JPH1080994A - Negative type image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a storing stability even under a high temperature, by forming a negative type image recording material using a polymer obtained by polymerizing monomers each having a specific structure represented by the formulas, a phenol derivative, an infrared absorbent and a novolac resin. SOLUTION: A negative type image recording material is comprises of a polymer obtained by polymerizing monomers each having a specific structure represented by formula I or II (wherein R1 is a hydrocarbon group of up to 20 carbon atoms which may have a hydrogen atom or a substituent group, R2 is a dihydric hydrocarbon group of up to 20 carbon atoms which may have a single bond or a substituent group, Ar is an aryl of up to 20 carbon atoms which may have a substituent group), a phenol derivative containing 3-5 benzene rings which have two or more hydroxymethyls or alkoxymethyls combined with the benzene rings, an infrared absorbent and a novolac resin. Therefore, it is possible to improve a storage stability even under a high temperature.

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 lithographic printing plate capable of directly making a plate by using an infrared laser from a digital signal of a computer or the like. Regarding plate materials.

[0002]

2. Description of the Related Art Conventionally, as a system for making a plate directly from digital data of a computer, an electrophotographic system, a photopolymerization system for exposing using a laser emitting blue or green light, and a silver salt on a photosensitive resin are known. Laminated ones, silver salt diffusion transfer methods, and the like have been proposed.

However, in the case of using the electrophotographic method, an image forming process such as charging, exposure, and development is complicated, and the apparatus is complicated and large. In the photopolymerization system, since the plate material is highly sensitive to blue or green light, it is difficult to handle in a bright room. In the methods (1) and (2), processing such as development is complicated because a silver salt is used.
Further, naturally, there is a disadvantage that silver is contained in the processing waste liquid.

On the other hand, the development of lasers in recent years has been remarkable. 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.

As an image recording material recordable by such 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,
If the image is formed and printed after long-term storage, especially after storage at high temperature, there is a problem that the non-image portion is stained.

[0006]

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 that emits infrared light, and furthermore, it is possible to obtain a stable plate during storage. An object of the present invention is to provide a negative type image recording material which is useful as a negative type lithographic printing plate material having excellent properties, especially storage stability at high temperatures.

[0007]

Means for Solving the Problems The inventors of the present invention pay attention to the constituent components of a negative-type image recording material, and as a result of intensive studies, a negative-type image recording material comprising the following (A) to (D): It has been found that the above object can be achieved by using a recording material, and the present invention has been completed. (A) a polymer having at least one of the structural units represented by the following general formula (i) or (ii),

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(In the formula, R ₁ represents a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent, and R ₂ represents a single bond or a carbon atom which may have a substituent. R ₃ represents a divalent hydrocarbon group having 20 or less atoms, and R ₃ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent, and Ar represents a carbon atom having a substituent. Number of atoms 2
And represents an aryl group of 0 or less. X is a single bond, -CO-O-
Or -CO-NR ₁₄ - indicates, wherein, R ₁₄ represents a hydrogen atom or have a substituent having 20 or less good carbon atoms hydrocarbon group. Y is a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent,
(= X) shows a -R ₁₅ or -N = N-R _16. Where R
₁₅ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent, and R ₁₆ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. X is O, S or N
Indicates -R _17, R ₁₇ represents a hydrocarbon group having up to good 20 carbon atoms which may have a substituent. Note that R ₃ , R ₁₄ ,
Any two of R ₁₅ , R ₁₆ and R ₁₇ may be linked to form a ring. (B) A phenol derivative having two or more hydroxymethyl or alkoxymethyl groups linked to a benzene ring in the molecule and containing 3 to 5 benzene rings which may have a substituent. (C) an infrared absorber, and (D) at least one novolak resin.

In the negative type image recording material of the present invention,
The energy of the irradiated infrared laser or the like is converted into heat by the (C) infrared absorbing agent, and (A) the specific polymer is decomposed by the heat and a strong acid group having a sulfur atom in the molecule (for example, a sulfonic acid group) Occurs. The strong acid group promotes a crosslinking reaction between the (B) phenol derivative and the (D) novolak resin, thereby performing image recording, that is, plate making of a recording material.

Hereinafter, the present invention will be described in detail. [(A) Polymer having structural unit represented by general formula (i) or (ii)] In the present invention, at least one of the structural units represented by general formula (i) or (ii) is used. A polymer having two components is used.

Here, in the general formula (i) or (ii),
R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group having 20 or less carbon atoms (eg, an alkyl group, an alkenyl group, an aralkyl group, and an aryl group). These hydrocarbon groups include, for example, a halogen atom, an alkoxy group,
It may have a substituent such as a nitro group, a cyano group and a carboxy group.

Specific examples include a hydrogen atom, a methyl group, an ethyl group, a carboxymethyl group, a chloromethyl group, a phenyl group and the like, and preferably a hydrogen atom or a methyl group.

R ₂ is a single bond or a divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent (eg, an alkylene group, an alkenylene group, an aralkylene group,
Arylene group).

Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, a methylpropylene group, a dimethylethylene group, a pentylene group, a hexylene group, an octylene group and a phenylene group. And a naphthylene group. These hydrocarbon groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group, and a carboxy group.

Preferred R ₂ is a single bond or a hydrocarbon group having 12 or less carbon atoms which may have a substituent.

R ₃ is a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, and an i-
Propyl, n-butyl, sec-butyl, t-butyl, hexyl, cyclohexyl, octyl,
2-ethylhexyl group, alkyl group such as dodecyl group, vinyl group, allyl group, 1-methylvinyl group, alkenyl group such as 2-phenylvinyl group, aralkyl group such as benzyl group, phenyl group, tolyl group, xylyl group, Cumenyl group,
And aryl groups such as a mesityl group, a dodecylphenyl group, a phenylphenyl group, and a naphthyl group.

These hydrocarbon groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group and a carboxy group. Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, a 2-methoxyethyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, an iodophenyl group, a methoxyphenyl group, a phenoxyphenyl group, and a nitrophenyl group. ,
Examples include a cyanophenyl group and a carboxyphenyl group.

Desirable R ₃ is an optionally substituted hydrocarbon group having 12 or less carbon atoms.

Ar represents an aryl group having 20 or less carbon atoms which may have a substituent. These aryl groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group, and a carboxy group.

Specifically, phenyl, tolyl, xylyl, cumenyl, mesityl, dodecylphenyl, phenylphenyl, naphthyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, methoxy Examples include a phenyl group, a phenoxyphenyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, and a nitronaphthyl group. Desirable Ar is an aryl group having 12 or less carbon atoms which may have a substituent.

X is a single bond, -CO-O- or -CO-
NR ₁₄ -is shown. Here, R ₁₄ is a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent (for example, a halogen atom, an alkoxy group, a nitro group, a cyano group, a carboxy group, etc.) (for example, an alkyl group, Alkenyl group, aralkyl group, aryl group). Preferred R
₁₄ is a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms such as a methyl group, an ethyl group and a phenyl group.

Y may have a hydrogen atom or a substituent
A good hydrocarbon group having 20 or less carbon atoms, -C (= X_Y)
-R_FifteenOr -N = NR₁₆Is shown. Where R_FifteenAnd R
₁₆Represents a substituent (eg, a halogen atom, an alkoxy
Group, nitro group, cyano group, carboxy group, etc.)
And a hydrocarbon group having 20 or less carbon atoms. X _Y
Is O, S or NR₁₇And R₁₇Has a substituent
And a hydrocarbon group having 20 or less carbon atoms.

Any two of R ₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be linked to form a ring.

Using at least one of the monomers represented by the following general formulas (I) to (V) among the structural units represented by the general formula (i) or (ii),
A polymer obtained by radical polymerization is used.

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In the general formulas (I) to (V), R ₁ is a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent (for example, an alkyl group, an alkenyl group, an aralkyl group, Aryl group). These hydrocarbon groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group, and a carboxy group.

Specific examples include a hydrogen atom, a methyl group, an ethyl group, a carboxymethyl group, a chloromethyl group, a phenyl group and the like, and preferably a hydrogen atom or a methyl group.

R ₂ represents a single bond or a divalent hydrocarbon group having 20 or less carbon atoms which may have a substituent (for example, an alkylene group, an alkenylene group, an aralkylene group,
Arylene group).

Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, a methylpropylene group, a dimethylethylene group, a pentylene group, a hexylene group, an octylene group and a phenylene group. And a naphthylene group. These hydrocarbon groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group, and a carboxy group.

Desirable R ₂ is a single bond or a hydrocarbon group having 12 or less carbon atoms which may have a substituent.

R ₄ , R ₇ and R _{8 each} represent an optionally substituted hydrocarbon group having 20 or less carbon atoms.

Specific examples of the hydrocarbon group include a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, hexyl group,
Cyclohexyl group, octyl group, 2-ethylhexyl group, alkyl group such as dodecyl group, vinyl group, allyl group,
1-methylvinyl group, alkenyl group such as 2-phenylvinyl group, aralkyl group such as benzyl group, phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, dodecylphenyl group, phenylphenyl group, naphthyl group, etc. Aryl groups.

These hydrocarbon groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group and a carboxy group. Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, a 2-methoxyethyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, an iodophenyl group, a methoxyphenyl group, a phenoxyphenyl group, and a nitrophenyl group. ,
Examples include a cyanophenyl group and a carboxyphenyl group.

Desirable R ₄ , R ₇ and R ₈ are a hydrocarbon group having 12 or less carbon atoms which may have a substituent.

Ar ₁ and Ar ₂ each represent an aryl group having 20 or less carbon atoms which may have a substituent. These aryl groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a cyano group, and a carboxy group.

Specifically, phenyl, tolyl, xylyl, cumenyl, mesityl, dodecylphenyl, phenylphenyl, naphthyl, fluorophenyl, chlorophenyl, bromophenyl, bromophenyl, iodophenyl, methoxy Examples include a phenyl group, a phenoxyphenyl group, a nitrophenyl group, a cyanophenyl group, a carboxyphenyl group, and a nitronaphthyl group. Desirable Ar ₃ and Ar ₄ are aryl groups having 12 or less carbon atoms which may have a substituent.

R ₅ is a halogen atom or an optionally substituted hydrocarbon group having 10 or less carbon atoms (eg, an alkyl group, an alkenyl group, an aralkyl group, an aryl group)
Or an alkoxy group having 10 or less carbon atoms.

Specifically, halogen atoms of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, n-propyl group, i-propyl group, allyl group, n-butyl group, sec-
-Butyl group, t-butyl group, hexyl group, cyclohexyl group, benzyl group, phenyl group, hydrocarbon groups such as tolyl group, 2-methoxyethyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group,
Examples include a hydrocarbon group having a substituent such as a methoxyphenyl group, and an alkoxy group such as a methoxy group and an ethoxy group.

Further, two R ₅ 's may be bonded to each other to form a condensed ring.

R ₆ has 2 carbon atoms which may have a substituent.
0 or less divalent hydrocarbon groups (for example, alkylene group,
Alkenylene, aralkylene, arylene).

Specifically, ethynylene, 1,2-cyclohexenylene, 1,2-phenylene, 4-chloro-1,2-phenylene, 4-nitro-1,2-phenylene, 4 -Methyl-1,2-phenylene group, 4-methoxy-1,2-phenylene group, 4-carboxy-1,2
-Phenylene group, 1,8-naphthalenylene group and the like.

N represents an integer of 0 to 4.

X is a single bond, -CO-O- or -CO-
NR ₁₄ -is shown. Here, R ₁₄ is a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent (for example, a halogen atom, an alkoxy group, a nitro group, a cyano group, a carboxy group, etc.) (for example, an alkyl group, Alkenyl group, aralkyl group, aryl group). Preferred R
₁₄ is a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms such as a methyl group, an ethyl group and a phenyl group.

Y represents a hydrogen atom or a substituent
A good hydrocarbon group having 20 or less carbon atoms, -C (= X_Y)
-R_FifteenOr -N = NR₁₆Is shown. Where R_FifteenAnd R
₁₆Represents a substituent (eg, a halogen atom, an alkoxy
Group, nitro group, cyano group, carboxy group, etc.)
And a hydrocarbon group having 20 or less carbon atoms. X _Y
Is O, S or NR₁₇And R₁₇Has a substituent
And a hydrocarbon group having 20 or less carbon atoms.

Among the compounds represented by the general formulas (I) to (V), preferred compounds are shown below.

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[0048]

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[0053]

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Formulas (I), (II), (IV) and (V)
Is a compound called active sulfonic acid ester, and can be generally synthesized from a corresponding sulfonic acid halide (preferably sulfonic acid chloride) and a corresponding hydroxy compound. In particular,
JP-A Nos. 2-100053 and 2-100054
Can be synthesized by the method described in the above item.

The compound represented by the general formula (III) is a compound called a disulfonyl compound.
As described in JP-A-100053 and JP-A-2-100054, it can be synthesized from the corresponding sulfonic acid halogenide (preferably sulfonic acid chloride) and sulfinic acid. It can also be synthesized by the method described in DE 38 04 316 A1.

In the present invention, the compounds of the general formulas (I) to (I)
At least one of the monomers represented by (V) is used, and a polymer obtained by radical polymerization is used. Among the monomers represented by general formulas (I) to (V), only one kind is used. The homopolymer used may be used,
A copolymer using two or more kinds may be used.

In the present invention, the polymer having at least one of the structural units represented by the general formula (i) or (ii), which is more preferably used, is a compound represented by the general formula (I)
It is a copolymer obtained by radical polymerization using at least one of the monomers represented by (V) and other known monomers.

Other monomers used in the copolymer include, for example, acrylic esters, methacrylic esters, acrylamides, methacrylamides, vinyl esters, styrenes, acrylic acid, methacrylic acid,
Known monomers such as acrylonitrile, maleic anhydride, and maleic imide are exemplified.

Specific examples of the acrylates 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, hydroxybenzyl acrylate, hydroxyphenethyl acrylate, dihydroxyphenethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, hydroxyphenyl Sulfonyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, 2- (hydroxyphenyl carbonyloxy) ethyl acrylate.

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, benzyl methacrylate, methoxybenzyl methacrylate, chlorobenzyl methacrylate, hydroxybenzyl methacrylate,
Hydroxyphenethyl methacrylate, dihydroxyphenethyl methacrylate, furfuryl methacrylate,
Examples include tetrahydrofurfuryl methacrylate, phenyl methacrylate, hydroxyphenyl methacrylate, chlorophenyl methacrylate, sulfamoylphenyl methacrylate, and 2- (hydroxyphenylcarbonyloxy) ethyl methacrylate.

Specific examples of acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-benzylacrylamide,
Hydroxyethylacrylamide, N-phenylacrylamide, N-tolylacrylamide, N- (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-phenylmethacrylamide, N-tolylmethacrylamide, N- (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, dimethoxystyrene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Examples thereof include iodostyrene, fluorostyrene, carboxystyrene, and the like.

Of these other monomers, particularly preferred are those having not more than 20 carbon atoms, such as acrylates, methacrylates, acrylamides, methacrylamides, vinyl esters, styrenes, and the like. Acrylic acid, methacrylic acid and acrylonitrile.

The proportion of the structural unit represented by the general formula (i) or (ii) contained in the copolymer using these is 5 to 5.
It is preferably 90% by weight, more preferably 1% by weight.
0 to 80% by weight.

The polymer having at least one of the structural units represented by formula (i) or (ii) used in the present invention preferably has a molecular weight of 2,000 or more in terms of weight average molecular weight. , More preferably 5,000 to
In the range of 300,000, and preferably 800 in number average molecular weight.
And more preferably in the range of 1000-250,000. Polydispersity (weight average molecular weight / number average molecular weight) is 1
The above is preferable, and the range is more preferably 1.1 to 10.

These polymers are random polymers,
Any of a block polymer and a graft polymer may be used, but a random polymer is preferable.

Solvents used in synthesizing the polymer used in the present invention include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-
Examples include dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.

As the radical polymerization initiator used in synthesizing the polymer used in the present invention, known compounds such as an azo initiator and a peroxide initiator can be used.

The general formula (i) or (i) used in the present invention
The polymer having at least one of the structural units represented by i) may be used alone or as a mixture. The amount of these polymers is 0.1 to 70% by weight, preferably 1 to 40% by weight, based on the total solid content of the image recording material.
In the image recording material. 0.1
If the amount is less than 10% by weight, no image can be obtained. On the other hand, when the addition amount is 70% by weight or more, non-image areas are stained during printing.

[(B) 3 to 5 benzene rings which have two or more hydroxymethyl or alkoxymethyl groups linked to the benzene ring in the molecule and may have a substituent; At least one of the phenol derivatives
seed. In the present invention, a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in the molecule is used. This hydroxymethyl group or alkoxymethyl group is connected to a benzene ring forming the skeleton of the phenol derivative. Is what it is. Here, the alkoxymethyl group preferably has 6 or less carbon atoms. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, s
An ec-butoxymethyl group and a t-butoxymethyl group are preferred.

A hydroxymethyl group or an alkoxymethyl group has two in the molecule from the viewpoint of the strength of the formed image.
Is essential, preferably three, and four
It is more preferred that the number be at least one. By including a plurality of benzene rings in which two of these hydroxymethyl groups or alkoxymethyl groups are linked, four or more of these groups can be contained in the phenol derivative. If these groups are less than two in a molecule, it is not preferable because an image is hardly formed. Further, the phenol derivative having an alkoxymethyl group is more preferable than the phenol derivative having a hydroxymethyl group in terms of stability during storage at a high temperature. Therefore, a phenol derivative having an alkoxymethyl group is more preferable.

The phenol derivative used herein preferably has a molecular weight of 1,200 or less. If the molecular weight exceeds 1,200, it is not preferable in terms of stability during storage.

Among these phenol derivatives, particularly preferred ones are listed below, but are not limited thereto.

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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 a method described in JP-A-6-28067, JP-A-7-64285, or the like.

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 EP632003A1 or the like.

In the present invention, the phenol derivative having a hydroxymethyl group or an alkoxymethyl group accounts for 5 to 70% by weight, preferably 10% by weight, based on the total solid content of the image recording material.
To 65% by weight, particularly preferably 15 to 60% by weight. 5% by weight of phenol derivative
If the amount is less than the above, the durability of the recording layer deteriorates. If the amount exceeds 70% by weight, the stability during storage is not preferable.

These phenol derivatives may be used alone or in combination of two or more.

[(C) 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, dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes Is mentioned.

Preferred dyes include, for example, those described in
125246, JP-A-59-84356, JP-A-5-84356
Cyanine dyes described in JP-A-9-202829 and JP-A-60-78787;
JP-A-58-181690, JP-A-58-194
No. 595, etc .;
Naphthoquinone dyes described in 112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744 and the like. JP-A-58-112
792 and the cyanine dyes described in British Patent No. 434,875, and the like.

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.

Further, as another preferred example of the dye, US Pat. No. 4,756,993 discloses a compound represented by the formula (I):
Near-infrared absorbing dyes described as (II) can be mentioned.

Among these dyes, particularly preferred are a cyanine dye, a squarylium dye, a pyrylium salt, and a nickel thiolate complex.

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).

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

These pigments may be used without surface treatment, or may be used after surface treatment. Methods of surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate).
Can be conceived on the surface of the pigment. 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)
It is described in.

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. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 1
986).

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 another layer may be provided and added thereto.

[(D) Novolak Resin] The novolak resin used in the present invention is a resin obtained by condensing phenols and aldehydes under acidic conditions.

Preferred novolak resins are, for example, novolak resins obtained from phenol and formaldehyde, novolak resins obtained from m-cresol and formaldehyde, novolak resins obtained from p-cresol and formaldehyde, and novolak resins obtained from o-cresol and formaldehyde. Resin, novolak resin obtained from octylphenol and formaldehyde,
Novolak resin obtained from m- / p-mixed cresol and formaldehyde, phenol / cresol (m-,
p-, o- or m- / p-, m- / o-, o- / p-
Or a novolak resin obtained from formaldehyde.

These novolak resins have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400
~ 60,000 are preferred.

In the present invention, these novolak resins are 5 to 90% by weight, preferably 10 to 85% by weight, particularly preferably 20 to 80% by weight, based on the total solid content of the image recording material.
Is used in the amount added. If the amount of the novolak resin is less than 5% by weight, the durability of the recording layer deteriorates.
Exceeding the weight percentage is not preferable in terms of both sensitivity and durability.

These novolak resins may be used alone, or two or more kinds may be used in combination.

[Other Components] In the present invention, the above-mentioned four components are essential, but 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 B
Y, oil black BS, oil black T-505
(Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI4255)
5), methyl violet (CI42535), ethyl violet, rhodamine B (CI145170B),
Malachite green (CI42000), methylene blue (CI52015), etc., or JP-A-62-29
Dyes described in Japanese Patent No. 3247 can be exemplified.

It is preferable to add these dyes since the image area and the non-image area can be easily distinguished after image formation. The amount of addition was 0.1 to the total solid content of the image recording material.
It is a ratio of 01 to 10% by weight.

Further, in the image recording material of the present invention, JP-A-62-251740 and JP-A-3-208514 are used in order to increase 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 alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N , N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like. The proportion of the nonionic surfactant and the amphoteric surfactant in the image recording material is 0.05 to 15% by weight.
And 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, epoxy compounds, vinyl ethers and the like may be added.

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 given, but 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 is laminated or vapor-deposited as described above.

As the support of the present invention, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. 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 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 about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an alkaline aqueous solution for removing the rolling oil on the surface is performed.

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 and roughening the surface, and a method of chemically roughening the surface. Is selectively dissolved. 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
After an alkali etching treatment and a neutralization treatment as necessary, an anodic oxidation treatment is performed as required to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes 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.

The conditions of the anodizing treatment vary depending on the electrolyte used, and 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, and the non-image area of the lithographic printing plate is easily damaged. The so-called "scratch dirt" to which is adhered easily occurs.

After the anodic oxidation treatment, the aluminum surface is subjected to a hydrophilic treatment if necessary. The hydrophilic treatment used in the present invention is described in U.S. Pat.
No. 66, No. 3,181,461, No. 3,280,7
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in No. 34 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. Pat. Nos. 3,276,868, 4,153,461 and 4,689,272 are disclosed. A method of treating with polyvinyl phosphonic acid as described above is used.

In the image recording material of the present invention, an undercoat layer can be provided on a support, if necessary.

Various organic compounds can be used as the components of the undercoat layer. For example, phosphonic acids having an amino group such as carboxymethylcellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, and may have a substituent. Organic phosphonic acids such as phenylphosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and Organic phosphoric acid such as glycerophosphoric acid, phenylphosphinic acid which may have a substituent,
Naphthyl phosphinic acid, organic phosphinic acids such as alkyl phosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochlorides of amines having a hydroxy group such as hydrochloride of triethanolamine are selected from, You may mix and use 2 or more types.

The coating amount of the organic undercoat layer is 2 to 200 mg /
m ² is appropriate.

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 alkaline aqueous solutions can be used. For example, sodium silicate, potassium silicate, tertiary
Sodium phosphate, same potassium, same ammonium, second
Sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium And the like. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine,
Organic alkaline agents such as diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents are used alone or in combination of two or more. Among these alkali agents, particularly preferred developers are aqueous silicate solutions such as sodium silicate and potassium silicate. The reason is that silicate components silicon oxide SiO ₂ and alkali metal oxide M
_This is because the developability can be adjusted by the ratio and concentration of ₂ O. For example, alkali metal silicates described in JP-A-54-62004 and JP-B-57-7427 are effective. Used for

In the case of further 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 needed 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.

The developing solution and the replenisher may contain, if necessary, a reducing agent such as a sodium salt or a potassium salt of an inorganic acid such as hydroquinone, resorcin, sulfurous acid and bisulfite, an organic carboxylic acid, an antifoaming agent, and a hard water. Softeners 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 solution can also be applied.

The lithographic printing plate obtained as described above can be subjected to a printing step after coating with a desensitizing gum if desired. However, when a lithographic printing plate having a higher printing durability is desired to be obtained, Is subjected to a burning process.

In the case of burning a lithographic printing plate, prior to burning, JP-B Nos. 61-2518 and 55-280.
No. 62, JP-A-62-131859 and JP-A-61-1596.
It is preferable to treat with a surface-regulating liquid as described in each of the publications No. 55.

[0137] As a method for this, a sponge or absorbent cotton impregnated with the surface conditioning liquid is applied onto a lithographic printing plate,
A method in which a printing plate is immersed in a vat filled with a surface-conditioning solution and applied, or an automatic coater is used. Further, it is more preferable to make the application amount uniform with a squeegee or a squeegee roller after the application.

The coating amount of the surface conditioning liquid is generally 0.03 to 0.8.
g / m ² (dry weight) is 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 if necessary. However, a surface conditioning solution containing a water-soluble polymer compound or the like can be used. When is used, so-called desensitizing treatment such as gumming can be omitted.

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

[0142]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. [Synthesis of polymer having at least one of structural units represented by general formula (i) or (ii)] With reference to JP-A-2-100053 and JP-A-2-100054, The following polymers were synthesized. All weight average molecular weights (GPC, polystyrene standard) are 1
It was in the range of 10,000 to 70,000.

[0143]

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[0144]

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[0145]

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[0146]

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[(B) Synthesis of a phenol derivative having two or more hydroxymethyl or alkoxymethyl groups in the molecule, containing 3 to 5 benzene nuclei, and having a molecular weight of 1,200 or less] Synthesis Example B-1) 20 g of 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene (manufactured by Honshu Chemical Industry Co., Ltd.) Trisp-PA) was added to a 10% aqueous potassium hydroxide solution, and the mixture was stirred and dissolved. Next, while stirring this solution, 60 ml of a 37% aqueous formalin 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).

[0148]

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(Synthesis Example B-2) The phenol derivative having a hydroxymethyl group obtained in Synthesis Example B-1 [HM-
1] 20 g was added to 1 liter of methanol, heated and stirred to dissolve. Next, 1 ml of concentrated sulfuric acid was added to this solution,
The mixture was heated under reflux for 12 hours. After the reaction, cool the reaction solution,
2 g of potassium carbonate was added. After sufficiently concentrating this mixture, 300 ml of ethyl acetate 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).

[0150]

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

[0152]

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[0153]

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[0154]

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[Examples 1 to 10] An aluminum plate (material 1050) having a thickness of 0.30 mm was washed with trichlorethylene and degreased, and then its surface was grained with a nylon brush and a 400 mesh pumicetone-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], a polymer having at least one of the structural units represented by formula (i) or (ii) of the present invention and a phenol derivative of the present invention By changing the type, 10 types of solution [P
-1] to [P-10] were adjusted. Each of the solutions was applied to the above-mentioned primed aluminum plate,
Dry at 0 ° C for 1 minute to make a negative type lithographic printing plate [P-1]
To [P-10]. Weight after drying is 1.7 g / m ²
Met.

Solution [P] The general formula (i) or (i)
Polymer having at least one of the structural units represented by i) 0.2 g Phenol derivative of the present invention 0.7 g Infrared absorber NK-3508 0.15 g (manufactured by Nippon Kogaku Pigment Research Institute Co., Ltd.) Novolak resin obtained from phenol and formaldehyde 1.5 g (weight average molecular weight 10,000) Dye in which the counter ion of Victoria Pure Blue BOH is converted to 1-naphthalene-sulfonic acid 0.05 g Megafac F-177 0.06 g (Dainippon Ink Chemical (Fluorine-based surfactant manufactured by Kogyo Co., Ltd.) Methyl ethyl ketone 15 g 1-methoxy-2-propanol 5 g Methyl alcohol 7 g Compounds used in solutions [P-1] to [P-10] are shown in Table 1.
Shown in

[0158]

[Table 1]

The obtained negative type lithographic printing plate material [P-1]
~ [P-10] at 55 ° C for 3 days and 5
After storage for days, the substrate was exposed to a YAG laser, a solid-state laser that emits infrared rays having a wavelength of 1064 nm. 130 ° C after exposure
For 1 minute, a developer (manufactured by Fuji Photo Film Co., Ltd.), DP-4 (1: 8), and a rinsing solution FR-3 (1:
Processed through an automatic processor charged with 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. On this occasion,
It was observed whether or not stains had occurred on the non-image portion of the printed matter. The results are shown in Table 2 below. In all of the samples stored at a high temperature for 3 days, good prints having no stain on the non-image area were obtained. On the other hand, when stored for 5 days, [P-1] ~
In [P-5], a little stain was observed. However, [P-
6) to [P-10], good prints without stains on non-image areas were obtained.

[Comparative Example 1] In the solution [P] used in Examples 1 to 10, the general formula (i) or (ii) of the present invention was used.
In place of the polymer having at least one of the structural units represented by the formula, diphenyliodonium hexafluorophosphate (described in Example of JP-A-7-20629) is used, and further, in place of the phenol derivative of the present invention. A negative type lithographic printing plate [Q] was prepared in the same manner as in Examples 1 to 10, except that a resole resin (weight average molecular weight: 1600) obtained from bisphenol A and formaldehyde was used. The obtained planographic printing plate material [Q] was stored at a high temperature of 55 ° C. for 3 days in the same manner as in Examples 1 to 10, and then an image was formed and printed. On this occasion,
It was observed whether or not stains had occurred on the non-image portion of the printed matter. The results are shown in Table 2 below. It was found that the non-image portion was stained.

When storage was not performed at a high temperature, no non-image portion stain was observed during printing even on the lithographic printing plate material [Q].

[Comparative Example 2] In the solution [P] used in Examples 1 to 10, the general formula (i) or (ii) of the present invention was used.
2,4,6-tris (trichloromethyl) -s-triazine (JP-A-7-27102), instead of the polymer having at least one of the structural units represented by
T-1) described in Example No. 9 and a resole resin (weight average molecular weight 1600) obtained from bisphenol A and formaldehyde were used in place of the phenol derivative of the present invention. In the same manner as in No. 10, a negative type lithographic printing plate material [R] was prepared. The obtained planographic printing plate material [R] was stored at a high temperature of 55 ° C. for 3 days in the same manner as in Examples 1 to 10, and then an image was formed and printed. 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 2 below. It was found that the non-image portion was stained. When storage at high temperature was not performed, no non-image portion stain was observed during printing even on the lithographic printing plate material [R].

[0163]

[Table 2]

As shown in Table 2, from the evaluation results of Examples 1 to 10 and Comparative Examples 1 and 2, the lithographic printing plate using the negative type image recording material of the present invention was found to be stable in storage at high temperatures. It turns out that it is excellent. Furthermore, it turns out that the storage stability at high temperature is more excellent when using the phenol derivative which has an alkoxymethyl group than when using the phenol derivative which has a hydroxymethyl group.

[Examples 11 to 21] In the following solution [S], a polymer having at least one of the structural units represented by formula (i) or (ii) of the present invention,
By changing the type of the phenol derivative of the present invention, 11
Various types of solutions [S-1] to [S-11] were prepared. Each of the solutions was applied to the undercoated aluminum plate used in [Examples 1 to 10], dried at 100 ° C. for 1 minute, and used for negative-working lithographic printing plates [S-1] to [S-11]. I got The weight after drying was 1.7 g / m2.

Solution [S] The general formula (i) or (i)
Polymer having at least one of the structural units represented by i) 0.2 g Phenol derivative of the present invention 0.7 g Infrared absorber NK-2014 0.15 g (manufactured by Japan Photographic Dye Laboratories) Novolak resin obtained from phenol and formaldehyde 1.5 g (weight average molecular weight 10,000) Dye in which the counter ion of Victoria Pure Blue BOH was converted to 1-naphthalene-sulfonic acid 0.03 g Megafac F-177 0.06 g (Dainippon Ink Chemical (Fluorine-based surfactant manufactured by Kogyo Co., Ltd.) Methyl ethyl ketone 15 g 1-methoxy-2-propanol 5 g Methyl alcohol 7 g Compounds used in solutions [S-1] to [S-11] are shown in Table-3.
Shown in

[0167]

[Table 3]

The obtained negative type lithographic printing plate material [S-1]
~ [S-11] at 55 ° C for 3 days and 5
After storage for days, the substrate was exposed to a semiconductor laser emitting infrared light having a wavelength of 830 nm. After the exposure, a heat treatment was performed at 130 ° C. for 1 minute, and a developer, DP-4, manufactured by Fuji Photo Film Co., Ltd.
(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, it was observed whether or not stains occurred on the non-image portion of the printed matter. The results are shown in Table 4 below. In all of the samples stored at a high temperature for 3 days, good prints having no stain on the non-image area were obtained. On the other hand, when stored for 5 days, some stains were observed in [S-1] to [S-5]. In [S-11], [S-
1) to [S-5], although slightly lighter, slightly stained. However, in [S-6] to [S-10], a good printed matter having no stain on the non-image portion was obtained.

[Comparative Example 3] In the solution [S] used in Examples 11 to 21, the general formula (i) or (i)
In place of the polymer having at least one of the structural units represented by i), diphenyliodonium hexafluorophosphate (described in Example of JP-A-7-20629) is used, and the phenol derivative of the present invention is further used. Instead, a resole resin (weight average molecular weight: 1600) obtained from bisphenol A and formaldehyde was used, and a negative type planographic printing plate [T] was prepared in the same manner as in Examples 11 to 21 except for these. The obtained lithographic printing plate material [T] was treated at a temperature of 55 ° C. in the same manner as in Examples 11 to 21.
After storage at a high temperature for 3 days, an image was formed and printed. 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 4 below. It was found that the non-image portion was stained.

In the case where storage was not performed at a high temperature, no non-image portion stain was observed during printing even on the lithographic printing plate material [T].

[Comparative Example 4] In the solution [S] used in Examples 11 to 21, the general formula (i) or (i)
Instead of a polymer having at least one of the structural units represented by i), 2,4,6-tris (trichloromethyl) -s-triazine (JP-A-7-271)
No. 029), and a resole resin (weight average molecular weight: 1600) obtained from bisphenol A and formaldehyde was used in place of the phenol derivative of the present invention. 21
A negative type lithographic printing plate material [U] was prepared in the same manner as described above.
The obtained lithographic printing plate material [U] was stored at a high temperature of 55 ° C. for 3 days in the same manner as in Examples 11 to 21, and then an image was formed and printed. At this time, it was observed whether or not stains occurred on the non-image portion of the printed matter. Table 4 shows the results.
The non-image portion was stained. When storage was not performed at a high temperature, no non-image portion stains were observed during printing even on the lithographic printing plate material [U].

[0172]

[Table 4]

As is clear from Table 4, Examples 11 to 21
From the evaluation results of Comparative Examples 3 and 4, it can be seen that the lithographic printing plate material using the negative image recording material of the present invention has excellent storage stability at high temperatures. Furthermore, it turns out that the storage stability at high temperature is more excellent when using the phenol derivative which has an alkoxymethyl group than when using the phenol derivative which has a hydroxymethyl group.

[0174]

According to the present invention, recording is performed using a solid-state laser and a semiconductor laser that emit infrared light.
It is possible to provide a negative image recording material which can be directly made from digital data from a computer or the like, and is useful as a negative lithographic printing plate material having excellent storage stability, particularly excellent storage stability at high temperatures.

Claims (1)

[Claims] 1. A negative image recording material comprising: (A) to (D): (A) a polymer having at least one of the structural units represented by the following general formula (i) or (ii): (Wherein, R ₁ represents a hydrogen atom or a hydrocarbon group having 20 or less carbon atoms which may have a substituent, and R ₂ represents a single bond or a carbon atom having 20 carbon atoms which may have a substituent. The following divalent hydrocarbon groups are shown, and R ₃ is an optionally substituted hydrocarbon group having 20 or less carbon atoms, and Ar is an optionally substituted hydrocarbon group having 20 carbon atoms. The following aryl groups are represented, where X is a single bond, -CO-O- or -CO-.
NR ₁₄ - indicates, wherein, R ₁₄ represents a hydrogen atom or have a substituent having 20 or less good carbon atoms hydrocarbon group. Y is a hydrogen atom or an optionally substituted hydrocarbon group having 20 or less carbon atoms, -C (= X _Y ) -R ₁₅
Or, -N = NR ₁₆ is shown. Here, R ₁₅ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent, and R ₁₆ represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. . X _Y is O, S or N-R _17, R ₁₇ represents a hydrocarbon group having up to good 20 carbon atoms which may have a substituent. Note that R ₃ , R ₁₄ , R ₁₅ , and R ₁₆
And any two of R ₁₇ may be linked to form a ring. (B) A phenol derivative having two or more hydroxymethyl or alkoxymethyl groups linked to a benzene ring in the molecule and containing 3 to 5 benzene rings which may have a substituent. (C) an infrared absorber, and (D) at least one novolak resin.