JP2001056562A - Image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an image recording material having high sensitivity by suppressing the diffusion of heat in the substrate of an image recording material with a photosensitive layer on the substrate and effectively utilizing heat in the photosensitive layer. SOLUTION: A heat insulating layer, a 1st photothermal conversion layer, a layer containing a water-insoluble and alkaline water-soluble high molecular compound and varying its solubility to alkaline water under the action of heat and a 2nd photothermal conversion layer are successively disposed on a substrate to obtain the objective image recording material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor, and more particularly to a lithographic printing plate for so-called direct plate making which can be written by heat of an infrared laser, a thermal head or the like, and can be directly made from digital signals of a computer or the like. The present invention relates to a heat-sensitive image recording material usable for an original plate and a lithographic printing plate precursor using the image recording material.

[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 making a plate directly from digital data of a computer,
Attention has been paid to those using these infrared lasers.

A positive lithographic printing plate material for an infrared laser for direct plate making is disclosed in Japanese Patent Application Laid-Open No. 7-285275. The present invention provides an aqueous alkali solution-soluble resin, a substance that absorbs light and generates heat, and substantially reduces the solubility of the aqueous alkali solution in a state of being thermally decomposable and not decomposed such as an onium salt or a quinonediazide compound. A lithographic printing plate material to which a positive photosensitive compound to be added is added.In the image area, the positive photosensitive compound acts as a dissolution inhibitor to substantially reduce the solubility of the aqueous alkali-soluble resin, and in the non-image area, The compound is decomposed by heat so that it no longer exhibits the dissolution inhibiting ability and can be removed by development to form an image.

[0004] Japanese Patent Application Laid-Open No. 7-20629 discloses a negative type lithographic printing plate material recordable with an infrared laser.
A recording material comprising an onium salt, a resole resin, a novolak resin, and an infrared absorber is described. The infrared laser is converted to thermal energy by an infrared absorber,
The onium salt is decomposed by the heat to form an image. That is, image recording, that is, plate-making of a recording material, is performed by promoting the crosslinking reaction between a binder and a crosslinking agent which is crosslinked by the acid, generated by the decomposition of the onium salt.

By the way, heat energy sufficient to change the solubility is applied to the laser-irradiated surface of the positive or negative photosensitive layer, but the deep part of the positive or negative photosensitive layer, that is, the lithographic printing plate precursor is used. In the vicinity of the support interface, the heat generated in the photosensitive layer diffuses through the support having high thermal conductivity, so that thermal energy cannot be efficiently used in this portion. Therefore, the image forming property of the positive or negative type lithographic printing plate material, that is, the ON / OFF (discretion) of the alkali development of the exposed portion / unexposed portion is not easily obtained, and low image quality is not obtained. There was a sensitivity problem.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide an image recording material having a photosensitive layer, which suppresses heat diffusion to a support, and further comprises a photosensitive layer. An object of the present invention is to provide a high-sensitivity image recording material by efficient heat utilization in the above.

[0007]

The above object can be attained by providing the following image recording material. (1) An image recording material comprising the following layers (a) to (d) provided in this order on a support. (A) a heat insulating layer, (b) a first light-to-heat conversion layer, (c) a layer containing a polymer compound that is insoluble in water and soluble in alkaline water, and whose solubility in alkaline water changes by the action of heat. ,
(D) a second light-to-heat conversion layer.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The positive image recording material of the present invention, on a support,
(A) a heat insulating layer, (b) a first light-to-heat conversion layer, (c) a layer containing a polymer compound that is insoluble in water and soluble in alkaline water, and whose solubility in alkaline water changes by the action of heat. ,
And (d) providing the second light-to-heat conversion layer in this order. The layer (c) which contains a polymer compound which is insoluble in water and soluble in alkaline water and whose solubility in alkaline water changes by the action of heat is mainly (c-1) insoluble in water and A layer containing a polymer compound soluble in alkaline water and having increased solubility in alkaline water by the action of heat; and (c-2) containing a polymer compound insoluble in water and soluble in alkaline water. And a layer whose solubility in alkaline water is reduced by the action of heat.
Hereinafter, the former may be referred to as a "positive photosensitive layer" and the latter as a "negative photosensitive layer". Hereinafter, an image recording material having a positive photosensitive layer may be referred to as a “positive image recording material”, and an image recording material having a negative photosensitive layer may be referred to as a “negative image recording material”. The image recording material of the present invention suppresses heat diffusion to the support by providing a heat insulating layer on the support, and provides a photothermal conversion layer on both sides of a positive photosensitive layer or a negative photosensitive layer. Because heat was applied from above and below the photosensitive layer,
Heat can be efficiently used in the photosensitive layer, and high-sensitivity image recording can be performed. Also,
The image forming material of the present invention is suitable for forming an image with heat or light, particularly an infrared laser based on a digital signal. Further, a lithographic printing plate precursor using this image recording material is suitable for direct plate making using an infrared laser, and a lithographic printing plate precursor with high sensitivity can be obtained.

Hereinafter, each layer of the positive or negative type image recording material will be sequentially described. First, a layer (a positive photosensitive layer and a negative photosensitive layer) containing a polymer compound that is insoluble in water and soluble in alkaline water and whose solubility in alkaline water changes by the action of heat will be described. [Positive photosensitive layer] When a positive photosensitive layer is irradiated with heat, for example, an infrared laser, the solubility of the portion in alkaline water increases to the extent necessary for image formation as compared to before the application of heat. is necessary. When the positive photosensitive layer is irradiated with an actinic ray such as an infrared laser beam, a photochemical reaction or the like occurs in the irradiated portion, and the solubility of the irradiated portion in alkaline water increases. Is formed. Such a positive photosensitive layer is already well-known, and any layer can be used without particular limitation as long as its solubility in alkaline water is reduced to the extent necessary for image formation by the action of heat. One example is described below.

<Polymer Compound Insoluble in Water and Alkali-Soluble> Examples of the polymer compound insoluble in water and soluble in alkaline water contained in the positive photosensitive layer include the following acidic groups (1) to (6): In the structure of the main chain and / or the side chain. (1) phenol group (-Ar-OH) (2) sulfonamide group _{(-SO 2 NH-R) (} 3) substituted sulfonamide-based acid group [(hereinafter, referred to as "active imide group".) - SO ₂ NHCOR , -SO ₂ NHSO
₂ R, -CONHSO ₂ R] (4) carboxylic acid group (-CO ₂ H) (5) sulfonic acid group (-SO ₃ H) (6) phosphoric acid group (-OPO ₃ H ₂₎

Here, Ar represents a divalent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent. Among them, preferred acid groups include
(1) phenolic hydroxyl group, (2) sulfonamide group,
(3) An active imide group is mentioned, and (1) a polymer compound having a phenolic hydroxyl group is particularly preferably used.

(1) Examples of the high molecular compound having a phenolic hydroxyl group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde, a condensation polymer of p-cresol and formaldehyde, Condensed polymer of m- / p-mixed cresol and formaldehyde, phenol and cresol (m-, p-,
Or a mixture of m- / p-) and a novolak resin such as a condensation polymer of formaldehyde, and a condensation polymer of pyrogallol and acetone.
Further, a polymer or copolymer having a phenol group in a side chain as described in [0016] of JP-A-11-17468, for example, a polymer or copolymer of N- (2-hydroxyphenyl) acrylamide can be used. .
Other monomers in the case of a copolymer include Japanese Patent Application No. 11-1.
Monomers described in [0053] of No. 56427 can be used. These resins may be used alone or in combination of two or more. If combined, see US Pat.
Phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a condensation polymer of t-butylphenol and formaldehyde or a condensation polymer of octylphenol and formaldehyde as described in JP-A-9 And a condensation polymer of aldehyde and formaldehyde.

(2) The polymer compound having a sulfonamide group has a monomer having a sulfonamide group as a main component. As the monomer having a sulfonamide group, a monomer comprising a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and a low-molecular compound having at least one polymerizable unsaturated bond in one molecule Is mentioned. Among them, acryloyl group,
Low molecular weight compounds having an allyl group or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group are preferred. Examples of such a compound include a polymer or copolymer containing a monomer having a sulfonamide group described in [0017] to [0020] of JP-A-11-17468. Other monomers in the case of a copolymer include Japanese Patent Application No. 11-156.
Monomers such as those described in No. 427 [0053] can be used.

(3) The polymer compound having an active imide group is described, for example, in JP-A-11-17468, [0021].
Or a polymer compound having an active imide group according to [0023], specifically, a polymer containing N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide as a monomer or Copolymers can be mentioned. As the other monomer in the case of a copolymer, a monomer described in [0053] of Japanese Patent Application No. 11-156427 can be used. (4) Examples of the alkali-soluble polymer having a carboxylic acid group include a polymer having, as a main monomer, a compound having at least one carboxylic acid group and at least one polymerizable unsaturated bond in the molecule. (5) Examples of the alkali-soluble polymer having a sulfonic acid group include a polymer having, as a main monomer, a compound having at least one sulfonic acid group and at least one polymerizable unsaturated bond in the molecule. (6) Examples of the alkali-soluble polymer having a phosphate group include, for example, a polymer mainly containing a compound having at least one phosphate group and at least one polymerizable unsaturated bond in the molecule.

In the present invention, the alkali-soluble polymer having a weight-average molecular weight of 2,000 or more and a number-average molecular weight of 500 or more, irrespective of a homopolymer or a copolymer, is preferable in view of film strength. More preferably, the weight average molecular weight is 5,000 to 300,000, and the number average molecular weight is 800
２５０250,000 and a degree of dispersion (weight average molecular weight / number average molecular weight) of 1.1 to 10. Among the above copolymers, those having a compounding weight ratio of the monomer having an acidic group of (1) to (6) to another monomer in the range of 50:50 to 5:95 from the viewpoint of image forming properties. Preferably, those in the range of 40:60 to 10:90 are more preferable.

Each of these alkali-soluble polymers may be used alone or in combination of two or more kinds. Particularly preferably 50 to 90
It is used in a weight% addition amount. When the amount of the alkali-soluble polymer is less than 30% by weight, the durability of the positive photosensitive layer is deteriorated.

In the positive photosensitive layer of the present invention, it is necessary that the solubility in alkaline water changes (increases in solubility) before and after the application of heat. Can be added. For example, when an onium salt is added to the positive photosensitive layer, the interaction with a polymer compound such as a phenol resin can suppress the solubility of the polymer compound such as the phenol resin in an alkali solution in a state where heat is not applied. it can. The onium salt is decomposed by heat and the solubility of the irradiated portion is restored, so that the irradiated portion can be removed by development.

<Onium Salt> Examples of such onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts. Suitable onium salts for use in the present invention include, for example, S.I. I. Schlesinger, Photog
r. Sci. Eng. , 18, 387 (1974),
T. S. Bal et al, Polymer, 21,
423 (1980), or diazonium salts described in JP-A-5-158230, U.S. Pat. No. 4,069,
No. 055 and 4,069,056, or JP-A-3-1
Ammonium salts described in JP-A-40140; C. N
eckeret al, Macromolecule
s, 17, 2468 (1984), C.I. S. Wen e
tal, Teh, Proc. Conf. Rad. Cu
ring ASIA, p478 Tokyo, Oct
(1988), U.S. Pat. Nos. 4,069,055 and 4,069,056;
V. Crivello et al, Macromol
ecules, 10 (6), 1307 (1977), C
hem. & Eng. News, Nov .; 28, p31
(1988), EP 104,143, U.S. Pat. Nos. 339,049 and 410,201,
Iodonium salts described in JP-A-150848 or JP-A-2-296514; V. Crivell
o et al, Polymer J. J .; 17, 73 (1
985); V. Crivello et al. J.
Org. Chem. , 43, 3055 (1978),
W. R. Watt et al, J.A. Polymer
Sci. , Polymer Chem. Ed. , 22,
1789 (1984); V. Crivello e
tal, Polymer Bull. , 14,279
(1985); V. Crivello et a
1, Macromolecules, 14 (5), 11
41 (1981); V. Crivello et
al, J. et al. Polymer Sci. , Polymer
Chem. Ed. , 17, 2877 (1979), European Patent Nos. 370,693, 233,567 and 2
Nos. 97,443 and 297,442; U.S. Pat.
933,377, 3,902,114, 41
0,201, 339,049, 4,760,0
No. 13, 4,734,444, 2,833,82
7, German Patent Nos. 2,904,626 and 3,60
The sulfonium salt described in JP-A-4,580 or 3,604,581; V. Crivello et a
1, Macromolecules, 10 (6), 13
07 (1977); V. Crivello e
tal, J.M. Polymer Sci. , Polym
erChem. Ed. , 17, 1047 (1979); S. Wen et al, T
eh, Proc. Conf. Rad. Curing A
SIA, p478 Tokyo, Oct (1988).

The counter ions of the above onium salts include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethyl Benzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol -5-sulfonic acid, 2-
Methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, p-toluenesulfonic acid, and the like.

Among these, in particular, hexafluorophosphoric acid,
Alkyl aromatic sulfonic acids such as triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are preferred. The addition amount of the onium salt is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 30% by weight.

<Infrared absorber> It is preferable to add an infrared absorber to the positive photosensitive layer of the present invention. When an infrared absorber is used in the positive photosensitive resin composition, a positive action is caused by interaction with a binder polymer having a specific functional group (development is suppressed in unexposed areas, released in exposed areas, and development is accelerated). Onium salt type structures are particularly preferred in that regard, and particularly preferred are cyanine dyes and pyrylium salts. Further, an onium-type cationic infrared absorber and a nonionic infrared absorber described below in the section of the photothermal conversion layer are also preferably used.

Further, the anionic infrared absorber described in Japanese Patent Application No. Hei 10-237634 can also be suitably used. This anionic infrared absorbing agent refers to a dye that substantially has no anionic structure in the mother nucleus of a dye that absorbs infrared light and has an anionic structure. For example, (a-1) anionic metal complex, (a-2) anionic carbon black,
(A-3) Anionic phthalocyanine. Here, the (a-1) anionic metal complex refers to an anion in which the central metal and the ligand in the complex part that substantially absorbs light become anions. (A-2) Examples of the anionic carbon black include carbon black to which an anionic group such as a sulfonic acid, carboxylic acid, or phosphonic acid group is bonded as a substituent. In order to introduce these groups into carbon black, the Carbon Black Handbook Third Edition (edited by Carbon Black Association, 1995)
As described on page 12 of the Carbon Black Association of Japan on April 5, 2002, a method of oxidizing carbon black with a predetermined acid may be used. (A-3) Anionic phthalocyanine refers to an anionic phthalocyanine in which the anion group described above in the description of (a-2) is bonded to the phthalocyanine skeleton as a substituent to form an anion as a whole. Further, [Ga ⁻ −] described in [0014] to [0105] of Japanese Patent Application No. 10-237634.
M-Gb] an anionic infrared absorbing agent represented by _m X ^{m +} [Ga-represents an anionic substituent, and Gb represents a neutral substituent. Xm + represents a cation having a valence of 1 to m including a proton, and m represents an integer of 1 to 6. ].

<Other Components> Further, the following components can be added to the positive photosensitive layer as needed. For example, a dye having a large absorption in the visible light region can be added to the positive photosensitive layer as a colorant for an image. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow #
103, oil pink # 312, oil green BG,
Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-
505 (all manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI425
55), methyl violet (CI42535), ethyl violet, rhodamine B (CI145170
B), malachite green (CI42000), methylene blue (CI52015), Aizen spiron blue C-RH (manufactured by Hodogaya Chemical Co., Ltd.) and the like,
-293247.

When these dyes are added, the distinction between the image area and the non-image area after image formation becomes clear, so it is preferable to add them. The addition amount is preferably 0.01 to 10% by weight based on the total solid content of the image recording material.

For the purpose of further improving the sensitivity, cyclic acid anhydrides, phenols and organic acids can be added. As cyclic acid anhydrides, US Pat.
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride described in US Pat. No. 5,128;
3,6-Endoxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like.

As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,4,4'-trihydroxybenzophenone, 2,
3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5' -Tetramethyltriphenylmethane and the like.

As the organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates described in JP-A-2-96755 and the like;
Examples thereof include phosphonic acids, phosphate esters, and carboxylic acids, and specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid,
Ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 4-cyclohexene -1,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like.

The proportion of the cyclic acid anhydrides, phenols and organic acids in the image recording material is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight.
0.1 to 10% by weight is particularly preferred.

The image-recording material of the present invention is prepared in accordance with JP-A-62-25 in order to improve the stability of processing under development conditions.
Non-ionic surfactants described in JP-A No. 1740 and JP-A-3-208514;
4, and an amphoteric surfactant described in JP-A-4-13149 can be added.

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

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

The proportion of the nonionic surfactant and amphoteric surfactant in the image recording material is 0.05 to 15% by weight.
Is preferable, and 0.1 to 5% by weight is more preferable.

In the image recording material of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure, and a dye or pigment as an image coloring agent can be added. Representative examples of the printing-out agent include a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, the combination of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, No. 53-36223, No. 54-74728, No. 60-
No. 3626, No. 61-143748, No. 61-151
Combinations of a trihalomethyl compound and a salt-forming organic dye described in JP-A-644 and JP-A-63-58440. The trihalomethyl compound includes an oxazole-based compound and a triazine-based compound, both of which have excellent temporal stability and give clear print-out images.

In the image recording material of the present invention, an epoxy compound, a vinyl ether compound, a phenol compound having a hydroxymethyl group or an alkoxymethyl group described in Japanese Patent Application No. 7-18120, and a Japanese Patent Application No. 9-32893.
It is preferable in view of storage stability to add a crosslinkable compound or the like having an alkali dissolution inhibiting action described in JP-A No. 7-No.

A plasticizer may be added to the image recording material of the present invention, if necessary, to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid Oligomers and polymers can be suitably used.

In the image recording material of the present invention, a surfactant for improving coating properties, for example, JP-A-62-170
For example, a fluorine-based surfactant described in JP-A-950-950 can be added. The preferable addition amount is 0.01 to 1% by weight of the total printing material, and more preferably 0.1 to 1% by weight.
0.5 to 0.5% by weight.

[Negative-type photosensitive layer] When a negative-type photosensitive layer is heated, it is necessary that the solubility of the negative-type photosensitive layer in alkaline water is reduced to the extent necessary for image formation as compared to before the application of heat. It is. Such a negative photosensitive layer is already well-known, and any layer can be used without particular limitation as long as its solubility in alkaline water is reduced by the action of heat to an extent necessary for image formation. An example will be described below.

As the high molecular compound insoluble in water and soluble in alkaline water contained in the negative photosensitive layer, those similar to the high molecular compound used in the positive photosensitive layer can be used. In particular, the following binders can be mentioned. <Binder> Examples of the binder used in the negative photosensitive layer of the present invention include a novolak resin and a polymer having a hydroxyaryl group in a side chain. The novolak resin that can be used as a binder in the present invention is a resin obtained by condensing phenols and aldehydes under acidic conditions. Preferred novolak resins include:
For example, novolak resin obtained from phenol and formaldehyde, novolak resin obtained from m-cresol and formaldehyde, novolak resin obtained from p-cresol and formaldehyde, novolak resin obtained from o-cresol and formaldehyde, novolak obtained from octylphenol and formaldehyde Resin, novolak resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol (m-, p-, o- or m- / p-, m- / o-, o
− / P-mixture) and a novolak resin obtained from formaldehyde.
These novolak resins have a weight average molecular weight of 800 to
200,000 and number average molecular weight of 400-60,00
0 is preferred.

Further, as the binder in the present invention, a polymer having a hydroxyaryl group in a side chain can also be preferably mentioned. In this polymer, a hydroxyaryl group refers to an aryl group in which one or more -OH groups are bonded. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group. From the viewpoint of availability and physical properties, a phenyl group or a naphthyl group is preferable.
Accordingly, the hydroxyaryl group is preferably a hydroxyphenyl group, a dihydroxyphenyl group, a trihydroxyphenyl group, a tetrahydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, or the like. These hydroxyaryl groups further include a halogen atom,
It may have a substituent such as a hydrocarbon group having 20 or less carbon atoms, an alkoxy group having 20 or less carbon atoms, and an aryloxy group having 20 or less carbon atoms. These hydroxyaryl groups are pendantly bonded to the polymer main chain as side chains of the polymer, but may have a linking group with the main chain.

The polymer having a hydroxyaryl group in the side chain suitably used in the present invention is a polymer containing any one of the structural units represented by the following general formulas (IX) to (XII). .

[0041]

Embedded image

(Where R¹¹Represents a hydrogen atom or a methyl group
Show. R¹²And R¹³Can be the same or different
And hydrogen atoms, halogen atoms, carbonization of 10 or less carbon atoms
Hydrogen group, alkoxy group having 10 or less carbon atoms, or carbon number
Shows up to 10 aryloxy groups. Also, R¹²And R
¹³Binds to form a fused benzene or cyclohexane ring
May be formed. R¹⁴Is a single bond or carbon number
It represents 20 or less divalent hydrocarbon groups. R^FifteenIs a single bond
Alternatively, a divalent hydrocarbon group having 20 or less carbon atoms is shown.
R¹⁶Is a single bond or a divalent carbon having 10 or less carbon atoms.
Shows a hydrogen group. X ¹Is a single bond, ether bond,
Represents a ether bond, an ester bond or an amide bond. p
Represents an integer of 1 to 4. q and r are each an integer of 0 to 3
Indicates a number. )

Among the structural units represented by the general formulas (IX) to (XII), examples of specific structural units suitably used in the present invention are shown below.

[0044]

Embedded image

[0045]

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[0046]

Embedded image

[0047]

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[0048]

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These polymers can be synthesized by a conventionally known method. For example, a polymer having a structural unit represented by the general formula (IX) is obtained by subjecting a corresponding styrene derivative in which a hydroxy group is protected as an acetic ester or t-butyl ether to a polymer by radical polymerization or anion polymerization, and then deprotecting the polymer. It is obtained by doing. Polymers having a structural unit represented by formula (X) are described in JP-A-64-32256 and JP-A-64-32256.
It can be synthesized by the method described in 4-35436 and the like. Further, the polymer having the structural unit represented by the general formula (XI) is obtained by reacting an amine compound having a hydroxy group with maleic anhydride to obtain a corresponding monomer, and then forming the polymer by radical polymerization. . Further, the polymer having the structural unit represented by the general formula (XII) is derived from a styrene having a functional group useful in synthesis such as chloromethylstyrene or carboxystyrene as a raw material to a monomer corresponding to the general (XII). And further obtained by making it into a rimer by radical polymerization.

In the present invention, a homopolymer composed of only the structural units represented by the general formulas (IX) to (XII) may be used, or a copolymer containing other structural units may be used. Other structural units suitably used include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, maleic anhydride Structural units introduced from known monomers such as acid imides are exemplified.

Specific examples of the acrylates that can be used include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate,
(N-, i-, sec- or t-) butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate, cyclohexyl Acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, 2- (p-
Hydroxyphenyl) ethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate,
Phenyl acrylate, chlorophenyl acrylate,
Sulfamoylphenyl acrylate and the like can be mentioned.

Specific examples of the methacrylates include methyl methacrylate, ethyl methacrylate,
(N- or i-) propyl methacrylate, (n-,
i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate , Trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, 2- (p
-Hydroxyphenyl) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate and the like.

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide,
Hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (p-hydroxyphenyl) acrylamide, N- (sulfamoylphenyl) acrylamide, N- (phenylsulfonyl) acrylamide, N- (tolylsulfonyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide and the like can be mentioned.

Specific examples of methacrylamides include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, N-butyl methacrylamide, N-benzyl methacrylamide, N-hydroxyethyl methacryl Amide,
N-phenyl methacrylamide, N-tolyl methacrylamide, N- (p-hydroxyphenyl) methacrylamide, N- (sulfamoylphenyl) methacrylamide, N- (phenylsulfonyl) methacrylamide, N
-(Tolylsulfonyl) methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide and the like.

Specific examples of vinyl esters include vinyl acetate, vinyl butyrate, vinyl benzoate and the like. Specific examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, propyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy methyl styrene, acetoxy methyl styrene, methoxy styrene, dimethoxy styrene , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

Of these monomers, particularly preferably used are acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes and acrylic acids having 20 or less carbon atoms. Methacrylic acid and acrylonitrile.

The proportion of the structural units represented by the general formulas (IX) to (XII) contained in the copolymers using them is 5 to 1
00% by weight, more preferably 1% by weight.
0 to 100% by weight. The molecular weight of the polymer used in the present invention is preferably 40% by weight average molecular weight.
00 or more, more preferably in the range of 10,000 to 300,000, preferably number-average molecular weight of 1000 or more,
More preferably, it is in the range of 2000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably in the range of 1.1 to 10. These polymers are random polymers, block polymers,
Although any of a graft polymer and the like may be used, a random polymer is preferable.

The binder used in the present invention may be used alone or in a combination of two or more. The amount of the binder added is 5 to 95% by weight, preferably 10 to 95% by weight, based on the total solid content of the image recording material.
%, Particularly preferably from 20 to 90% by weight. If the amount of the binder is less than 5% by weight, the durability of the recording layer is deteriorated. If the amount exceeds 95% by weight, no image is formed.

In order to reduce the solubility as described above, an acid generator which is decomposed by light or heat to generate an acid is added to the negative photosensitive layer, and a crosslinking agent, an infrared absorber, and Other components besides these can be added. <Acid Generator> The acid generator refers to a compound that generates an acid by irradiation with light having a wavelength of 200 to 500 nm or heating at 100 ° C. or higher, and includes a photoinitiator for photocationic polymerization and a photoinitiator for photoradical polymerization. And a known compound capable of generating an acid upon thermal decomposition, such as a known photo-decoloring agent, a photo-discoloring agent, or a known acid generator used for micro resists, and mixtures thereof. For example, I. Sch
Lessinger, Photogr. Sci. En
g. , 18, 387 (1974); S. Bal e
tal, Polymer, 21, 423 (1980)
Diazonium salts described in U.S. Pat. No. 4,069,05
Nos. 5,069,056 and Re27,992, and the ammonium salts described in JP-A-4-365049; C. Necker etal, Ma
cromolecules, 17, 2468 (198
4), C.I. S. Wen et al, Teh, Pro
c. Conf. Rad, CuringASIA, p47
8 Tokyo, Oct (1988); U.S. Pat.
The phosphonium salts described in the specifications of JP-A Nos. 069,055 and 4,069,056; V. Crivello
et al, Macromolecules, 10
(6), 1307 (1977), Chem. & En
g. News, Nov .; 28, p31 (1988), EP 104,143, US 339,049.
No. 410,201, JP-A No. 2-15
No. 0848 and JP-A-2-296514. V. Crivellot a
1, Polymer J. 17, 73 (1985),
J. V. Crivello et al. J. Org.
Chem. 43, 3055 (1978); R. W
att et al, J.A. Polymer Sci. ,
Polymer Chem. Ed. , 22,1789
(1984); V. Crivello et a
l, Polymer

Bull. , 14, 279 (1985),
J. V. Crivello et al, Macrom
olecules, 14 (5), 1141 (198
1). V. Crivello et al, J. Mol. P
polymer Sci. , Polymer Chem.
Ed. , 17, 2877 (1979), EP 37
Nos. 0,693, 390,214, 233,567
Nos. 297,443 and 297,442; U.S. Pat. Nos. 4,933,377; 161,811;
No. 10,201, No. 339,049, No. 4,760,
No. 013, No. 4,734,444, No. 2,833,8
No. 27, German Patent Nos. 2,904,626 and 3,60
4,580, 3,604,581, the sulfonium salt described in each specification,

J. V. Crivello et al,
Macromolecules, 10 (6), 1307
(1977); V. Crivello et a
1, J .; Polymer Sci. , Polymer
Chem. Ed. , 17, 1047 (1979); S. Wen et al, Te
h, Proc. Conf. Rad. Curing AS
IA, p. 478, Tokyo, Oct (1988). Also, benzyl sulfonates described in U.S. Pat. No. 5,135,838 and U.S. Pat. No. 5,200,544, JP-A Nos. 2-100054 and 2-10
Active sulfonic acid esters and disulfonyl compounds described in JP-A-5-0055 and JP-A-9-197671,
Haloalkyl-substituted S- described in -271029;
Triazines can also be mentioned.

In the present invention, these acid generators are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 25% by weight, more preferably 0.5 to 50% by weight based on the total solid content of the negative photosensitive layer.
20% by weight is added to the negative photosensitive layer of the present invention. When the addition amount is less than 0.01% by weight, no image is obtained, and when the addition amount is more than 50% by weight, non-image areas are stained during printing. . These compounds may be used alone or in combination of two or more.

<Cross-Linking Agent> Examples of the cross-linking agent include a methylol compound described in Japanese Patent Application No. 9-234406, an alkoxymethyl compound, a resole resin and the like, and a cross-linking agent described in Japanese Patent Application No. 11-151412. The following are mentioned. (I) an aromatic compound substituted with an alkoxymethyl group or a hydroxymethyl group (ii) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group (iii) an epoxy compound (i) an alkoxymethyl Examples of the aromatic compound substituted with a group or a hydroxymethyl group include an aromatic compound and a heterocyclic compound poly-substituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. [Formula 14] and [Formula 1]
5] are preferably mentioned. In the above formula, L _{1 to} L ₈ each independently represent a hydroxymethyl group or an alkoxymethyl group substituted with an alkoxy group having 18 or less carbon atoms, such as methoxymethyl, ethoxymethyl and the like.

(Ii) Compounds having an N-hydroxymethyl group, an N-alkoxymethyl group or an N-acyloxymethyl group include those disclosed in European Patent Publication No. 0,133,216 (hereinafter referred to as EP-A), West German Patent No. 3,6
No. 34,671, No. 3,711,264, monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate, EP-A
And the alkoxy-substituted compounds disclosed in Japanese Patent No. 0,212,482. As a more preferred example,
For example, a melamine-formaldehyde derivative having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups or N-acyloxymethyl groups is exemplified, and among them, N-alkoxymethyl derivatives are particularly preferred.

(Iii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds containing one or more epoxy groups. For example, a reaction product of bisphenol A with epichlorohydrin, a reaction product of a low molecular weight phenol-formaldehyde resin with epichlorohydrin and the like can be mentioned. Other examples include epoxy resins described and used in U.S. Pat. No. 4,026,705 and British Patent 1,539,192.

The crosslinking agent (i) to (iii) which can be used in the present invention is from 5 to 80% by weight, preferably from 10 to 75% by weight, more preferably from 10 to 75% by weight, based on the total solids of the image recording material. Ranges from 20 to 70% by weight. If the amount of the crosslinking agent is less than 5% by weight, the durability of the photosensitive layer of the resulting lithographic printing plate precursor will be deteriorated. If it exceeds 80% by weight, it is not preferable from the viewpoint of storage stability. .

Further, as a crosslinking agent, the above-mentioned Japanese Patent Application No.
Phenol derivatives shown in [0078] to [0084] of No. 151412 are exemplified.

<Infrared Absorber> It is preferable to add an infrared absorber to the negative photosensitive layer of the present invention.
When an infrared absorber is used for the negative photosensitive layer, the energy given by the laser that emits infrared light is converted into thermal energy by the infrared absorber, and the heat decomposes the acid generator to form an image. Is done.
That is, the acid generated by the decomposition of the acid generator promotes the crosslinking reaction between the crosslinking agent crosslinked by the acid and the binder, thereby performing image recording, that is, plate-making of the recording material. Therefore, a wavelength of 760 nm is used as an infrared absorber.
It is not particularly limited as long as it absorbs infrared rays of from 1200 nm to 1200 nm and absorbs it to effectively convert energy into heat. Preferred infrared absorbers have a wavelength of 76.
Dyes or pigments having an absorption maximum at 0 nm to 1200 nm are exemplified, and the infrared absorber described in the section of the positive photosensitive layer and the infrared absorber described in the section of the light-to-heat conversion layer described later are suitably used.

<Other Components> In the negative photosensitive layer of the present invention, various compounds other than these may be added as necessary. For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY,
Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000) , Methylene blue (CI5
2015) or the dyes described in JP-A-62-293247. These dyes are preferably added because the image area and the non-image area can be easily distinguished after image formation. The addition amount is
The proportion is 0.01 to 10% by weight based on the total solid content of the image recording material.

Further, in the image recording material of the present invention, JP-A-62-251740 and JP-A-3-208514 are used in order to widen the stability of processing under development conditions.
Non-ionic surfactants described in JP-A-59-121044, JP-A-4-13149.
An amphoteric surfactant such as that described in JP-A No. 2-211 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the amphoteric surfactant include:
Alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, Daiichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the image recording material is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

Further, a plasticizer may be added to the image recording material of the present invention, if necessary, in order to impart flexibility to the coating film. For example, 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 a polymer. In addition to these, epoxy compounds, vinyl ethers and the like may be added.

The thickness of the positive photosensitive layer and the negative photosensitive layer is such that the dry weight of the coating film from the photosensitive layer coating solution is 0.01 to 5 g / m ^2. Is a guide. If the weight is less than 0.01 g / m ^2, it is difficult to obtain a sufficient thickness as an image recording material, and 5 g / m ^2.
When the ratio exceeds the above range, the image formability is likely to be lowered.

[Heat Insulating Layer] Next, the heat insulating layer which is a layer constituting the positive or negative image recording material of the present invention will be described. The heat insulating layer is provided to prevent the heat generated in the light-to-heat conversion layer and the positive photosensitive layer or the negative photosensitive layer from diffusing to the support. Therefore, it is preferable that the heat-insulating layer has low heat transfer, and it is preferable that the heat-insulating layer be a layer containing an organic polymer binder as a main component from the viewpoint of easy formation of the layer. Preferred heat insulating layers include the following (1) to (5).

(1) Japanese Patent Publication No. 61-54219 (2)
In addition to the epoxy resin compositions shown in the right column of the page, line 11 to the same column, line 35, polyurethane resin, phenol resin, acrylic resin, alkyd resin, polyester resin, polyamide resin, polyimide resin, melamine resin,
Urea resin, benzoguanamine resin, diallyl phthalate resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, polycarbonate resin, polyacrylonitrile-butadiene copolymer, polyether resin, Polyether sulfone resin and the like.

(2) Water-soluble polyamide or alcohol-soluble polyamide. Examples of the water-soluble polyamide include a molecule obtained by reacting a polyamide with a cyclic sulfonic acid ester as shown in page 2, upper left column, line 13 to page 3, lower right column, line 1 of JP-A-48-72250. Polyamides containing a sulfonic acid group or a sulfonate group therein, such as N, N'-di (γ) as shown in page 2, lower left column, line 1 to page 4, upper left column, line 6 of JP-A-50-7605. Polyamide containing basic nitrogen obtained by copolymerizing (aminopropyl) piperazine and the like, and polyamide obtained by quaternizing these polyamides with acrylic acid and the like. JP-A-55-74537, lower right column, line 1, A copolymerized polyamide containing a polyether segment having a molecular weight of 150 to 1500 shown in the lower right column, line 2 on page 3, and α- (N, N′-dialkylamino) -ε- Rorakutamu ring-opening polymerization or α- (N, N'- dialkylamino)-.epsilon.-caprolactam ring-opening copolymerized polyamide obtained in such a ε- caprolactam. Further, examples of the water-soluble polyamide include polyamides having an ether bond obtained by copolymerizing any one of dicarboxylic acids, diamines and cyclic amides having an ether bond in the molecule. Further, as the alcohol-soluble polyamide, dibasic acid fatty acid and diamine, ω
-Amino acids, lactams or linear polyamides synthesized by known methods from lactams or derivatives thereof,
Not only homopolymers but also copolymers and block polymers can be used. Typical examples are nylon 3,
4, 5, 6, 8, 11, 12, 13, 66, 610, 6
/ 10, 13/13, polyamide from meta-xylylenediamine and adipic acid, polyamide from trimethylhexamethylenediamine or isophoronediamine and adipic acid, ε-caprolactam / adipic acid / hexamethylenediamine / 4,4′-diaminodicyclohexyl Methane copolymerized polyamide, ε-caprolactam / adipic acid / hexamethylenediamine / 2,4,4′-trimethylhexamethylenediamine copolymerized polyamide, ε-caprolactam / adipic acid / hexamethylenediamine /
Isophoronediamine copolymerized polyamide, or a polyamide containing these components, their N-methylol,
-Alkoxymethyl derivatives can also be used.

(3) A heat insulating layer containing an epoxy compound described in [0034] to [0071] of JP-A-11-123888 and a compound having a carboxyl group. Examples of the epoxy compound contained in the heat insulating layer include an epoxy compound obtained by reacting epihalohydrin with a hydroxyl group-containing compound. Specific examples of the hydroxyl group-containing compound include methanol, ethanol, propanol,
Pentanol, cyclohexanol, octanol, undecanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-butene-1,4-diol, 5-hexene-
1,2-diol, 7-octene-1,2-diol,
3-mercapto-1,2-propanediol, hydroquinone, dihydroxyanthraquinone, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, bisphenol A, bisphenol S, phenol formaldehyde novolak resin, resole resin, resorcinbenzaldehyde resin,
Pyrogallol acetone resin, hydroxystyrene polymer and copolymer, glycerin, diglycerin, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, polyvinyl alcohol, cellulose and derivatives thereof And hydroxyethyl (meth) acrylate polymers and copolymers.

The compounds having a carboxyl group contained in the heat insulating layer include those described in the publications [0042] to [0097]
49], the aliphatic polyamine compound having an aromatic ring, the aromatic polyamine compound,
Dicyandiamide, adipic hydrazide, imidazoles, an amino compound such as an amino group-containing resin such as a melamine resin, or an amine adduct compound and a carboxylic acid, which are reaction products of these amino compounds and an epoxy compound such as the epoxy compound, Compounds reacted at a ratio such that at least one terminal is a carboxyl group are exemplified. Specific examples of carboxylic acids include malonic acid, succinic acid, malic acid, thiomalic acid, racemic acid, citric acid,
Divalent organic carboxylic acids such as glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid and dimer acid, and trivalent organic carboxylic acids such as trimellitic acid; 3,9-bis (2-carboxyalkyl) 2,4,8,10-tetraoxaspiroundecane and the like. A carboxy-modified unvulcanized rubber can also be used. Specifically, natural rubber, butadiene, isoprene, styrene, acrylonitrile, carboxy-modified homopolymer or copolymer selected from acrylates, for example, carboxy-modified polybutadiene, carboxy-modified styrene-butadiene copolymer, Examples thereof include carboxy-modified acrylonitrile-butadiene copolymer and carboxy-modified methyl methacrylate-butadiene copolymer. Furthermore,
A compound obtained by subjecting the above polycarboxylic acid to an esterification reaction with polyethylene glycol or polypropylene glycol can also be used. The compound preferably has carboxyl groups at both ends.

As the compound having a carboxyl group,
Acrylic acid having one or two carboxyl groups in the molecule described in [0056] to [0058] of the publication, in addition to the reaction product of the amino compound or amine adduct compound and the carboxyl group-containing compound, Α, β-unsaturated compounds such as methacrylic acid;
Polymers or copolymers containing an unsaturated compound in the molecule are mentioned.

Further, as a crosslinking agent in the heat insulating layer composition,
It is preferable to include at least one compound selected from the group consisting of the amine compound and the amine adduct compound as described above, and to crosslink the functional group with the compound from the viewpoint of solvent resistance during printing and printing durability. Furthermore, polyamidoamine obtained by reacting the above-mentioned polyamine compound and carboxylic acid so that both terminals become amino groups can also be mentioned.

(4) Water-soluble (hydrophilic) resin (polymer)
Things to use. In this case, those which are soluble in the developer are more preferable. Specifically, acrylic acid copolymers such as polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyhydroxyethyl acrylate, and polyvinylpyrrolidone; Copolymer;
Polyethylene glycol polyoxyethylene, polypropylene glycol, ethylenediamine, hexaethylenediamine, polyurethane resin, polyhydroxymethylurea, polyhydroxymethylmelamine resin, water-soluble cellulose such as soluble starch, CMC (carboxymethylcellulose), hydroxyethylcellulose, guar gum, Polysaccharides such as tragacanth gum and xanthan gum; and water-soluble polymers such as sodium alginate, gelatin, casein, and milk casein.

(5) Those using a resin emulsion. Examples of such an emulsion include synthetic resin emulsions such as styrene-butadiene rubber (SBR), styrene-methyl methacrylate-butadiene rubber (SMBR), acrylic resin, acryl-styrene resin, and vinyl acrylate resin.

A mixture may be dispersed in the heat-insulating layer in order to increase the heat-insulating ability. Preferred mixtures include falite, limestone, mica, clay, synthetic clay, alumina,
Silica, calcium carbonate, calcium aluminate and the like can be mentioned. Although the thickness of the heat insulating layer varies depending on the type of the resin binder, it is a standard to set the thickness so that the dry weight of the coating film from the coating solution for the heat insulating layer is 0.01 to 3 g / m ^2. . If the weight is less than 0.01 g / m ^2, it becomes difficult to prevent diffusion of heat generated in the photosensitive layer and the photothermal conversion layer. Further, if it exceeds 3 g / m ² , the image formability tends to deteriorate, so that it is preferably within the above range. The point is that the photosensitive layer needs to have a thickness to prevent loss of heat energy required for a photochemical reaction or a thermochemical reaction.

[First and Second Light-to-Heat Conversion Layers] Next, the light-to-heat conversion layers will be described. The light-to-heat conversion layer is a layer containing at least a light-to-heat conversion agent and a binder or a layer formed by vapor deposition of an inorganic substance. As the photothermal conversion agent, an organic compound and / or an inorganic compound can be appropriately selected and used. As the organic compound, for example, 3
Dyes and dyes having an absorption in the wavelength range of 50 to 1200 nm can be mentioned. Specifically, cyanine dyes, rhodocyanine dyes, oxonol dyes, carbocyanine dyes, dicarbocyanine dyes, tricarbocyanine dyes Chemical Formula 1 ", tetracarbocyanine dyes, pentacarbocyanine dyes, styryl dyes, aminium dyes, diimonium dyes, pyrylium dyes, metal-containing dyes such as metal phthalocyanines and metalloporphyrins, and the like. .Rev.) Vol. 92, 1
The compounds described on page 197 (1992) can be used. Inorganic compounds that absorb in the wavelength range of 350 to 1200 nm include graphite, carbon black, metal powder particles, metal oxide powders such as cobalt tetroxide, iron oxide, chromium oxide, copper oxide, and titanium black. Particles, metal nitride powder such as niobium nitride, metal oxide powder such as tantalum carbide, metal sulfide powder, and the like.
Further, various magnetic powder particles and the like used for magnetic paints and the like can also be suitably used. As the binder for the light-to-heat conversion layer, any binder can be used without any limitation as long as it can sufficiently hold the light-to-heat conversion agent. As such a binder, a known binder that dissolves or disperses the photothermal conversion agent is used. Examples of the binder include nitrocellulose, cellulose such as ethyl cellulose, cellulose derivatives, polymethyl methacrylate, acrylic acid esters such as polybutyl methacrylate, homopolymers and copolymers of methacrylic acid esters, polystyrene, α
-Homopolymers and copolymers of styrene monomers such as methylstyrene. Various synthetic rubbers such as isoprene and styrene-butadiene, homopolymers of vinyl esters such as polyvinyl acetate and copolymers such as vinyl acetate and vinyl chloride, polyurea, polyurethane, polyester, and various condensation polymers such as polycarbonate and , "J. Ima
ging Sci. , P59-64, 30 (2), (1
986) (Frechet et al.) And Polymers
in Electronics Symposium
Series, P11, 242, T. Davidso
n, Ed. , ACS Washington, DC (1
984) (Ito, Willson) "," Micro
electronic Engineering, P3
-10, 13 (1991) (E, Reichmani
s, L .; F. Thompson), a binder used in a so-called “chemical amplification system”, and the like can be used. In addition to the photothermal conversion agent and the binder,
Additives can be used. The additive improves the mechanical strength of the first layer, improves laser recording sensitivity, improves the dispersibility of the dispersion in the light-to-heat conversion layer,
It is added for various purposes such as improving the adhesion to an adjacent layer.

Preferred photothermal conversion layers include those described in the following (1) to (5). (1) It has a softening point in the range of 25 to 200 ° C. described in JP-A-11-91257 and a maximum value of the rate of weight loss during thermal decomposition of 0.1 to 5% by weight / ° C. And a light-to-heat conversion layer containing a polymer having film forming ability and a light-to-heat conversion agent. Examples of the polymer include polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyvinyl phenyl ketone, polystyrenes, methacrylate resins such as polymethyl methacrylate, and acrylics such as polymethyl acrylate. Resin, acrylamide resin such as poly N-methyl methacrylamide, phenol resin such as phenol novolak, cresol novolak, etc.
8] and [0009].
Further, as the photothermal conversion agent, carbon black, black pigments such as nigrosine, metal complexes, metal oxides, metal salts,
Examples thereof include photothermal conversion agents described in the publications [0011] to [0013] such as metal powder.

Further, as a preferable light-to-heat conversion layer, a layer using a water-soluble binder as a binder is exemplified. As the water-soluble binder, for example, polyvinyl alcohol,
Polyvinyl acetal, polyvinylpyrrolidone, nylon, polyacrylamide, polyalkylene oxide,
Gelatin, casein, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxyethyl starch, gum arabic, saccharose octaacetate, ammonium alginate, sodium alginate, polyvinylamine, polyethylene oxide, polyacrylic acid and the like, among which polyvinyl alcohol, polyvinyl Acetal, nylon, polyacrylamide and polyalkylene oxide are preferred. Further, as the photothermal conversion agent, a near-infrared light absorber, for example, carbon black, cyanine, polymethine, azurenium, squarium, thiopyrylium, naphthoquinone, organic compounds such as anthraquinone dyes, phthalocyanine, azo, Thioamide-based organometallic complexes and the like are preferably used. These can be used alone or in combination of two or more. Of these, cyanine-based, polymethine-based, squarium-based dyes, and carbon black are preferred. When carbon black is used, the dispersed particle size is preferably set to 0.5 μm or less.

(2) JP-A-11-34494 [0
010] and the photothermal conversion layer containing a layered inorganic compound, a laser absorbing dye and a binder described in [0015] to [0020]. As the layered inorganic compound, a swellable inorganic layered compound is preferable, and as these compounds, for example, bentonite,
Examples include swelling viscosity minerals such as hectorite, saponite, beederite, nontronite, stevensite, beidellite, and montmorillonite, swellable synthetic mica, and swellable synthetic smectite. These swellable inorganic layered compounds have a laminated structure composed of unit crystal lattice layers having a thickness of 10 to 15 angstroms, and the substitution of metal atoms in the lattice is significantly larger than other clay minerals. As a result, the lattice layer causes a shortage of positive charge, and Na ⁺ ,
Cations such as Ca ²⁺ and Mg ²⁺ are adsorbed. The cations interposed between these layers are called exchangeable cations and exchange with various cations. In particular, when the cations between the layers are Li ⁺ , Na ^+, etc., since the ionic radius is small, the bond between the layered crystal lattices is weak, and the swells greatly with water. When shear is applied in this state, it is easily cleaved and forms a stable sol in water. Bentonite and swellable synthetic mica have a strong tendency and are preferred for the purpose of the present invention.
Particularly, water-swellable synthetic mica is preferable. Examples of the water-swellable synthetic mica include Na tetrathick mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ Na or Li teniolite (NaLi) Mg ₂ (Si ₄ O
₁₀₎ F ₂ Na or Li hectorite (NaLi) / 3Mg ₂ / 3L
i _1/3 Si ₄ O ₁₀ ) F _{2 and the} like. The laser-absorbing dye is preferably a dye that absorbs in the visible to infrared wavelength region, such as a cyanine dye, a phthalocyanine dye, a naphthalocyanine dye, an anthraquinone dye, and a pyrylium dye. As the binder, hydrophilic polymers such as gelatin and polyvinyl alcohol, polystyrene, acryl, and other hydrophobic polymers can be used, but swell, cleave, and disperse layered inorganic compounds, particularly water-swellable synthetic mica. Above, a hydrophilic polymer is desirable.

(3) The heat-sensitive layer described in JP-A-11-138737, which contains at least a photothermal conversion substance and a compound which is cured by heating, can be used. As light-to-heat conversion materials, the publications [0042] to [0]
046] described above.
Examples of the compound which is cured by heating include (1) compounds having two or more ethylenically unsaturated groups in one molecule described in [0048] to [0074] and [0075] to [0080] in the same publication. A combination of substances that generate a radical by heating as described in (2) [008
2] [0095] Compounds having two or more ethylenically unsaturated groups in one molecule, [0096] to [0101]
4]. A combination of the compound having two or more thiol groups in one molecule and a substance which generates a radical by heating as described in (3), [0105] to [010]
9], a combination of the epoxy compound described above and an amino resin. Preferred composition ratios include the composition ratios described in the publications [0154] to [0159].

(4) A light-to-heat conversion layer containing a light-to-heat conversion substance and a self-oxidizing substance described in JP-A-11-129039. The self-oxidizing substance in this light-to-heat conversion layer is added in order to facilitate the decomposability by the light-to-heat conversion substance, and nitro compounds such as nitrocellulose, ammonium nitrate, potassium nitrate and sodium nitrate, organic peroxides, azo compounds, Diazo compounds or hydrazine derivatives are preferably used. In particular, nitrocellulose is a polymer, and therefore has a suitable viscosity in a solution state, and has a hydroxyl group in the molecule, so that it is easy to form a crosslinked structure of the thermosensitive layer, which is preferable. This nitrocellulose is not intended for explosive use, but is preferably industrial nitrocellulose. Further, the viscosity of the nitrocellulose is preferably from 1/16 to 3 seconds, more preferably from 1/8 to 1 second, even more preferably from 1/8 to 1 / second.
2 seconds. Examples of the photothermal conversion material include carbon black, black pigments, green pigments, metal complexes, inorganic compounds, metal compounds, metal powders, dyes absorbing infrared rays or near infrared rays described in the above publications [0070] to [0084]. Can be used. The light-to-heat conversion layer may further contain a binder as described in [0108].

(5) A heat-sensitive layer containing a photothermal conversion substance and a thermally decomposable compound described in JP-A-11-59005 can be used. The thermally decomposable compound is used to enhance thermal decomposition by a photothermal conversion substance, and a compound having an allyl bond or a benzyl group and a hydroxyl group is used. (An allyl group includes a substituted allyl group such as a cinnamyl group, and a benzyl group includes a substituted benzyl group such as a benzhydryl group or a trityl group.)
Allyl bond or benzyl group-containing alcohols such as alcohols having a carboxyl group such as alkenyl alcohols having higher functionality and benzyl alcohol, benzyl acid, tropic acid, etc., allyl phenol, allyl biphenol, allyl bisphenol, allyl bisphenol A type epoxy Allylphenols such as compounds,
Glycidyl ethers such as ethylene glycol (allyl or benzyl) glycidyl ether, propylene glycol (allyl or benzyl) glycidyl ether, polyethylene glycol (allyl or benzyl) glycidyl ether, and polypropylene glycol (allyl or benzyl) glycidyl ether are exemplified.

Further, a linear polymer having a hydroxyl group and an allyloxy group or a benzyloxy group in a side chain may be mentioned. This polymer is obtained by etherifying a linear polymer having a hydroxyl group and a halogen group in a side chain with sodium (allyl alkoxide or benzyl alkoxide). As a linear polymer,
Copolymers of vinyl alcohol and vinyl halide may be mentioned.If necessary, maleic acid, fumaric acid, oleic acid, cinnamic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, elaidic acid and esters thereof A copolymer to which a monomer having an ethylenic double bond such as a compound, acrylamide, methacrylamide, or vinyl acetate may be used. Further, [003]
4] A line having a hydroxyl group and an allyloxycarbonyl group or a benzyloxycarbonyl group in a side chain obtained by esterifying the linear polymer having a hydroxyl group and a carboxyl group in the side chain with allyl alcohol or benzyl alcohol. Polymers. In addition, the above-mentioned publication [0060]
And the binder described in [0061] can be added.

As the light-to-heat conversion material added to the light-to-heat conversion layer, in addition to those shown above, cationic infrared absorbers having the following onium salt structures (CA-1 to C-1)
A-44) can be used.

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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In the above structural formula, T ⁻ represents a monovalent counter anion, and is preferably a halogen anion (F ⁻ , Cl ⁻ ,
Br ^-, I ^-), a Lewis acid anion _{^{(BF 4 -, PF 6 -}} , S
bCl ₆ ⁻ , ClO ₄ ⁻ ), an alkylsulfonic acid anion,
Aryl sulfonate anion.

The alkyl of the alkyl sulfonic acid is
A linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl,
Isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, and 2-norbornyl groups be able to. Among these, straight-chains having 1 to 12 carbon atoms, 3 to 12 carbon atoms.
And a cyclic alkyl group having 5 to 10 carbon atoms is more preferred.

The aryl of the aryl sulfonic acid may be one having one benzene ring, one having two or three benzene rings forming a condensed ring, and one having a benzene ring and a five-membered unsaturated ring forming a condensed ring. Represents a formed one, and specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenabutenyl group, and a fluorenyl group, and among these, a phenyl group and a naphthyl group are more preferable. .

Further, nonionic infrared absorbing agents represented by the following NA-1 to NA-12 can also be preferably used.

[0111]

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[0112]

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[0113]

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[0114]

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In the present invention, in order to effectively diffuse heat from the first and second light-to-heat conversion layers to the positive photosensitive layer or the negative photosensitive layer, the first or second light-to-heat conversion layer needs to have a light-to-heat conversion layer. It is preferable to add at least 1% by weight of the agent to the total solid content of the light-to-heat conversion layer, more preferably 3% by weight.
% By weight, more preferably 5% by weight. Addition amount is 1
When the amount is less than the weight percentage, the amount of heat transferred from the light-to-heat conversion layer to the photosensitive layer is small, and the meaning of providing the light-to-heat conversion layer is lost. If the addition amount exceeds 50% by weight, the coatability and the developability of the non-image area are liable to decrease, so the addition amount is preferably smaller than 50% by weight. Further, the total amount of the photothermal conversion agent contained in the first and second photothermal conversion layers is at least 2% by weight.
It is preferable that Furthermore, the relative ratio of the light-to-heat conversion agent contained in the first light-to-heat conversion layer and the second light-to-heat conversion layer is such that the ratio of the second layer to the first layer is 1:99 to 80:20, preferably 1: 9. The ratio is preferably 7 to 3: from the viewpoint of image forming properties. The film thickness of the first and second light-to-heat conversion layers is such that the dry weight of the coating film from the light-to-heat conversion layer coating solution is 0.
01-5 g / m ² , preferably 0.02-3 g / m ²
It is preferable that the film thickness be in the range of m ² . Further, it is preferable that the total weight of the first and second light-to-heat conversion layers is at least 0.02 g / m ² . Also,
In the positive-type or negative-type image recording material, the first light-to-heat conversion layer and the second light-to-heat conversion layer may have the same or different compositions and thicknesses.

[Support] The support of the positive or negative image recording material of the present invention is a plate which is dimensionally stable and is, for example, paper or plastic (for example, polyethylene, polypropylene, polystyrene, etc.). 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.), and paper or plastic film on which the above-mentioned metal is laminated or vapor-deposited.

Preferred examples of the support include a polyester film and an aluminum plate. Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in aluminum alloys include silicon, iron, manganese,
Copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The total content of foreign elements in the alloy is 10% by weight or less. Particularly preferred aluminum in the present invention is pure aluminum. However, completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate used as the support in the present invention is approximately 0.1 mm to
About 0.6 mm, preferably 0.15 mm to 0.4 m
m, particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like is performed to remove the rolling oil on the surface. The surface roughening treatment of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. Further, as an electrochemical surface roughening method, there is a method of performing an alternating current or a direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment, if necessary, and then subjected to an anodic oxidation treatment, if necessary, in order to enhance the water retention and abrasion resistance of the surface. You. As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. . The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The conditions of the anodizing treatment vary depending on the electrolyte used, and thus cannot be specified unconditionally.
It is appropriate that the current density is 5 to 60 A / dm2, the voltage is 1 to 100 V, and the electrolysis time is 10 seconds to 5 minutes. If the amount of the anodic oxide coating is less than 1.0 g / m2, the film resistance is insufficient or the non-image area is easily damaged. So-called "scratch dirt" is likely to occur.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. U.S. Pat. No. 2,714,075 discloses a hydrophilic treatment that can be used in the present invention.
No. 66, No. 3,181,461, No. 3,280,
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in U.S. Pat. Nos. 734 and 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, potassium fluorozirconate disclosed in JP-B-36-22063, U.S. Pat.
276,868, 4,153,461, and 4,689,272, and the like, such as a method of treating with polyvinyl phosphonic acid.

[Undercoat Layer] In the image recording material of the present invention, an undercoat layer can be provided on the support, if necessary. Various organic compounds are used as the undercoat layer component,
For example, carboxymethylcellulose, dextrin,
Phosphonic acids having an amino group such as gum arabic and 2-aminoethylphosphonic acid; phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid which may have a substituent Organic phosphonic acids such as acids; organic phosphoric acids such as phenylphosphoric acid, naphthyl phosphoric acid, alkyl phosphoric acid and glycerophosphoric acid optionally having substituents; phenylphosphinic acid, naphthylphosphinic acid optionally having substituents; Organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid; amino acids such as glycine and β-alanine; and hydrochlorides of amines having hydroxyl groups such as hydrochloride of triethanolamine.
You may mix and use more than one kind. It is also preferable to undercoat the aforementioned diazonium compound. The coating amount of the organic undercoat layer is suitably from 2 to 200 mg / m2, and preferably from 5 to 100 mg / m2. The above coating amount is 2m
If it is less than g / m 2, sufficient film properties cannot be obtained, and 200
The same is true even if it is larger than mg / m2.

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

[Preparation of Positive or Negative Image Forming Material and Lithographic Printing Plate Precursor] The positive or negative image forming material of the present invention is prepared by dissolving the components of each of the layers constituting the same in a solvent, as described above. It can be manufactured by sequentially applying on a support. As the solvent used herein, 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-butyllactone, toluene,
Water and the like can be mentioned, but it is not limited thereto. These solvents are used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is 1
Preferably, it is about 50% by weight. As a method of applying, various methods can be used, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating,
Roll coating and the like can be mentioned. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the image recording film deteriorate.

As described above, a lithographic printing original plate can be produced using the produced image recording material of the present invention. This lithographic printing plate precursor can be recorded with an infrared laser, and thermal recording with an ultraviolet lamp or a thermal head is also possible. In the present invention, the wavelength 760
It is preferable that the image is exposed by a solid-state laser or a semiconductor laser that emits infrared rays having a wavelength of from 1200 nm to 1200 nm.
In the present invention, the developing treatment may be performed immediately after the exposure, or a heat treatment may be performed between the exposure step and the developing step. When performing heat treatment, the conditions are 60 ° C to 150 ° C.
It is preferable to carry out within 5 seconds to 5 minutes. As a heating method, various conventionally known methods can be used. For example, a method of heating while contacting the recording material with a panel heater or a ceramic heater, and a non-contact heating method with a lamp or hot air are used. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced.

After performing a heat treatment as required, the lithographic printing plate precursor of the present invention is preferably developed with water or an alkaline aqueous solution.

When an alkaline aqueous solution is used, a conventionally known alkaline aqueous solution can be used as a developer and a replenisher for the lithographic printing plate precursor of the present invention. For example, sodium silicate, potassium potassium, tribasic sodium phosphate,
Same potassium, same ammonium, dibasic sodium phosphate,
Same potassium, same ammonium, sodium carbonate, same potassium, same ammonium, sodium hydrogen carbonate, same potassium, same ammonium, sodium borate, same potassium,
Same ammonium, sodium hydroxide, same ammonium,
And inorganic alkali salts such as the same potassium and the same lithium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used.

These alkaline agents are used alone or in combination of two or more. An example of a particularly preferable developer among these alkaline agents is an aqueous solution of a silicate such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and concentration of silicon oxide SiO2, which is a component of silicate, and alkali metal oxide M2O (M represents an alkali metal). The alkali metal silicates described in JP-A-54-62004 and JP-B-57-7427 are effectively used.

Further, when developing using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is added to the developing solution to replace the developing solution in the developing tank for a long time. It is known that a large number of lithographic printing plate precursors can be processed. This replenishment system is also preferably applied in the present invention.

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 developing residue and improving the ink affinity of the printing plate image area. . Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Preferred organic solvents include benzyl alcohol and the like. It is also preferable to add polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof.

Further, the developing solution and the replenisher may contain, if necessary, an inorganic salt-based reducing agent such as hydroquinone, resorcinol, sodium or potassium sulfite or bisulfite, an organic carboxylic acid, an antifoaming agent, hard water Softeners can also be added.

Examples of such a developer containing a surfactant, an organic solvent and a reducing agent include, for example, those described in
Benzyl alcohol described in No. 77401,
A developer composition comprising an anionic surfactant, an alkali agent and water, comprising an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite as described in JP-A-53-44202; Developer composition,
Examples thereof include a developer composition containing an organic solvent, an alkali agent, and water having a solubility in water of 10% by weight or less at room temperature described in JP-A-55-155355, which is also suitable for the present invention. Used for

The lithographic printing plate precursor developed using the developing solution and the replenisher described above is a washing solution, a rinsing solution containing a surfactant or the like, or a desensitizing solution containing gum arabic or a starch derivative. Post-processed. As the post-processing of the lithographic printing plate precursor of the present invention, these processings can be used in various combinations.

In recent years, especially in the plate making and printing industries, automatic developing machines for printing plate materials have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally includes a developing section and a post-processing section, and includes a device for transporting a printing plate material, each processing solution tank, and a spray device. The developing process is performed by spraying each pumped processing liquid from a spray nozzle. Recently, a method is also known in which a printing plate material is immersed and conveyed by a submerged guide roll or the like into a processing liquid tank filled with a processing liquid to perform processing. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like.

Further, a so-called disposable processing method in which processing is performed with a substantially unused processing solution can also be applied.

The lithographic printing plate precursor obtained as described above can be subjected to a printing step after applying a desensitized gum as required. Burning treatment may be performed for the purpose of further improving printing durability. When burning the lithographic printing plate precursor, before burning,
1-2518, 55-28062 and JP-A-62-2
It is preferable to treat with a surface-regulating liquid as described in JP-A-31859 and JP-A-61-159655.

[0137] As a method for this, a sponge or absorbent cotton impregnated with the surface-regulating liquid is applied on the lithographic printing plate precursor, or the printing plate is immersed in a vat filled with the surface-regulating liquid. A coating method, coating by an automatic coater, or the like is applied. Further, it is preferable to make the application amount uniform with a squeegee or a squeegee roller after the application. Generally, the application amount of the surface conditioning liquid is 0.03 to 0.1.
8 g / m2 (dry weight) is suitable.

The lithographic printing plate precursor to which the surface conditioning liquid has been applied is dried, if necessary, and then heated at a high temperature using a burning processor (for example, BP-1300, a burning processor sold by Fuji Photo Film Co., Ltd.). Heated. The heating temperature and time in this case depend on the type of the component forming the image, but are preferably in the range of 180 to 300 ° C. and 1 to 20 minutes.

The lithographic printing plate precursor that has been subjected to the burning treatment can be subjected to a conventional treatment such as washing with water or gumming, if necessary, but contains a water-soluble polymer compound and the like. When a surface conditioning liquid is used, a so-called desensitizing treatment such as gumming can be omitted.

The lithographic printing plate precursor obtained by such a process is applied to an offset printing machine or the like and used for printing a large number of sheets.

[0141]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In Examples 1 to 3 and Comparative Example 1, a positive image recording material and a lithographic printing plate precursor using the same were used. In Examples 4 to 6 and Comparative Example 2, a negative image recording material and a negative image recording material were used. The planographic printing plate precursor to be used is shown. Example 1 <Preparation of Support> An aluminum plate (material 1050) having a thickness of 0.3 mm was washed with trichlorethylene and degreased, and then its surface was grained using a nylon brush and a 400 mesh pumice-water suspension. Washed well with water. This aluminum plate was etched by immersing it in a 25% aqueous sodium hydroxide solution at 45 ° C. for 9 seconds, washed with water, and further immersed in 20% nitric acid for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, the aluminum plate was provided with a direct current anodic oxide film of 3 g / m ² at a current density of 15 A / dm ² using 7% sulfuric acid as an electrolytic solution, washed with water and dried, and further coated with the following undercoat solution A, The coating was dried at 90 ° C. for 1 minute. The coating amount of the dried coating film was 10 mg / m ² .

(Composition of undercoat liquid A) 0.50 g of β-alanine 95 g of methanol 5.0 g of water <Formation of heat-insulating layer> For 1 minute. The coating amount of the heat insulation layer is
After drying, the concentration was adjusted to 0.01 g / m ² . Phenol formaldehyde novolak (molecular weight 1500) 5.0 g Propylene glycol monomethyl ether 1000 g

<Formation of First Light-to-Heat Conversion Layer> Next, the following coating liquid for a light-to-heat conversion layer was applied for 1 minute using a rotary coating machine (Wheyer), and the coating was placed in an oven at 100 ° C. for 2 minutes. After drying for 1 minute, a first light-to-heat conversion layer was formed. The coating amount of the first light-to-heat conversion layer was 0.2 g / m ² after drying. Infrared absorbing cyanine dye represented by the following structural formula 0.3 parts by weight Polyvinyl alcohol (Poval, Type 205, manufactured by Kuraray Co., Ltd.) 6 parts by weight Isopropyl alcohol 5 parts by weight 20 parts by weight ion-exchanged water

[0144]

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<Coating of Positive-Type Photosensitive Layer> A coating solution for a photosensitive layer having the following composition was applied so that the coating amount was 1.8 g / m ² to form a photosensitive layer. (Coating solution for positive photosensitive layer) Binder (the following copolymer P) 1.0 g Infrared absorber (IR-1) 0.20 g Dye 0.02 g ・ Fluorine-based surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.) 0.05 g ・ γ-butyrolactone 3.0 g ・ Methyl ethyl ketone 8.0 g ・ 1-methoxy- 2-propanol 7.0 g

[0146]

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(Synthesis of Copolymer P) 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and 500 ml of a three-necked flask equipped with a stirrer, a condenser and a dropping funnel were charged. Acetonitrile 200
ml and the mixture was stirred while cooling in an ice-water bath.
To this mixture, 36.4 g (0.36 mol) of triethylamine was dropped by a dropping funnel over about 1 hour. After completion of the dropwise addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes.

To the reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in a hot water bath. After completion of the reaction, the obtained mixture was added to 1 L of water while stirring the water, and the obtained mixture was stirred for 30 minutes. The mixture was filtered to remove the precipitate, and 500 m of water was added to the precipitate.
After adding slurry to obtain a slurry, the slurry is filtered,
By drying the obtained solid, a white solid of N- (p-aminosulfonylphenyl) methacrylamide was obtained (yield 46.9 g).

Next, 5.04 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 100 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
0210 mol), 2.05 g of ethyl methacrylate (0.
0180 mol), 1.11 g of acrylonitrile (0.0
21 mol) and 20 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a water bath. 2,2 ′ as a radical polymerization initiator was added to this mixture.
0.15 g of -azobis (2,4-dimethylvaleronitrile) (trade name: "V-65", manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65 ° C. To this reaction mixture, 5.04 g of N- (p-aminosulfonylphenyl) methacrylamide, 2.05 g of ethyl methacrylate, 1.11 g of acrylonitrile,
20 g of N, N-dimethylacetamide and the above “V-6”
5 ", and a mixture of 0.15 g was dropped by a dropping funnel over 2 hours. After the completion of the dropwise addition, the obtained mixture was further cooled to 65%.
Stirred at C for 2 hours. After the completion of the reaction, 40 g of methanol was added to the mixture, and the mixture was cooled. The obtained mixture was poured into 2 L of water while stirring the mixture, and the mixture was stirred for 30 minutes. 15 g of a solid copolymer P was obtained. When the weight average molecular weight (polystyrene standard) of the copolymer P was measured by gel permeation chromatography, it was 5.3 × 10 5
^{Was 4} .

<Coating of Second Light-to-Heat Conversion Layer> The same coating solution as that for the first light-to-heat conversion layer was applied and dried under the same conditions.

Example 2 A lithographic printing plate precursor was prepared in the same manner as in Example 1, except that the coating solution for the positive photosensitive layer was changed to the one having the following composition. <Coating of Coating Solution for Positive Type Photosensitive Layer> Binder (m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 3500, unreacted cresol 0.5% by weight)) 1.0 g・ Infrared absorber (IR-2) 0.20 g ・ Copolymer P synthesized by the above method 1.0 g ・ Dye in which the counter anion of Victoria Pure Blue BOH is changed to 1-naphthalenesulfonic acid anion 0.02 g ・ Fluorine type Surfactant (Megafac F-177, manufactured by Dainippon Ink & Chemicals, Inc.) 0.05 g • γ-butyrolactone 3.0 g • Methyl ethyl ketone 8.0 g • 1-methoxy-2-propanol 7.0 g

[0152]

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The above photosensitive solution was applied so that the coating amount was 1.8 g / m ² .

Example 3 A lithographic printing plate precursor was prepared in the same manner as in Example 1 except that the composition for the heat insulating layer was changed to the following composition. (Coating solution for heat insulating layer)-Poly (p-hydroxystyrene) (molecular weight 8,000) 5.0 g-Propylene glycol monomethyl ether 1000 g

Comparative Example 1 On the undercoat layer of the support of Example 1, the coating liquid for a positive photosensitive layer of Example 1 was applied and dried so that the coating weight after drying was 1.8 g / m ^2. Thus, a lithographic printing plate precursor was prepared.

<Evaluation of Sensitivity> As shown in Table 1 below, the lithographic printing plate precursors of Examples 1 to 3 and Comparative Example 1 were converted into a semiconductor laser having a wavelength of 840 nm or a wavelength of 10 mm.
Exposure was performed using a 64 nm YAG laser. Which laser is used was appropriately selected as shown in Table 1 below according to the absorption wavelength of the infrared absorbing dye contained therein.
After the exposure, an automatic developing machine (“P”) was charged with a developing solution DP-4 and a rinsing solution FR-3 (1: 7) manufactured by Fuji Photo Film Co., Ltd.
S processor 900VR ", Fuji Photo Film Co., Ltd.
Developed using the following method. Two levels of developer DP-4 were prepared, one diluted 1: 6 and one diluted 1:12.

The line width of the non-image area obtained with the developing solution diluted 1: 6 of DP-4 was measured, the irradiation energy of the laser corresponding to the line width was determined, and the sensitivity index (mJ) was obtained.
/ Cm ² ). The smaller the measured value (mJ / cm ² ), the higher the sensitivity of the lithographic printing plate precursor. As shown in Table 1, it can be seen that all of Examples 1 to 3 have small measured values and excellent sensitivity. On the other hand, Comparative Example 1 in which the photosensitive layer was directly provided without providing the heat insulating layer on the support was inferior in sensitivity.

[0158]

[Table 1]

Example 4 <Preparation of Support> A support having an undercoat layer was prepared in the same manner as in Example 1. <Formation of Heat Insulation Layer> The following heat insulation layer solution was applied on the support and dried at 100 ° C. for 1 minute. The coating amount of the heat insulation layer is
After drying, the concentration was adjusted to 0.01 g / m ² . Phenol formaldehyde novolak (molecular weight 1500) 5.0 g Propylene glycol monomethyl ether 1000 g <Formation of first light-to-heat conversion layer> Next, the following coating solution for the light-to-heat conversion layer is applied for 1 minute using a rotary coating machine (Woeller). And drying the coating in an oven at 100 ° C. for 2 minutes,
A first light-to-heat conversion layer was formed. The coating amount of the first light-to-heat conversion layer was 0.2 g / m ² after drying. Infrared absorbing cyanine dye represented by the following structural formula 0.3 parts by weight Polyvinyl alcohol (Poval, Type 205, manufactured by Kuraray Co., Ltd.) 6 parts by weight Isopropyl alcohol 5 parts by weight 20 parts by weight ion-exchanged water

[0160]

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<Formation of Negative-Type Photosensitive Layer> A coating solution for a negative-type photosensitive layer shown below was coated on the above-mentioned photothermal conversion layer and then heated to 100 ° C.
For 1 minute. The coating weight after drying is 1.3 g / m ²
Met. (Coating solution for negative photosensitive layer) Acid generator X-2 (the following structural formula) 0.15 g Infrared absorption represented by the following formula (B-1) 0.10 g Marka Linker MS-4P (manufactured by Maruzen Petrochemical) 1.5 g (weight average molecular weight 10,000) Crosslinking agent KZ-9 (the following structural formula) 0.25 g Crosslinking agent MM-1 (Structural formula below) 0.25 g Fluorosurfactant 0.03 g (MegaFac F-177, manufactured by Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone ··········· 15 g 1-methoxy-2-propanol ········· 10 g methyl alcohol ······················· 5g

[0162]

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[0163]

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[0164]

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<Formation of Second Light-to-Heat Conversion Layer> A lithographic printing plate precursor was prepared under the same conditions as for the first light-to-heat conversion layer.

Example 5 A lithographic printing plate precursor was prepared in the same manner as in Example 4 except that the infrared absorbing agent used in the coating solution for the negative photosensitive layer was changed to the following compound (B-2).

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Example 6 A lithographic printing plate precursor was prepared in the same manner as in Example 4 except that the coating solution for the heat insulating layer was changed to the following. (Coating solution for heat insulating layer)-Poly (p-hydroxystyrene) (molecular weight 8,000) 5.0 g-Propylene glycol monomethyl ether 1000 g

Comparative Example 2 The coating weight after drying the coating solution for a negative photosensitive layer of Example 4 on the undercoat layer of the support used in Example 4 was 1.3.
g / m ² and dried to prepare a lithographic printing plate precursor.

<Evaluation of Sensitivity> The negative type lithographic printing original plates of Examples 4 to 6 and Comparative Example 2 were treated with a wavelength of 840.
Scanning exposure was performed using a semiconductor laser emitting infrared light of about nm. After the exposure, a heat treatment was performed at 110 ° C. for 15 seconds using a panel heater, and then a developer manufactured by Fuji Photo Film Co., Ltd.
Developed with P-4 (1: 8 water dilution). At this time, the amount of energy required for recording was calculated based on the line width and laser output of the obtained image, the loss in the optical system, and the scanning speed, and used as an index indicating sensitivity. As shown in Table 2, it can be seen that all of Examples 4 to 6 have small measured values and excellent sensitivity. On the other hand, in Comparative Example 2 in which the photosensitive layer was directly provided without providing the heat insulating layer on the support, the sensitivity was poor.

[0171]

[Table 2]

[0172]

According to the image recording material of the present invention, a heat insulating layer is provided on a support to suppress heat diffusion to the support, and a photothermal conversion layer is provided on both sides of a positive photosensitive layer or a negative photosensitive layer. Is provided so that heat is applied from above and below the photosensitive layer, so that heat can be efficiently used in the photosensitive layer, and high-sensitivity image recording can be performed. Further, the image forming material of the present invention is suitable for forming an image with heat or light, particularly an infrared laser based on a digital signal. Further, a lithographic printing plate precursor using this image recording material is suitable for direct plate making using an infrared laser, and a lithographic printing plate precursor with high sensitivity can be obtained.

Continued on front page F term (reference) 2H025 AA01 AB03 AC08 AD01 AD03 BE00 BE07 CB17 CB29 CB45 CB52 CC11 DA40 FA10 FA17 2H114 AA06 AA15 BA01 BA05 DA23 DA34 FA15 GA05

Claims (1)

[Claims] 1. An image recording material comprising the following layers (a) to (d) provided in this order on a support. (A) a heat insulating layer, (b) a first light-to-heat conversion layer, (c) a layer containing a polymer compound that is insoluble in water and soluble in alkaline water, and whose solubility in alkaline water changes by the action of heat. ,
(D) a second light-to-heat conversion layer.