20 to 80% by weight, more preferably 3%.
It is contained in an amount of 0 to 60% by weight.

(Binder Resin) A binder resin is used in the recording layer, if necessary. As the binder resin, polyester resin, polyvinyl acetal resin, polyurethane resin, polyamide resin, cellulose resin, olefin resin, vinyl chloride resin, (meth) acrylic resin, styrene resin, polycarbonate, polyvinyl alcohol , Polyvinylpyrrolidone, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, rubber resin and the like. Further, a resin having an unsaturated bond in the resin, for example, a diallyl phthalate resin and its derivative, chlorinated polypropylene, etc., can be polymerized with the above-mentioned compound having an ethylenically unsaturated bond, so that it is suitably used depending on the application. Can be used. As the binder resin, one kind or a combination of two or more kinds of the above-mentioned resins can be used. These binder resins are preferably used in an amount of 500 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the polymerizable compound. By adding the specific infrared absorbing agent to such a radical polymerization layer, it is possible to improve the sensitivity and accelerate the radical polymerization reaction. (Other Compounds) In the radical polymerization layer, various additives used in combination with conventionally known photopolymerizable compounds can be appropriately used as long as the effects of the present invention are not impaired. A thermal polymerization inhibitor is mentioned as an additive. Specific examples include hydroquinone, pyrogallol, p-methoxyphenol, catechol, β-naphthol, quinone-based compounds such as 2,6-di-t-butyl-p-cresol and phenolic compounds, and ethylenically unsaturated bond. It is used in an amount of 10 parts by weight or less, and preferably about 0.01 to 5 parts by weight, based on 100 parts by weight of the total of the polymerizable compound having a.

Compounds that can be added as oxygen quenchers are described in US Pat. No. 4,772,541, column 11, line 58-12.
N, N-dialkylaniline derivatives such as the compounds described in the 35th column of the column can be mentioned. Further, in order to improve the film quality, a plasticizer can be used, and examples thereof include phthalic acid esters, trimellitic acid esters, adipic acid esters, other saturated or unsaturated carboxylic acid esters, citric acid esters, and epoxidation. Soybean oil, epoxidized linseed oil, stearic acid epoxys, orthophosphoric acid esters, phosphorous acid esters, glycol esters and the like can be mentioned.

It is also preferable to use an acid generator in combination as an additive that generates an acid by heating and accelerates the decomposition of the radical generator. As the acid generator, those described in detail in the description of the acid cross-linking layer below can be used. A radical polymerization layer can be formed by appropriately selecting the above components, dissolving them in a suitable solvent, and coating them on a support. The coating amount after drying is 0.01 to 5. 0 g
/ M ² is preferable.

When a radical polymerization layer is used as the recording layer, an oxygen impermeable overcoat layer may be provided adjacent to the layer in order to prevent polymerization inhibition by oxygen. As a material for the overcoat layer, a water-soluble resin such as polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, or polyvinylpyrrolidone is preferable, and a film thickness of about 0.2 to 3 μm is suitable. If necessary, a dye or a content that does not absorb the light from the light source used for recording may be added to the overcoat layer as a filter agent.

<Acid Crosslinking Layer> When the image recording material of the present invention is used in the acid crosslinking layer, a compound capable of generating an acid by light or heat (hereinafter referred to as an acid generator) and the generated acid as a catalyst are used. And a binder polymer capable of reacting with the cross-linking agent in the presence of an acid to form a layer containing these. In this acid cross-linking layer, the acid generated by decomposition of the acid generator by irradiation with light or heating promotes the action of the cross-linking agent, resulting in a strong cross-linking structure between the cross-linking agents or between the cross-linking agent and the binder polymer. Is formed, which results in
Alkali solubility is reduced and it becomes insoluble in the developer.

As the acid cross-linking agent layer having such characteristics, known layers having similar characteristics can be used. For example, a layer made of a radiation-sensitive composition containing a resole resin, a novolac resin, a latent Bronsted acid, and an infrared absorber described in JP-A-7-20629 can be mentioned. Here, the "latent Bronsted acid" refers to a precursor that decomposes to produce Bronsted acid, and is a compound having both properties of the acid generator and the acid crosslinking agent in the present invention. Bronsted acid
It is believed to catalyze the matrix-forming reaction between the resole resin and the novolac resin, and examples of Bronsted acids suitable for this purpose are trifluoromethanesulfonic acid and hexafluorophosphonic acid. Furthermore, ionic latent Bronsted acids are preferred, examples of which include onium salts, especially iodonium, sulfonium, phosphonium, selenonium, diazonium, and arsonium salts. Nonionic latent Bronsted acids can also be preferably used, for example, the following compounds: RCH ₂ X, RCHX ₂ , RCX ₃ , R (C
H ₂ X) ₂ , and R (CH ₂ X) ₃ , where X is C
1, Br, F, or CF ₃ , SO ₃ , and R is
An aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group).

Further, a recording layer containing an acid-crosslinkable compound and a high molecular weight binder described in JP-A No. 11-95415 is also preferable. This is a compound capable of generating an acid upon irradiation with actinic rays, for example, a salt such as diazonium, phosphonium, sulfonium, and iodonium, an organohalogen compound, an orthoquinone-diazidosulfonyl chloride, and an organometallic / organohalogen compound, A compound having at least one bond capable of crosslinking in the presence of the acid, for example, an amino compound having at least two functional groups such as an alkoxymethyl group, a methylol group and an acetoxymethyl group, an alkoxymethyl group as a functional group, a methylol group A photosensitive layer containing at least a di-substituted aromatic compound having an acetoxymethyl group, a resole resin and a furan resin, an acrylic resin synthesized from a specific monomer, and the like, which can be used. .

The acid cross-linking layer according to the present invention contains an acid generator, a cross-linking agent, a binder polymer, and the like. Next, these compounds will be individually described. (Acid Generator) In the present invention, the compound (acid generator) which generates an acid by light or heat means irradiation with infrared rays or 100 ° C.
It means a compound that decomposes to generate an acid by the above heating.
As the acid generated, pKa of sulfonic acid, hydrochloric acid, etc. is 2
The following strong acids are preferred. Examples of the acid generator preferably used in the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts. Specifically, US 4,708,9
The compounds described in JP-A No. 25 and JP-A No. 7-20629 can be mentioned. Particularly, iodonium salts, sulfonium salts, and diazonium salts having sulfonate ion as a counter ion are preferable. Examples of the diazonium salt include diazonium compounds described in US Pat. No. 3,867,147,
The diazonium compounds described in U.S. Pat. No. 2,632,703, JP-A-1-102456, and JP-A-1-102456
The diazo resin described in each publication of 102457 is also preferable. Also, US 5,135,838 and US 5,
The benzyl sulfonates described in 200,544 are also preferred. Furthermore, JP-A No. 2-100054,
JP-A 2-100055 and JP-A 9-197671
Also preferred are the active sulfonic acid esters and disulfonyl compounds described in No. In addition, JP-A-7-2710
29, haloalkyl-substituted S-
Triazines are also preferred.

These acid generators are added in an amount of 0.01 to 50% by weight, preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, based on the total solid content of the acid crosslinking layer. It is added to the crosslinked layer. If the addition amount is less than 0.01% by weight, an image cannot be obtained. On the other hand, if the addition amount exceeds 50% by weight, stains are generated on the non-image area during printing.

These compounds may be used alone,
Moreover, you may use it in combination of 2 or more type. Since the acid generators listed here can be decomposed by irradiation with ultraviolet rays, the use of the recording layer having such a form enables image recording not only by infrared rays but also by irradiation with ultraviolet rays.

(Acid Crosslinking Agent) The crosslinking agent which can be used in the acid crosslinking layer according to the present invention is not particularly limited as long as it is a compound capable of being crosslinked by an acid, but the phenol derivative represented by the following general formula (I) ( Hereinafter, appropriately referred to as a low molecular weight phenol derivative), a polynuclear phenolic compound having 3 or more phenol rings having 2 or 3 hydroxymethyl groups on the ring represented by the following general formula (II) in the molecule A cross-linking agent and a mixture of the low molecular weight phenol derivative and a polynuclear phenolic cross-linking agent and / or a resole resin are preferably used.

[0114]

[Chemical 38]

In the formula, Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. R ¹ and R ^{2, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. R ³ represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. m is 2 to 4
Indicates an integer. n shows the integer of 1-3. X represents a divalent linking group, and Y represents a monovalent to tetravalent group having the above partial structure.
A valent linking group or a functional group whose terminal is a hydrogen atom,
Z represents a monovalent to tetravalent linking group or a functional group which does not exist when Y is a terminal group or exists depending on the number of Y linking groups.

[0116]

[Chemical Formula 39]

In the formula, A represents an r-valent hydrocarbon linking group having 1 to 20 carbon atoms, and r represents an integer of 3 to 20. p is
An integer of 2-3 is shown. Regarding the phenol derivative represented by the general formula (I), the applicant of the present application has previously filed Japanese Patent Application No. 11-352210, paragraph number [0098] to
As described in detail in [0155], the polynuclear phenolic cross-linking agent represented by the general formula (II) and having 3 or more phenol rings having 2 or 3 hydroxymethyl groups on the ring in the molecule Also, paragraph number [0156] to the same specification
This is described in detail in [0165].

These crosslinking agents may be used alone,
Moreover, you may use it in combination of 2 or more types. In the present invention, the crosslinking agent is used in an amount of 5 to 70% by weight, preferably 10 to 65% by weight, based on the total solid content of the acid crosslinking layer. If the addition amount of the cross-linking agent is less than 5% by weight, the film strength of the image portion when an image is recorded is deteriorated, and if it exceeds 70% by weight, the stability during storage is not preferable.

Examples of the binder polymer that can be used in the acid cross-linking layer of the present invention include polymers having a side chain or main chain of an aromatic hydrocarbon ring to which a hydroxy group or an alkoxy group is directly bonded. The alkoxy group preferably has 20 or less carbon atoms from the viewpoint of sensitivity. Further, as the aromatic hydrocarbon ring, a benzene ring, a naphthalene ring or an anthracene ring is preferable from the availability of raw materials. These aromatic hydrocarbon rings may have a substituent other than a hydroxy group or an alkoxy group, for example, a substituent such as a halogen group or a cyano group, but from the viewpoint of sensitivity, other than a hydroxy group or an alkoxy group. It is preferable not to have a substituent of.

In the present invention, the binder polymer which can be preferably used is a polymer having a constitutional unit represented by the following general formula (III) or a phenol resin such as a novolac resin.

[0121]

[Chemical 40]

In the formula, Ar² Is a benzene ring, naphthalene
Indicates a ring or anthracene ring. R ^FourIs a hydrogen atom or
Represents a methyl group. R^Five Is a hydrogen atom or 20 carbon atoms
Not more than 30 alkoxy groups are shown. X1 is a single bond or
Contain at least one atom selected from C, H, N, O and S
And a divalent linking group having 0 to 20 carbon atoms. k
Represents an integer of 1 to 4.

In the present invention, as the binder polymer,
A homopolymer consisting only of the structural unit represented by the general formula (III) may be used, or a copolymer having a structural unit derived from another known monomer may be used together with the specific structural unit. good. The proportion of the structural unit represented by the general formula (III) contained in the copolymer using these is 50
It is preferably ˜100% by weight, more preferably 60-100% by weight. The weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000,
The number average molecular weight is preferably 1,000 or more, more preferably 2000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10. These polymers may be random polymers, block polymers, graft polymers, etc., but are preferably random polymers.

Next, the novolaks will be described. Examples of the novolak resin preferably used in the present invention include phenol novolak, o-, m-, p-various cresol novolaks, and copolymers thereof, and halogen-based novolaks using phenol substituted with an alkyl group. To be The weight average molecular weight of these novolac resins is preferably 1000 or more, more preferably 2000.
The number average molecular weight is preferably 100.
0 or more, more preferably 2000 to 15000
Is the range. The polydispersity is preferably 1 or more, more preferably 1.1 to 10.

Further, it is also a preferable embodiment to use a polymer having a heterocyclic group having an unsaturated bond in the ring as the binder polymer. Here, the term “heterocycle” refers to one in which at least one heteroatom other than carbon is included in the atoms constituting the ring system. The hetero atom used is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a silicon atom. It is considered that the use of the polymer having such a heterocyclic group facilitates the chemical structural reaction due to the function of the lawn pair existing in the present heterocycle, and forms a film having good printing durability.

The binder polymers used in the present invention described above may be used alone or in combination of two or more kinds. These polymers are added in a proportion of 20 to 95% by weight, preferably 40 to 90% by weight, based on the total solid content of the acid crosslinked layer. When the addition amount is less than 20% by weight, the strength of the image area is insufficient when an image is formed. If the addition amount exceeds 95% by weight, no image is formed.

Also in this acid cross-linking layer, the sensitivity can be improved by containing the infrared absorber. When forming the acid cross-linked layer, various additives such as a surfactant can be used together for the purpose of improving coatability and film quality.

Examples of the positive type recording layer include an interaction releasing system (heat-sensitive positive), an acid catalyst decomposition system, and a polarity conversion system. These are described below in order. <Interaction-releasing system (heat-sensitive positive)> The interaction-releasing system is composed of the above-mentioned surface-aligned infrared-absorbing alkali-soluble resin and, if desired, a general known alkali-soluble resin and the above-mentioned general infrared absorbing agent. It

As the alkali-soluble resin which can be used in the positive type recording layer, as mentioned above, a homopolymer having an acidic group in the main chain and / or side chain in the polymer, a copolymer thereof or a copolymer thereof is used. A mixture of Above all,
Those having an acidic group listed in the following (1) to (6) in the main chain and / or side chain of the polymer are preferable from the viewpoint of solubility in an alkaline developer and manifestation of dissolution inhibiting ability.

(1) Phenol group (-Ar-OH) (2) Sulfonamide group (-SO ₂ NH-R) (3) Substituted sulfonamide acid group (hereinafter referred to as "active imide group") [- _{SO 2 NHCOR, -SO 2 NHSO 2} R, -CO
NHSO ₂ R] (4) carboxylic acid group (-CO ₂ H) (5) sulfonic acid group (-SO ₃ H) (6) phosphoric acid group (-OPO ₃ H ₂₎

<Acid-catalyzed Decomposition System> The chemical amplification layer is preferably formed on the exposed surface of the uppermost layer of the recording layer, and it is a compound (acid generator) which generates an acid by the action of light or heat, and A compound (acid-decomposable compound) that cleaves a chemical bond by using an acid as a catalyst to increase the solubility in an alkali developing solution is an essential component. The chemical amplification layer may further contain a polymer compound which is a binder component for forming this, and the following acid-decomposable compound itself is a polymer compound which functions as a binder component or a precursor thereof. It may be.

[Acid-decomposable compound] In the present invention, a compound that cleaves a chemical bond with an acid as a catalyst to increase the solubility in an alkali developing solution is a compound having a bond group capable of being decomposed by an acid in the molecule. It can be replaced. Such a compound is described in JP-A No. 9-171254, "(b) Compound having at least one decomposable bond with an acid".
Can be used. The coupling capable of being decomposed by an acid, for _{example, - (CH 2 CH 2 O} ) n -
A group (n represents an integer of 2 to 5) and the like can be preferably mentioned. Among such compounds, it is preferable to use the compound represented by the following general formula (1) from the viewpoint of sensitivity and developability.

[0133]

[Chemical 41]

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

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

Other acid-decomposable compounds applicable to the present invention include JP-A-48-89603 and 51-12.
0714, 53-333429, 55-129.
No. 95, No. 55-126236, No. 56-17345.
Compounds having C--O--C bond described in JP-A-60-
-37549, Si described in No. 60-12146
Compound having --O--C bond, JP-A-60-3625
Other acid-decomposable compounds described in JP-A No. 60-10247 and JP-A-62-2 can be mentioned.
Compounds having an Si-N bond described in JP-A No. 22246, carbonic acid esters described in JP-A No. 62-251743, orthocarbonic acid esters described in JP-A No. 62-209451, and JP-A-62. -280841 orthotitanate, JP-A-62-62
Orthosilicic acid esters described in JP-A-280842, JP-A-63-010153 and JP-A-9-1712.
No. 54, No. 10-55067, No. 10-111564.
No. 10-87733, No. 10-153853,
No. 10-228102, No. 10-268507, No. 282648, No. 10-282670, EP-08.
84547 Al, acetals, ketals and orthocarboxylic acid esters, JP-A-64-2440.
The compound having a C—S bond described in No. 38 can be used.

Among the above acid-decomposable compounds, JP-A Nos. 53-133429, 56-17345 and 60 are particularly preferable.
-121446, 60-37549, and 62-2
09451, 63-0101053, JP-A-9-1
71254, 10-55067, 10-111.
No. 564, No. 10-87733, No. 10-15385.
No. 3, No. 10-228102, No. 10-268507
No. 282648, No. 10-282670, EP
0884647Al C-O-described in each specification
Compounds having a C bond, compounds having a Si—O—C bond, orthocarbonates, acetals, ketals and silyl ethers are preferable. Among these acid-decomposable compounds, a polymer compound having an acetal or ketal moiety in the main chain repeatedly and whose solubility in an alkaline developer is increased by the acid generated is preferably used.

These acid-decomposable compounds may be used alone or in combination of two or more. The amount of addition is 5 to 70% by weight, preferably 10 to 50% by weight, more preferably 15% by weight based on the total solid content of the chemical amplification layer.
It is added to the layer in a proportion of ˜35% by weight. If the addition amount is less than 5% by weight, stains on non-image areas are likely to occur,
On the other hand, if the addition amount exceeds 70% by weight, the film strength of the image area becomes insufficient, which is not preferable.

(Dissolution Inhibitor) In forming a positive recording layer using the image recording material of the present invention, an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, an aromatic sulfonic acid ester compound and the like are further added. A substance that is thermally decomposable and that substantially reduces the solubility of the alkali-soluble resin when not decomposed can be used in combination.
Addition of these compounds 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. The onium salt is 1 to 50% by weight based on the total solid content of the image recording material.
It is preferably added, more preferably 5 to 30% by weight, and particularly preferably 10 to 30% by weight.

Further, for the purpose of further improving the sensitivity,
Cyclic acid anhydrides, phenols, and organic acids can also be used together. The ratio of the above cyclic acid anhydride, phenols and organic acids in the image recording material is 0.05 to
It is preferably 20% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 0.1 to 10% by weight.

In addition to these, epoxy compounds,
Vinyl ethers, further, a phenol compound having a hydroxymethyl group described in JP-A-8-276558, a phenol compound having an alkoxymethyl group, and JP-A-11-160860 previously proposed by the present inventors.
The cross-linking compound having an alkali dissolution suppressing action described in JP-A No. 2003-242242 can be appropriately added depending on the purpose.

Further, in the image recording material of the present invention, in order to extend the stability of processing against developing conditions, JP-A-62-251740 and JP-A-3-208514 are used.
Nonionic surfactants as described in JP-A-59-121044 and JP-A-4-13149.
Amphoteric surfactants such as those described in the publication can be added.

In the image recording material of the present invention, a printout agent for obtaining a visible image immediately after heating by exposure,
Dyes or pigments as image colorants can be added.
If necessary, a plasticizer is added to the image recording material of the present invention 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, oligomers of acrylic acid or methacrylic acid. And polymers are used.

A lithographic printing plate precursor is prepared by dissolving a coating liquid for a recording layer containing the image recording material of the present invention or a coating liquid component for a desired layer such as a protective layer in a solvent and coating it on a suitable support. It can be manufactured. 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, dimethoxy. Ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene,
Examples thereof include water, but are not limited thereto. These solvents may be used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. The coating amount (solid content) of the recording layer obtained on the support after coating and drying varies depending on the use, but is generally preferably 0.5 to 5.0 g / m ² for the photosensitive printing plate. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the recording layer deteriorate. 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.

In the coating solution for the recording layer using the image recording material of the present invention, a surfactant for improving the coating property, for example, a fluorine-based agent as described in JP-A-62-170950. Surfactants can be added. The preferable addition amount is 0.01 to 1% by weight, and more preferably 0.05 to 0.5% by weight, based on the entire image recording material.

As a support used when the recording layer of the present invention is applied to a lithographic printing plate precursor, a dimensionally stable plate-like material is used, and examples thereof include paper and plastic (eg, paper).
Polyethylene, polypropylene, polystyrene, etc.) laminated paper, 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, etc.), paper laminated with the above metal, or vapor-deposited, or a plastic film is included.

As the support used in the lithographic printing plate precursor according to the 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. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a slight amount of a foreign element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of foreign elements in the alloy is at most 10% by weight. 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 m.
m-0.4 mm, particularly preferably 0.2 mm-0.3 m
m.

Prior to the roughening of the aluminum plate, if desired, a degreasing treatment for removing the rolling oil on the surface is carried out with, for example, a surfactant, an organic solvent or an alkaline aqueous solution. The surface roughening treatment of the aluminum plate is carried out by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically melting the surface and a method of selectively melting the surface chemically. It is performed by the method. 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. 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 alkali etching treatment and neutralization treatment, if necessary, and then, if desired, subjected to anodization treatment in order to enhance 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 sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is generally 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 weight solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , voltage 1 to 100 V, electrolysis time 10 seconds to 5 minutes are suitable. If the amount of the anodic oxide film is less than 1.0 g / m ² , printing durability may be insufficient, or the non-image area of the planographic printing plate may be easily scratched.
So-called "scratch stains" tend to occur in which ink adheres to the scratched portion during printing. 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. 14,066, No. 3,181,461, No. 3,2
There are alkali metal silicate (eg sodium silicate aqueous solution) methods such as those disclosed in 80,734 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 Japanese Patent Publication No. 36-22063 and US Pat. Nos. 3,276,868 and 4,153,46.
The method of treating with polyvinylphosphonic acid as disclosed in No. 1 and No. 4,689,272 is used.

The lithographic printing plate precursor according to the invention has a recording layer containing the image recording material of the invention on a support, and an undercoat layer may be provided between them if necessary. 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, optionally substituted phenylphosphonic acid, 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.

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, wavelengths of 720 to 120
Solid-state lasers, semiconductor lasers, and the like that emit infrared rays of 0 nm are included. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser and a semiconductor laser are particularly preferable.

As the developer and replenisher for the lithographic printing plate precursor according to the invention, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium silicate, sodium triphosphate, potassium triphosphate, tertiary
Ammonium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, boric acid Ammonium,
Inorganic alkali salts such as sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are mentioned. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkaline agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents may be used alone or in combination of two or more. Among these alkaline agents, a particularly preferable developer is an aqueous silicate solution such as sodium silicate or potassium silicate. The reason is that silicon oxide SiO ₂ which is a component of silicate and alkali metal oxide
This is because the developing property can be adjusted by the ratio and concentration of M ₂ O. For example, JP-A-54-62004,
An alkali metal silicate as described in JP-B-57-7427 is effectively used.

Further, in the case of developing using an automatic processor, an aqueous solution (replenisher) having a higher alkali strength than the developing solution.
It is known that a large amount of PS plate can be processed by replacing the developing solution in the developing tank for a long period of time without adding the developing solution 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 sodium salt and potassium salt of inorganic acid such as hydroquinone, resorcin, sulfurous acid and bisulfite, an organic carboxylic acid, a defoaming agent and a water softener. It can also be added. The printing plate developed with the above-mentioned developing solution and replenishing solution 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-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, automatic developing machines for printing plates have been widely used in the plate making / printing industry 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.

The photosensitive lithographic printing plate precursor using the image recording material of the present invention will be described. Unnecessary if there are unnecessary image areas (for example, film edge traces of the original film) on the lithographic printing plate obtained by imagewise exposure, development, washing with water and / or rinsing and / or gumming. The image area 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 for a predetermined time as it is, and then rinsing with water. A method described in JP-A-59-174842, in which an active ray guided by an optical fiber is applied to an unnecessary image portion and then developed, can also be used.

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 the planographic printing plate is subjected to a burning treatment, before the burning treatment, Japanese Patent Publication Nos. 61-2518, 55-28062,
It is preferable to treat with a surface-adjusting solution as described in JP-A Nos. 62-31859 and 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 coating amount of the surface conditioning solution 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 the surface treatment containing a water-soluble polymer compound etc. When a liquid 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.

[0160]

[Synthesis example]

(Synthesis Example 1, synthesis of DB-1) 24.0 g of cresol-formaldehyde resin (m-cresol: p-cresol molar ratio 6: 4) was dissolved in 200 ml of methanol,
Further, 0.54 g of sodium methoxide was added, and the mixture was stirred at room temperature for 10 minutes. After stirring, the solvent was distilled off under reduced pressure to obtain a cresol-formaldehyde resin in which a part (about 5%) of the phenol skeleton was dissociated into a phenoxide. Further, the resin is treated with N, N-dimethylformaldehyde 150
After dissolving in ml, the following cyanine dye A (7.6 g) was added, and the mixture was stirred at room temperature for 5 hours. After stirring, the reaction solution was treated with water 1500 m.
1, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain a polymer compound having an infrared absorbing group (DB-1
A) was obtained. Furthermore, the obtained (DB-1A) was added to N, N
-Dissolved in 150 ml of dimethylformaldehyde, 9.0 g of hexafluoropropene trimer was added, 2.0 g of triethylamine was slowly added while cooling with water, and the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 500 ml of diluted hydrochloric acid, and the separated product was collected by filtration, washed with water, and dried to obtain a surface-aligned infrared absorbing alkali-soluble resin (DB-1) 36.5.
g was obtained. The absorption maximum of absorption measured by depositing the obtained (DB-1) on a PET film is 815 nm,
The weight average molecular weight measured by GPC using standard polystyrene was about 9,000.

[0161]

[Chemical 42]

(Synthesis Example 2, Synthesis of DB-3) 24.0 g of cresol-formaldehyde resin (m-cresol: p-cresol molar ratio 6: 4) was added to 200 ml of methanol.
, 0.54 g of sodium methoxide was added, and the mixture was stirred at room temperature for 10 minutes. After stirring, the solvent was distilled off under reduced pressure to obtain a cresol-formaldehyde resin in which a part (about 5%) of the phenol skeleton was dissociated into a phenoxide. Further, the resin was dissolved in 150 ml of N, N-dimethylformaldehyde, 7.6 g of the above cyanine dye A was added, and the mixture was stirred at room temperature for 5 hours. After stirring, add 1 part of the reaction solution to water.
The mixture was poured into 500 ml, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain a polymer compound (DB-3A) having an infrared absorbing group. The obtained (DB-3A) was mixed with 400 ml of acetone, 1.0 g of triethylamine was added, and the mixture was stirred for 10 minutes. Further, 4.3 g of perfluorooctanoyl chloride was gradually added dropwise while cooling with water,
Stir at room temperature for 4 hours. The reaction solution was poured into 8000 ml of water, and the precipitate was collected by filtration, washed with water and dried to obtain a surface-aligned infrared absorbing alkali-soluble resin (DB-3) 3
2.1 g was obtained. The absorption maximum of absorption measured by depositing (DB-3) on a PET film was 815 nm, and the weight average molecular weight by GPC measurement using standard polystyrene was about 7,000.

(Synthesis Example 3, Synthesis of DB-5) In a nitrogen atmosphere, 0.4 g of 60% sodium hydride was washed twice with hexane and dried under reduced pressure. Tetrahydrofuran (5 ml) was added to the washed sodium hydride suspension, and while cooling with ice, poly (4-hydroxystyrene) (manufactured by Maruzen Petrochemical Co., Ltd.) 12.0 g of tetrahydrofuran (150 m)
1) The solution was added dropwise over 15 minutes to generate phenoxide in which a part (about 10%) of the phenolic hydroxy of poly (4-hydroxystyrene) was dissociated. After stirring at room temperature for 10 minutes, 7.6 g of the above cyanine dye A was added, and the mixture was stirred at room temperature for 5 hours. After stirring, the reaction solution was poured into 1500 ml of water, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to give a polymer compound having an infrared absorbing group (DB-5A).
Got Further, the obtained (DB-5A) was dissolved in 100 ml of N, N-dimethylformaldehyde, 6.8 g of hexafluoropropene trimer was added, 1.5 g of triethylamine was slowly added while cooling with water, and the mixture was stirred at room temperature for 6 hours. The reaction solution was poured into 300 ml of diluted hydrochloric acid, and the separated product was collected by filtration, washed with water, and dried to obtain 24.3 g of a surface-aligned infrared absorbing alkali-soluble resin (DB-5). The absorption maximum of absorption measured by depositing the obtained (DB-5) on a PET film was 815 nm, and the weight average molecular weight by GPC measurement using standard polystyrene was about 13,000.

(Synthesis Example 4, Synthesis of DB-9) 24.0 g of cresol-formaldehyde resin (m-cresol: p-cresol molar ratio 6: 4) was added to 200 ml of methanol.
, 0.54 g of sodium methoxide was added, and the mixture was stirred at room temperature for 10 minutes. After stirring, the solvent was distilled off under reduced pressure to obtain a cresol-formaldehyde resin in which a part (about 5%) of the phenol skeleton was dissociated into a phenoxide. Further, the resin was dissolved in 150 ml of N, N-dimethylformaldehyde, 7.6 g of the above cyanine dye A was added, and the mixture was stirred at room temperature for 5 hours. After stirring, add 1 part of the reaction solution to water.
The mixture was poured into 500 ml, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain a polymer compound (DB-9A) having an infrared absorbing group. The obtained (DB-9A) was mixed with 400 ml of acetone, 4.0 g of triethylamine was added, and the mixture was stirred for 10 minutes. Furthermore, stearoyl chloride 1
A mixture of 2.1 g and acetone 6 g was gradually added dropwise while cooling with water, and the mixture was stirred at room temperature for 5 hours. The reaction solution is water 8000
It is then poured into a glass plate, and the precipitate is collected by filtration, washed with water and dried to obtain a surface alignment type infrared absorbing alkali-soluble resin (DB-
9) 38.2 g was obtained. The absorption maximum of absorption measured by forming (DB-9) on a PET film was 815 nm, and the weight average molecular weight by GPC measurement using standard polystyrene was about 6,000.

[Production of Substrate] Aluminum 0.3 mm thick
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 12 mg / m²Met.

[0166] [Undercoat liquid]   ・ The following compound 0.3g   ・ Methanol 100g   ・ Water 1g

[0167]

[Chemical 43]

(Example 1) A coating amount of 1.0 g of the following photosensitive solution 1 comprising the image recording material of the present invention was applied to the obtained substrate.
/ M ² (after drying), then apply TABAI
Wi-Fi router, PERFECT OVEN PH200
The nd Control was set to 7 and dried at 140 ° C. for 50 seconds to obtain a lithographic printing plate precursor 1.

[0169] [Photosensitive liquid 1]   Surface-oriented infrared absorbing alkali-soluble resin (DB-1) 0.75g   2.37 g of the specific copolymer 1 described in JP-A-11-288093   2-methoxy-4- (N-phenylamino) benzene   Diazonium hexafluorophosphate 0.03g   Tetrahydrophthalic anhydride 0.19g   The counter ion of ethyl violet was 6-hydroxy-β-     Naphthalenesulfonic acid 0.05g   Fluorine-based surfactant (MegaFac F176PF,     Dainippon Ink and Chemicals Co., Ltd.) 0.035g   Fluorine-based surfactant (MegaFac MCF-312,     Dainippon Ink and Chemicals Co., Ltd.) 0.05g   Paratoluenesulfonic acid 0.008g   Bis-p-hydroxyphenyl sulfone 0.063 g   N-Dodecyl stearate 0.06g   γ-butyrolactone 13 g   Methyl ethyl ketone 24g   1-methoxy-2-propanol 11g

Example 2 The following photosensitive solution 2 was applied to the obtained substrate so that the coating amount was 1.6 g / m ² , and
The planographic printing plate precursor 2 was obtained by drying under the same conditions as in Example 1. [Photosensitive solution 2] m, p-cresol novolak 1.80 g (m / p ratio = 6/4, weight average molecular weight 8000, containing unreacted cresol 0.5% by weight) octylphenol novolac (weight average molecular weight: 2500) 015 g Surface-aligned infrared absorbing alkali-soluble resin (DB-1) 0.56 g 2-methoxy-4- (N-phenylamino) benzene diazonium hexafluorophosphate 0.03 g Tetrahydrophthalic anhydride 0.10 g Ethyl violet counterion 6-hydroxy-β-naphthalene sulfonic acid 0.063 g Fluorosurfactant (Megafuck F176PF, Dainippon Ink and Chemicals, Inc.) 0.035 g Fluorosurfactant (Megafuck MCF-312) , Manufactured by Dainippon Ink and Chemicals, Inc. 0.1 g bis -p- hydroxyphenyl sulfone 0.08g Methyl ethyl ketone 16g 1-methoxy-2-propanol 10g

Examples 3 to 6 In the photosensitive solution 1 of Example 1, instead of the m, p-cresol novolac and the phenol oligomer (IR-10) of Synthesis Example 4, an alkali-soluble resin shown in Table 1 below was used. Lithographic printing plate precursors 3 to 6 were obtained in the same manner as in Example 1 except that was used.

[0172]

[Table 1]

Comparative Example 1 In the photosensitive solution 1 of Example 1, the amount of m, p-cresol novolac was 0.474 g.
Except that 0.155 g of the above cyanine dye A was used instead of the phenol oligomer (IR-10), and a lithographic printing plate precursor 7 was obtained in the same manner as in Example 1.

(Comparative Example 2) In the photosensitive solution 1 of Example 1, a surface alignment type infrared absorbing alkali-soluble resin (DB-
Example 1 except that 0.58 g of the polymer compound (DB-1A) having an infrared absorbing group of Synthesis Example 1 and 0.17 g of m, p-cresol novolac used in Photosensitive Solution 4 were used instead of 1). A lithographic printing plate precursor 8 was obtained in the same manner as.

(Comparative Example 3) In the photosensitive solution 2 of Example 2, a surface alignment type infrared absorbing alkali-soluble resin (DB-
0.105 g of cyanine dye A instead of 1) and 0.45 g of m, p-cresol novolak used in Photosensitive Solution 2
A lithographic printing plate precursor 9 was obtained in the same manner as in Example 2 except that was used.

(Example 7, Comparative Example 4) [Production of Substrate] The following photosensitive solution A was applied to the substrate used in Example 1.
Was applied and dried at 100 ° C. for 2 minutes to form a layer (A). The coating amount after drying was 0.8 g / m ² . Then, the following photosensitive solutions B-1 and B-2 were applied and dried at 100 ° C. for 2 minutes to form a layer (B) (upper layer) to obtain lithographic printing plate precursors 10 and 11. The total coating amount of the photosensitive liquid after drying was 1.2 g / m ² .

[0177] [Photosensitive solution A]   ・ Copolymer 1 0.75 g   ・ Phthalocyanine dye B 0.04 g   -P-toluenesulfonic acid 0.002 g   ・ Tetrahydrophthalic anhydride 0.05g   ・ The counter anion of Victoria Pure Blue BOH is 1-naphthalene     Dye 0.015g made into sulfonate anion   -Fluorine-based surfactant (MegaFac F-177,     Dainippon Ink and Chemicals Co., Ltd.) 0.02g   ・ Γ-Butyrolactone 8g   ・ Methyl ethyl ketone 7g   ・ 1-Methoxy-2-propanol 7 g

[0178]

[Chemical 44]

[0179] [Photosensitive liquid B-1, 2]   Novolak resin (compounds listed in Table 2, amount listed in Table 2)   ・ Surface alignment type infrared absorbing alkali-soluble resin (DB-9)       Or cyanine dye A (compounds listed in Table 2, amount listed in Table 2)   -Stearate n-dodecyl 0.01 g   -Fluorine-based surfactant (MegaFac F-177,     Dainippon Ink and Chemicals Co., Ltd.) 0.05g   ・ Methyl ethyl ketone 7g   ・ 1-Methoxy-2-propanol 7 g

[0180]

[Table 2]

[Evaluation of lithographic printing plate precursor] [Scratch resistance test] Obtained lithographic printing plate precursor 1 of the invention
To 6, 10 and lithographic printing plate precursors 7, 8, 9, 1 of Comparative Examples
1 is a rotary ablation tester (TOYO
SEIKI) was used and rubbed 40 times with Abraser Felt CS5 under a load of 250 g. Then, Fuji Photo Film Co., Ltd. developer DT-1 (diluted 1: 8) and Fuji Photo Film Co., Ltd. Finisher F
Using a PS processor 900H manufactured by Fuji Photo Film Co., Ltd. charged with P2W (diluted at 1: 1), development was carried out at a liquid temperature of 30 degrees and a development time of 12 seconds. The electric conductivity of the developing solution at this time was 45 mS / cm.

The scratch resistance was evaluated according to the following criteria. Party A: The optical density of the photosensitive film in the rubbed part did not change at all. B: The optical density of the photosensitive film in the rubbed part was slightly observed visually. 丙: The optical density of the photosensitive film in the rubbed part was 2 / of non-rubbing part
Table 3 shows the results of the scratch resistance evaluation for those with a score of 3 or less.

[0183]

[Table 3]

As is clear from Table 3, the lithographic printing plate precursor using the image recording material of the present invention as the recording layer was found to have excellent scratch resistance.

[Evaluation of Image Formability] The lithographic printing plate precursors 1 to 7 of the invention and the lithographic printing plate precursor 7 of Comparative Examples thus obtained,
Test patterns 8 and 10 were drawn in an image form with a Trendsetter manufactured by Creo at a beam intensity of 9 w and a drum rotation speed of 150 rpm. First, the lithographic printing plate precursors 1 to 10 exposed under the above-mentioned conditions were developed by Fuji Photo Film Co., Ltd. developer DT-1 (diluted by 1: 9.5) and Fuji Photo Film Co., Ltd. finisher FP.
Using a PS processor 900H manufactured by Fuji Photo Film Co., Ltd. charged with 2 W (diluted 1: 1), the liquid temperature was kept at 30 ° C. and the development time was 12 seconds. The electric conductivity of the developer at this time was 40 mS / cm.

The presence or absence of ablation during exposure was visually confirmed. In addition, the exposed area (non-image area) after development was visually observed for stains or coloration due to the residual film of the recording layer that had poor development. The results are shown in Table 4.

[0187]

[Table 4]

As is clear from Table 4, in the lithographic printing plate precursor using the image recording material of the present invention in the recording layer, a high quality image without stain is formed on the non-image area after development, and ablation occurs. It was found that the image forming property was excellent. From each of the above examples, the recording material containing the surface-aligned infrared-absorbing alkali-soluble resin of the present invention can be recorded with high sensitivity by an infrared laser, is excellent in scratch resistance, and has a high image quality without stains in the non-image area. It was found that the image was formed and the occurrence of ablation was suppressed. That is, the surface alignment type infrared absorbing alkali-soluble resin of the present invention was useful as an image recording material.

[0189]

INDUSTRIAL APPLICABILITY The image recording material of the present invention is capable of recording with high sensitivity to an infrared laser, is excellent in stain resistance of the non-image area and is excellent in scratch resistance of the image area, and can form a high quality image. Has the effect. Further, the novel polymer compound having an infrared absorbing ability of the present invention, which can be suitably used for this image recording material, is useful as an image recording material.

Claims (2)

[Claims] 1. A polymer compound comprising (A) a structural unit having an alkali-soluble functional group, (B) a structural unit having a surface-orienting functional group, and (C) a structural unit having an infrared absorbing ability. An image recording material which contains and whose solubility in an alkali developing solution changes upon irradiation with infrared rays. 2. A polymer compound comprising (A) a structural unit having an alkali-soluble functional group, (B) a structural unit having a surface-orienting functional group, and (C) a structural unit having an infrared absorbing ability.