JPH1016423A - Negative image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative image recording material which makes it possible to make a plate directly from digital data and gives a recorded image having good film strength and printability. SOLUTION: A recording material is composed of (A) at least one kind of polymer having hydroxyaryl groups on the side chain, (B) a heat curing agent such as a phenol derivative preferably having a hydroxymethyl group or an alkoxymethyl group linked to two or more benzene rings in a molecule, (C) an oxygen generating agent which is decomposed by heating at 100 deg.C or above to generate oxygen, and (D) an infrared absorbing agent of dye or pigment which absorbs infrared rays of 720-1200nm wavelength. Preferable hydroxyaryl groups of side chain of the polymer (A) include hydroxyphenyl, dihydroxyphenyl, trihydroxyphenyl, tetrahydroxyphenyl, hydroxynaphthyl, and dihydroxynaphthyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material which can be used as a lithographic printing plate material, and more particularly to a so-called direct plate making negative type image recording which can directly make a plate using an infrared laser from a digital signal of a computer or the like. About the material.

[0002]

2. Description of the Related Art Conventionally, a system for making a plate directly from digital data of a computer includes (1) an electrophotographic method, (2) a photopolymerization system for exposing using a laser emitting blue or green light, (3) ) A silver salt is laminated on a photosensitive resin, and (4) a salt diffusion transfer method is proposed. However, in the case of (1) the method using electrophotography, the process of image formation such as charging, exposure, development and the like is complicated, and the apparatus is complicated and large. In the case of the photopolymerization system (2), since the printing plate is highly sensitive to blue and green light, it is difficult to handle it in a bright room. (3),
The method (4) uses silver salts, which makes processing such as development complicated, and of course has the disadvantage that silver is contained in the processing waste liquid.

On the other hand, the development of lasers in recent years has been remarkable, and in particular, solid-state lasers and semiconductor lasers that emit infrared light having a wavelength of 760 nm to 1200 nm can be easily obtained with high output and small size. These lasers are very useful as a recording light source when making a plate directly from digital data of a computer or the like. But,
Many photosensitive recording materials that are practically useful have a photosensitive wavelength of 76.
Since it is a visible light region of 0 nm or less, an image cannot be recorded with these infrared lasers. Therefore, a material that can be recorded by an infrared laser is desired.

[0004] As such an image recording material recordable by an infrared laser, there is a recording material comprising an onium salt, a resole resin, a novolak resin, and an infrared absorber described in JP-A-7-20629. . Also,
JP-A-7-271029 describes a recording material comprising a haloalkyl-substituted s-triazine, a resole resin, a novolak resin, and an infrared absorber. However, in a plate material using these image recording materials,
The film strength of the image portion was insufficient, and as a result, the printing durability during printing was insufficient.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to make a plate directly from digital data of a computer or the like by recording using a solid-state laser or a semiconductor laser emitting infrared rays. An object of the present invention is to provide a negative type image recording material which is excellent as a planographic printing plate material having excellent image film strength and good printing durability during printing.

[0006]

Means for Solving the Problems The present inventor pays attention to the constituent components of a negative-type image recording material, and as a result of diligent studies, the negative-type image recording material comprises the following (A) to (D). It has been found that the above objects can be achieved by using materials, and the present invention has been completed. (A) at least one polymer having a hydroxyaryl group in the side chain, (B) a thermal crosslinking agent, (C) an acid generator, and (D) an infrared absorber.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component of the present invention will be described in detail. [(A) Polymer Having Hydroxyaryl Group in Side Chain] In the present invention, the hydroxyaryl group is -OH
An aryl group in which one or more groups are bonded. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group.
From the viewpoints of availability and physical properties, a phenyl group or a naphthyl group is preferred. 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 are
Further, it may have a substituent such as a halogen atom, 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 attached to the polymer main chain as side chains of the polymer,
It may have a linking group between itself and 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 (I) to (IV). .

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ may be the same or different, and represent a hydrogen atom,
It represents a halogen atom, a hydrocarbon group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, or an aryloxy group having 10 or less carbon atoms. Also, R ² and R ³ combine to
A condensed benzene ring or cyclohexane ring may be formed. R ⁴ is a single bond or 2 of 20 carbon atoms or less.
Represents a monovalent hydrocarbon group. R ⁵ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms. R ⁶ represents a single bond or a divalent hydrocarbon group having 10 or less carbon atoms.
X1 represents a single bond, an ether bond, a thioether bond, an ester bond or an amide bond. p shows the integer of 1-4. q and r each represent an integer of 0 to 3. )

[0009] Among the structural units represented by the general formulas (I) to (IV), examples of specific structural units suitably used in the present invention are shown below.

[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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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 (I) 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 the general formula (II) 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 (III) 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. . The polymer having the structural unit represented by the general formula (IV) is derived from a styrene having a functional group useful for synthesis, such as chloromethylstyrene or carboxystyrene, as a raw material to a monomer corresponding to the general formula (IV). Then, the polymer is obtained by radical polymerization.

The polymer used in the present invention may be a homopolymer consisting of only the structural units represented by the general formulas (I) to (IV), but may be a copolymer containing other structural units. There may be. 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 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,
Sulfamoyl phenyl acrylate.

Specific examples of 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, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, and dimethoxystyrene. , Chlorostyrene, dichlorostyrene, bromostyrene, iodostyrene, fluorostyrene, carboxystyrene and the like.

Among 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 ratio of the constitutional units represented by the general formulas (I) to (IV) contained in the copolymer using these is from 5 to 1
00% by weight, more preferably 1% by weight.
0 to 100% by weight. Further, the molecular weight of the polymer used in the present invention is preferably 4000 in terms of weight average molecular weight.
And more preferably in the range of 10,000 to 300,000, preferably in the number average molecular weight of 1,000 or more, and more preferably 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 polymers used in the present invention may be used alone or as a mixture. These polymers are used in an amount of 20 to 95% by weight, preferably 4% by weight, based on the total solid content of the image recording material.
It is added to the image recording material at a ratio of 0 to 90% by weight.
When the addition amount is less than 20% by weight, the strength of the image portion is insufficient when an image is formed. When the amount exceeds 95% by weight, no image is formed.

[(B) Thermal Crosslinking Agent] The thermal crosslinking agent suitably used in the present invention includes a hydroxymethyl group, an alkoxymethyl group linked to two or more benzene rings in the molecule,
It is a compound having an epoxy group or a vinyl ether group. Specifically, methylol melamine, resole resin,
Epoxidized novolak resins, urea resins, and the like are included. Further, compounds described in "Crosslinking Agent Handbook" (written by Shinzo Yamashita and Tosuke Kaneko, Taiseisha Co., Ltd.) are also preferable. In particular, a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule is preferable because the strength of an image portion when an image is formed is good. Specifically, a resole resin can be used.

However, these thermal crosslinking agents are naturally unstable to heat, and the storage stability of the image recording material after storage is not very good. In contrast,
A phenol derivative having a hydroxymethyl group or an alkoxymethyl group linked to two or more benzene rings in the molecule, containing 3 to 5 benzene nuclei, and having a molecular weight of 1,200 or less is stable when stored. The property is also good,
It is most preferably used in the present invention. As the alkoxymethyl group, those having 6 or less carbon atoms are preferable. Specifically, methoxymethyl, ethoxymethyl, n-propoxymethyl, i-propoxymethyl, n-butoxymethyl, i-butoxymethyl, sec-butoxymethyl and t-butoxymethyl are preferred. further,
Alkoxy-substituted alkoxy groups such as 2-methoxyethoxy group and 2-methoxy-1-propyl group are also preferable.

Among these phenol derivatives, particularly preferred ones are described below.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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(In the formula, L ^{1 to} L ⁸ may be the same or different and represent a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.)

The phenol derivative having a hydroxymethyl group is prepared by reacting a corresponding phenol compound having no hydroxymethyl group (compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. Obtainable. At this time, the reaction is preferably performed at a reaction temperature of 60 ° C. or lower in order to prevent resinification and gelation. Specifically, it can be synthesized by the methods described in JP-A-6-282067 and JP-A-7-64285. The phenol derivative having an alkoxymethyl group can be obtained by reacting the corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, the reaction is preferably performed at a reaction temperature of 100 ° C. or less in order to prevent resinification and gelation. Specifically, it can be synthesized by a method described in European Patent EP632003A1 or the like.

In the present invention, the thermal crosslinking agent is used in an amount of 5 to 70% by weight, preferably 10 to 65% by weight, based on the total solid content of the image recording material. If the added amount of the thermal crosslinking agent is less than 5% by weight, the film strength of the image area at the time of image recording deteriorates, and if it exceeds 70% by weight, it is not preferable from the viewpoint of storage stability. These phenol derivatives may be used alone or in combination of two or more.

[(C) Acid Generator] In the present invention, the acid generator is a compound which is decomposed by heating at 100 ° C. or more to generate an acid. The generated acid is preferably a strong acid having a pKa of 2 or less, such as sulfonic acid and hydrochloric acid. Examples of the acid generator suitably used in the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts. Specific examples include compounds described in JP-A-7-20629. Particularly, an iodonium salt, a sulfonium salt, and a diazonium salt having a sulfonate ion as a counter ion are preferable. Also preferred are haloalkyl-substituted s-triazines described in JP-A-7-271029.

The acid generator particularly preferably used in the present invention is a compound represented by the following formulas (V) to (IX).

[0038]

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(In the formula, R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ may be the same or different and represent a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Reference numeral ¹³ represents a halogen atom, a hydrocarbon group having 10 or less carbon atoms which may have a substituent, or an alkoxy group having 10 or less carbon atoms.
Ar ¹ and Ar ² may be the same or different, and represent an aryl group having 20 or less carbon atoms which may have a substituent. R ¹⁶ represents a divalent hydrocarbon group having 25 or less carbon atoms which may have a substituent. n shows the integer of 0-4. )

Among the compounds represented by formulas (V) to (IX), particularly preferred compounds are shown below. These compounds are described in, for example, JP-A Nos. 2-100054 and 2
The compound can be synthesized by the method described in No. -100055.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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Also, the applicant of the present invention filed in Japanese Patent Application No.
Polymeric acid generators described in No. 9444 are also preferred.

These compounds are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 25% by weight based on the total solid content of the image recording material.
%, More preferably 0.5 to 15% by weight. If the amount is less than 0.01% by weight, no image can be obtained. On the other hand, if the amount exceeds 50% by weight, non-image areas are stained during printing.
These compounds may be used alone or in combination of two or more.

[(D) Infrared absorber] The infrared absorber used in the present invention has a wavelength of 760 nm to 1200.
It is a dye or pigment that effectively absorbs infrared rays of nm.
Preferably, it is a dye or a pigment having an absorption maximum at a wavelength of 760 nm to 1200 nm. As the dye, commercially available dyes and known dyes described in literatures (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, azo dye, metal complex salt azo dye, pyrazolone azo dye, naphthoquinone dye, anthraquinone dye, phthalocyanine dye, carbonium dye,
Dyes such as quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes are exemplified. Preferred dyes include, for example, JP-A-58-125246, JP-A-59-84356,
JP-A-59-202829, JP-A-60-78787
Cyanine dyes described in JP-A-58-17
No. 3696, JP-A-58-181690, JP-A-58-181690
Methine dyes described in JP-A-194595, JP-A-58-112793, JP-A-58-224793.
JP-A-59-48187, JP-A-59-7399
No. 6, JP-A-60-52940, JP-A-60-637
No. 44, etc .;
Examples thereof include squarylium dyes described in JP-A-8-112792 and cyanine dyes described in British Patent No. 434,875.

Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is preferably used, and a substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also preferable. Pyrylium salt, JP-A-57-142645
No. (U.S. Pat. No. 4,327,169) described in JP-A-58-181051, JP-A-58-220143, JP-A-59-41363, and JP-A-59-41363.
Nos. -84248, 59-84249, 59-14
Pyrylium compounds described in JP-A Nos. 6063 and 59-146061, cyanine dyes described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fairness 5-13
Pyrylium compounds disclosed in JP-A-514 and JP-A-5-19702 are also preferably used. Another preferred example of the dye is U.S. Pat. No. 4,756,993.
Near-infrared absorbing dyes described in the specification as formulas (I) and (II) can be mentioned. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.

The pigment used in the present invention includes:
Commercial Pigment and Color Index (CI) Handbook, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, 1977)
Annual Publication), “Latest Pigment Application Technology” (CMC Publishing, 1986)
Pigments described in "Printing Ink Technology", CMC Publishing, 1984). Examples of the type of the pigment include a black pigment, a yellow pigment, an orange pigment, a brown pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a fluorescent pigment, a metal powder pigment, and a polymer-bound pigment. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Preferred among these pigments is carbon black.

These pigments may be used without being subjected to a surface treatment, or may be used after being subjected to a surface treatment. Examples of the surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. No. The above surface treatment methods are described in “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). I have.

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm.
Is preferably within the range. Pigment particle size 0.01μ
When it is less than m, the dispersion is not preferred in terms of stability in the coating solution for the photosensitive layer, and when it exceeds 10 μm, it is not preferred in terms of uniformity of the image recording layer. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. As the disperser, an ultrasonic disperser,
Sand mills, attritors, pearl mills, super mills, ball mills, impellers, dispersers, KD mills, colloid mills, dynatrons, three-roll mills, pressure kneaders and the like can be mentioned. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

These dyes or pigments are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight, based on the total solid content of the image recording material.
10 to 10% by weight, particularly preferably 1.0 to 10
It can be added to the image recording material in a proportion of% by weight. If the amount of the pigment or the dye is less than 0.01% by weight, the sensitivity is lowered, and if it exceeds 50% by weight, the non-image area is stained during printing. These dyes or pigments may be added to the same layer as other components, or a separate layer may be provided and added thereto.

[Other Components] In the present invention, (A)
Although the four components (D) to (D) are essential, 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 # 10
1, oil yellow # 103, oil pink # 312,
Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black B
S, 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 (CI
42000), methylene blue (CI52015), and the dyes described in JP-A-62-293247. These dyes are
After image formation, it is preferable to add it because the distinction between the image area and the non-image area becomes clear. The addition amount is preferably 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, monoglyceride stearic acid, and polyoxyethylene nonyl phenyl ether. 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 surfactant (for example, trade name Amogen K, Daiichi Kogyo Co., Ltd.
Manufactured). The proportion of the nonionic surfactant and amphoteric surfactant in the image recording material is 0.0%
It is preferably from 5 to 15% by weight, more preferably from 0.1 to 5% by weight.
% 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, and the like are used.

The image recording material of the present invention can be usually produced by dissolving each of the above-mentioned components in a solvent and coating the solution on a suitable 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 preferably 1 to 50% by weight. The amount of coating (solid content) on the support obtained after coating and drying varies depending on the application, but generally 0.5 to 5.0 g / m ² is preferred for a lithographic printing plate material. 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.

In the image recording layer of the present invention, a surfactant for improving coating properties, for example, JP-A-62-17
A fluorine-based surfactant as described in JP-A-0950 can be added. The preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total solid content of the image recording material.

The support used in the present invention is a dimensionally stable plate-like material, such as paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, metal plate ( For example, aluminum, zinc, copper, etc.), plastic film (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate,
Cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic film on which a metal such as the metal plate is laminated or vapor-deposited. As the support of the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate having good dimensional stability and relatively low cost is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Aluminum which is particularly preferred 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 in the present invention is approximately 0.1 mm to 0.6 mm, preferably 0.15 m.
m to 0.4 mm, particularly preferably 0.2 mm to 0.3 m
m. When this aluminum plate is used as a support, the surface of the aluminum plate can be roughened from the viewpoint of adhesion to the recording layer formed thereon.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution is performed to remove the rolling oil on the surface. The surface roughening treatment of the aluminum plate
The method is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface.
As a mechanical method, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, a method combining both of them can be used as disclosed in JP-A-54-63902. The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as necessary,
If desired, anodizing treatment is performed to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes for forming 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.

Anodizing treatment conditions vary depending on the electrolyte to be used, and thus cannot be specified unconditionally. However, in general, the concentration of the electrolyte is 1 to 80% by weight, the solution temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , a voltage of 1 to 100 V, and an electrolysis time of 10 seconds to 5 minutes are appropriate. When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image portion of the lithographic printing plate is easily scratched,
So-called "scratch stains" in which ink adheres to scratches during printing are likely to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. U.S. Pat. Nos. 2,7,7
No. 14,066, No. 3,181,461, No. 3,2
There is an alkali metal silicate (e.g., sodium silicate aqueous solution) method as disclosed in U.S. Pat. Nos. 80,734 and 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Patent Nos. 3,276,868 and 4,153,461.
And the method of treating with polyvinyl phosphonic acid as disclosed in JP-A No. 4,689,272.

In the image recording material of the present invention, an undercoat layer can be provided on a support, if necessary. Various organic compounds are used as the undercoat layer component. For example, carboxymethyl cellulose, dextrin, gum arabic,
Phosphonic acids having an amino group such as aminoethylphosphonic acid, and organic phosphones such as optionally substituted phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid Acids, organic phosphoric acids such as phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid, and glycerophosphoric acid, which may have a substituent, phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid, and glycerol which may have a substituent It is selected from organic phosphinic acids such as phosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxy group such as hydrochloride of triethanolamine. Good. The coating amount of the organic undercoat layer is 2
To 200 mg / m ² are suitable.

As described above, a lithographic printing plate using the image recording material of the present invention can be prepared. This lithographic printing plate material is image-exposed by a solid-state laser and a semiconductor laser that emit infrared rays having a wavelength of 760 nm to 1200 nm. In the present invention, the developing treatment may be performed immediately after the laser irradiation, but it is preferable to perform the heating treatment between the laser irradiation step and the developing step. The heat treatment is preferably performed in a range of 80 ° C. to 150 ° C. for 10 seconds to 5 minutes. 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 image recording material of the present invention is developed with an alkaline aqueous solution. As the developer and replenisher for the image recording material of the present invention, conventionally known aqueous solutions of alkaline agents can be used. Examples of the alkaline agents contained therein include sodium silicate, potassium silicate, sodium phosphate tribasic, potassium phosphate tribasic, ammonium phosphate tribasic, sodium phosphate dibasic, potassium phosphate dibasic, Ammonium diphosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate,
And inorganic alkali salts such as ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide. Also, monomethylamine,
Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, Organic alkali agents such as pyridine are also used. These alkali agents are used alone or in combination of two or more. Particularly preferred developers among these alkaline agents are sodium silicate,
It is an aqueous solution of a silicate such as potassium silicate. The reason is that the developability can be adjusted by the ratio and the concentration of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O which are the components of the silicate. For example, JP-A-54-62004 discloses An alkali metal silicate described in JP-B-57-7427 is effectively used.

In the case of developing using an automatic developing machine, an aqueous solution having a higher alkali strength than the developing solution (replenisher)
It has been known that a large amount of lithographic printing plate material can be processed without replacing the developing solution in the developing tank for a long time by adding to the developing solution. 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 as required for the purpose of accelerating 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. Further, if necessary, the developer and replenisher may be hydroquinone, resorcin, sulfurous acid,
A reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as bisulfite, an organic carboxylic acid, an antifoaming agent, and a water softener can also be added. The printing plate developed using the above developer and replenisher is post-treated with washing water, a rinsing solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As the post-processing when the image recording material of the present invention is used as a printing plate material, these processings can be used in various combinations.

In recent years, in the plate making / printing industry, 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 consists of a developing section and a post-processing section, and consists of a device for transporting printing plate material, each processing solution tank and a spray device, and pumps the exposed printing plate horizontally while pumping it. Each processing liquid is sprayed from a spray nozzle to perform development processing.
Recently, a method has been known in which a printing plate material is immersed and transported by a submerged guide roll or the like in a processing liquid tank filled with a processing liquid, and the processing is performed. In such an automatic processing, the processing can be performed while replenishing each processing liquid with a replenisher according to the processing amount, the operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitized gum as required, but when a lithographic printing plate having even higher printing durability is desired. Is subjected to a burning process.
When the lithographic printing plate is to be burned, before burning, the lithographic printing plate is prepared as described in JP-B-61-2518, JP-B-55-28062, JP-A-62-31859 and JP-A-61-159655. It is preferable to treat with a surface liquid. As a method, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied on a lithographic printing plate, or a method in which the printing plate is immersed in a vat filled with the surface conditioning solution and applied, Application by an automatic coater or the like is applied. Also,
Making the amount of the coating uniform with a squeegee or a squeegee roller after the coating gives more preferable results. Generally, the application amount of the surface conditioning liquid is 0.03 to 0.8.
g / m ² (dry weight) is appropriate.

The lithographic printing plate to which the surface conditioning liquid has been applied is dried if necessary, and then heated to a high temperature using a burning processor (for example, a burning processor: BP-1300 sold by Fuji Photo Film Co., Ltd.). Is done. The heating temperature and time in this case depend on the type of the component forming the image, but may be 1 to 180 ° C. to 300 ° C.
A range of up to 20 minutes is preferred. The burned lithographic printing plate can be subjected to conventional treatments such as washing with water and gumming as needed, but a surface conditioning solution containing a water-soluble polymer compound or the like is used. In such a case, a so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0075]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. [(A) a polymer having a hydroxyaryl group in the side chain (hereinafter referred to as the polymer of the present invention) [BP-1],
[Synthesis of BP-2] p-acetoxystyrene 16.2
g (0.10 mol), m-acetoxystyrene 16.2
g (0.10 mol) in 120 ml of butyl acetate,
Under a nitrogen stream and stirring, a polymerization reaction was carried out by adding 0.033 g of azobisisobutyronitrile (AIBN) three times every two hours at 80 ° C., and finally continuing stirring for another two hours. The reaction solution was poured into 600 ml of hexane,
A white polymer precipitated. After drying the obtained polymer, it was dissolved in 150 ml of methanol. An aqueous solution of 9.6 g (0.24 mol) of sodium hydroxide / 50 ml of water was added thereto, and the mixture was heated under reflux for 3 hours to hydrolyze. Thereafter, 200 ml of water was added to dilute the mixture, and the mixture was neutralized with hydrochloric acid to precipitate a white polymer.
The precipitated polymer was separated by filtration, washed with water and dried to obtain 22 g of a polymer. By NMR measurement, it was confirmed that the composition of this polymer was poly (hydroxystyrene) having a p / m molar ratio of about 50/50, and that the weight average molecular weight was 28,000 by GPC measurement (the polymer of the present invention [ BP-1]). Further, similarly, the following Table 1
Was synthesized according to the present invention [BP-2].

[Synthesis of Polymer [BP-3] of the Present Invention]
By reacting chloromethylstyrene (a mixture of m- and p-forms) with 2,4-dihydroxybenzoic acid under basic conditions, (2,4-dihydroxyphenyl) carbonyloxymethylstyrene is obtained. The polymer [BP-3] of the present invention shown in Table 1 below was synthesized by radical polymerization with butyl acrylate.

[Polymer of the present invention [BP-4], [BP
Synthesis of -5]] Polyvinyl alcohol, p-hydroxybenzaldehyde and benzaldehyde were used as starting materials, and an acetalization reaction was carried out under acidic conditions in the same manner as in Synthesis Example 3 of JP-A-64-35436. The polymer [BP-4] of the present invention was synthesized. Furthermore, similarly, the polymer [BP-5] of the present invention shown in Table 2 below
Was synthesized.

[Polymers of the Invention [BP-6] to [BP
-7] with p-aminophenol and maleic anhydride as starting materials and N- (p-hydroxyphenyl)
A maleimide was synthesized and then subjected to a polymerization reaction with reference to US Pat. No. 5,079,129, and the polymer [B
P-6] was synthesized. In a similar manner, the polymer [BP-7] of the present invention shown in Table 2 below was synthesized.

[0079]

[Table 1]

[0080]

[Table 2]

[Synthesis of (B) Thermal Crosslinking Agent [HM-1] of the Present Invention] 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4- Hydroxyphenyl) ethyl] benzene 20g (Honshu Chemical Industry Co., Ltd.)
Trisp-PA) was added to a 10% aqueous potassium hydroxide solution, and the mixture was stirred and dissolved. Then, while stirring this solution,
60 ml of a 37% formalin aqueous solution was gradually added at room temperature over 1 hour. After further stirring at room temperature for 6 hours, the mixture was poured into a dilute sulfuric acid aqueous solution. The precipitate was filtered, washed sufficiently with water, and recrystallized from 30 ml of methanol to obtain 20 g of a white powder of a phenol derivative having a hydroxymethyl group [HM-1] having the following structure. The purity was 92% (liquid chromatography method).

[0082]

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[Synthesis of (B) Thermal Crosslinking Agent [MM-1] of the Present Invention] 20 g of the phenol derivative having a hydroxymethyl group [HM-1] obtained in the above synthesis example was added to 1 liter of methanol and heated. Stir and dissolve. Next, 1 ml of concentrated sulfuric acid was added to this solution, and the mixture was heated under reflux for 12 hours. After the completion of the reaction, the reaction solution was cooled, and 2 g of potassium carbonate was added. After sufficiently concentrating this mixture, ethyl acetate 300 m
1 was added. This solution was washed with water and concentrated to dryness to obtain 22 g of a white solid of a phenol derivative having a methoxymethyl group [MM-1] having the following structure. The purity was 90% (liquid chromatography method).

[0084]

Embedded image

Further, the following phenol derivatives were synthesized in the same manner.

[0086]

Embedded image

[0087]

Embedded image

[0088]

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[Examples 1 to 12] An aluminum plate (material 1050) having a thickness of 0.30 mm was washed with trichloroethylene and degreased, and then its surface was grained with a nylon brush and a 400 mesh pumicestone-water suspension. And washed well with water. This plate was immersed in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds to perform etching and washing with water.
It was further immersed in 2% HNO ₃ 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 plate was provided with a 3 g / m ² DC anodic oxide film at a current density of 15 A / dm ² using 7% H ₂ SO ₄ as an electrolytic solution, and then washed and dried. Next, the following undercoat liquid was applied to this aluminum plate, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 10 mg / m ² . (Undercoat liquid) β-alanine 0.1 g Phenylphosphonic acid 0.05 g Methanol 40 g Pure water 60 g

Next, in the following solution [P], by changing the type of the composition of the present invention, ten types of solutions [P-1] to
[P-12] was adjusted. Each of the solutions was applied to the above-mentioned primed aluminum plate, dried at 100 ° C. for 1 minute, and used for negative-type lithographic printing plates [P-1] to [P-1].
2] was obtained. The weight after drying was 1.7 g / m ² .

Solution [P] Polymer of the present invention 1.5 g Thermal cross-linking agent 0.7 g Acid generator 0.2 g Infrared absorber NK-3508 (trade name) 0.15 g (manufactured by Nippon Photographic Dye Laboratories) 1-naphthalene-0.05 g of counter ion of Victoria Pure Blue BOH Sulfonic acid dye Fluorosurfactant Megafac F-177 (trade name) 0.06 g (manufactured by Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone 15 g 1-Methoxy-2-propanol 5 g Methyl alcohol 7 g The compounds used in the solutions [P-1] to [P-12] are shown in Table 3 below.

[0092]

[Table 3]

(In the table, the resole resin is obtained by reacting bisphenol A with formaldehyde under alkaline conditions (weight average molecular weight: 1600).)

The obtained negative type lithographic printing plate material [P-1]
To [P-12] were exposed with a solid-state laser YAG laser emitting infrared light having a wavelength of 1064 nm. After exposure, 130
After heating at ℃ for 30 seconds, Fuji Photo Film Co., Ltd.
Developer, DP-4 (1: 8), rinse solution FR-3
Processing was carried out through an automatic processor equipped with (1: 7). Next, gum GU-7 (1: 1) manufactured by Fuji Photo Film Co., Ltd.
The plate was processed by using the above, and printed by a Heidel KOR-D machine. At this time, the number of good prints obtained was observed. The results are shown in Table 4 below. In each case, 30,000 or more printed matters were obtained. In particular, it has two or more hydroxymethyl groups or alkoxymethyl groups in the molecule and has 3 to 5 benzene nuclei.
[P-3] to [P-12] using a phenol derivative having a molecular weight of 1,200 or less resulted in good printed matter of 40,000 or more.

[Comparative Example 1] A novolak resin obtained by reacting m-cresol with formaldehyde in the solution [P-1] used in Example 1 in place of the polymer [BP-1] under acidic conditions. (Weight average molecular weight 2
500), and a negative planographic printing plate [Q] was prepared in the same manner as in Example 1 except for this. The obtained planographic printing plate material [Q] was formed and printed in the same manner as in Example 1. At this time, the number of good prints obtained was observed. The results are shown in Table 4 below. Only less than 30,000 printed materials were obtained.

Comparative Example 2 In the solution [P-2] used in Example 2, a novolak resin obtained by reacting m-cresol and formaldehyde under acidic conditions instead of the polymer [BP-1] (Weight average molecular weight 2
500), and a negative planographic printing plate [R] was prepared in the same manner as in Example 2 except for this. The obtained planographic printing plate material [R] was formed and printed in the same manner as in Example 2. At this time, the number of good prints obtained was observed. The results are shown in Table 4 below. Only less than 30,000 printed materials were obtained.

[0097]

[Table 4]

From the results of Examples 1 to 12 and Comparative Examples 1 and 2, the lithographic printing plate material using the negative type image recording material of the present invention was superior to the conventional product in terms of printing durability during printing. You can see that there is.

[Examples 13 to 24, Comparative Examples 3 and 4] The negative type lithographic printing plate material [P-1] prepared in Examples 1 to 12
〔[P-12] and the negative type lithographic printing plates [Q] and [R] prepared in Comparative Examples 1 and 2 were stored at a high temperature of 60 ° C. for 3 days before image exposure. Thereafter, the first embodiment
Images were formed in the same manner as in No. 12 and printed with a Heidel KOR-D machine. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. The results are shown in Table 5 below. A phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule, containing 3 to 5 benzene nuclei, and having a molecular weight of 1,200 or less was used [P-3] to [P-3]. In the case of -12], no stain was generated in the non-image portion, but other than these, slight or slight stain was generated. Accordingly, among the negative type lithographic printing plate materials of the present invention, the negative lithographic printing plate material has two or more hydroxymethyl groups or alkoxymethyl groups in the molecule, and contains 3 to 5 benzene nuclei, and further has a molecular weight of 1,200 or less. It can be seen that when the phenol derivative is used, the storage stability at high temperatures is excellent.

[0100]

[Table 5]

[Examples 25 to 30] In the following solution [S], eleven kinds of solutions [S-1] to [S-6] were prepared by changing the kind of the compound represented by the general formula of the present invention. did. Each of the solutions was applied to the primed aluminum plate used in [Examples 1 to 12], dried at 100 ° C. for 1 minute, and used for negative type lithographic printing plates [S-1] to [S-].
6] was obtained. The weight after drying was 1.8 g / m ² .

Solution [S] Polymer of the present invention 1.6 g Thermal cross-linking agent 0.8 g Acid generator 0.2 g Infrared absorber NK-2014 (trade name) 0.15 g (manufactured by Japan Photographic Dye Laboratories Co., Ltd.) 1-naphthalene-0.05 g of counter ion of Victoria Pure Blue BOH Sulfonic acid dye Fluorosurfactant Megafac F-177 (trade name) 0.06 g (manufactured by Dainippon Ink and Chemicals, Inc.) Methyl ethyl ketone 15 g 1-Methoxy-2-propanol 5 g Methyl alcohol 7 g Compounds used in solutions [S-1] to [S-6] are shown in Table 6 below.
Shown in

[0103]

[Table 6]

(In the table, the resole resin is obtained by reacting bisphenol A with formaldehyde under alkaline conditions (weight average molecular weight: 1600).)

The obtained negative type lithographic printing plate material [S-1]
To [S-6] were exposed with a semiconductor laser emitting infrared light having a wavelength of 830 nm. After the exposure, a heat treatment was performed at 120 ° C. for 1 minute, and a developing solution manufactured by Fuji Photo Film Co., Ltd., DP-4
(1: 8), and processed through an automatic developing machine charged with a rinsing liquid FR-3 (1: 7). Subsequently, the plate surface was treated with gum GU-7 (1: 1) manufactured by Fuji Photo Film Co., Ltd., and printing was performed with a Heidel KOR-D machine. At this time, the number of good prints obtained was observed. The results are shown in Table 7 below. In each case, 30,000 or more printed matters were obtained. In particular, two
A phenol derivative having at least 3 hydroxymethyl groups or alkoxymethyl groups, containing 3 to 5 benzene nuclei, and having a molecular weight of 1,200 or less was used [S
In [-3] to [S-6], good printed matter of 40,000 or more was obtained.

[Comparative Example 5] A novolak resin obtained by reacting m-cresol with formaldehyde in the solution [S-1] used in Example 25 in place of the polymer [BP-1] under acidic conditions. (Weight average molecular weight 2
500), and in the same manner as in Example 25, a negative type lithographic printing plate [T] was prepared. The resulting lithographic printing plate material [T] was formed and printed in the same manner as in Example 25. At this time, the number of good prints obtained was observed.
The results are shown in Table 7 below, but less than 30,000 printed materials were obtained.

Comparative Example 6 In the solution [S-2] used in Example 26, a novolak resin obtained by reacting m-cresol and formaldehyde under acidic conditions instead of the polymer [BP-1] (Weight average molecular weight 2
500), and a negative type planographic printing plate [U] was prepared in the same manner as in Example 26 except for this. The resulting planographic printing plate material [U] was formed and printed in the same manner as in Example 26. At this time, the number of good prints obtained was observed.
The results are shown in Table 7 below, but less than 30,000 printed materials were obtained.

[0108]

[Table 7]

According to Examples 25 to 30 and Comparative Examples 5 and 6,
It can be seen that the lithographic printing plate material using the negative image recording material of the present invention has excellent printing durability during printing.

[0110]

According to the present invention, a plate can be directly made from digital data of a computer or the like by recording using a solid-state laser and a semiconductor laser that emit infrared light.
Further, it is possible to provide a negative type image recording material which is excellent as a negative type lithographic printing plate material having excellent film strength of a recorded image and excellent printing durability during printing.

Claims (1)

[Claims] 1. A negative type image recording material comprising the following (A) to (D). (A) at least one polymer having a hydroxyaryl group in the side chain, (B) a thermal crosslinking agent, (C) an acid generator, and (D) an infrared absorber.