JPH117131A - Negative image recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the recording material to form a printing plate directly from digital data of computers and the like and to enhance flexibility of a film and sensitivity at the time of recording by using at least one of specified dinuclear phenol derivatives for a compound cross-linkable compound by an acid. SOLUTION: This negative image recording material comprises the compound A cross-linkable by an acid, a binder polymer B, a compound C for producing an acid by heat, and an infrared absorber D and the compound A is at least one kind of the dinuclear phenol derivatives represented by the formula in which each of R<1> and R<2> and R<4> and R<5> is an H atom or a <=12 C hydrocarbon group; each of R<3> and R<6> is an H atom or a -(R<7> O)m -R<8> ; R<7> is a <=12 C divalent hydrocarbon group; R<8> is an H atom or a <=12 C divalent hydrocarbon group; (m) is 0, 1, 2, or 3; and each of k1 and k2 is 2, 3, or 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lithographic printing plate material, a color proof, an image recording material which can be used as a photoresist and a color filter. In particular, the present invention relates to an image recording material that can be directly made by scanning an infrared laser based on a digital signal from a computer or the like and that can be used as a so-called direct plate making lithographic printing plate material.

[0002]

2. Description of the Related Art Heretofore, as a system for directly making a plate from digital data of a computer, an electrophotographic system, a photopolymerization system for exposing with 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, the processes of image formation such as charging, exposure, and development are complicated, and the apparatus is complicated and large. In the case of the photopolymerization system, since a plate material having high sensitivity to blue or green light is used, handling in a bright room becomes difficult. The methods (1) and (2) have drawbacks in that processing such as development becomes complicated because silver salts are used, and 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 have become easily available 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. However, many photosensitive recording materials that are practically useful have a photosensitive wavelength in the visible light range of 760 nm or less, and therefore cannot record images 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 phenol resin and a spectral sensitizer described in US Pat. No. 4,708,925. However, this image recording material is a positive type utilizing the effect of suppressing dissolution in a developer, which is exhibited by an onium salt and a phenol resin, and is not a negative type as in the present invention. On the other hand, as a negative type image recording material, a substance which absorbs light and generates heat, an alkali-soluble resin, and a specific material having 4 to 8 benzene nuclei in a molecule described in JP-A-8-276558. There is a recording material composed of a phenol derivative. However, this image recording material had insufficient sensitivity at the time of laser exposure.

[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 to provide a negative-type image recording material having excellent recording sensitivity.

[0007]

Means for Solving the Problems The present inventor paid attention to the components of a negative-type image recording material, and as a result of diligent studies, the above object was achieved by using a phenol derivative having a specific functional group as a crosslinking agent. They have found that this can be achieved and have completed the present invention. That is, the present invention provides (A) a compound capable of crosslinking by an acid, (B) a binder polymer,
(C) a compound which generates an acid by heat and (D) an infrared absorber, and the compound which is crosslinked by the (A) acid is
A negative type image recording material characterized by being at least one of binuclear phenol derivatives represented by the following general formula (I).

[0008]

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In the formula, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent. X represents a linking group consisting of three or more nonmetallic elements containing at least one carbon atom. R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms, and R ³ and R ⁶ each independently represent a hydrogen atom or — (R ⁷ O) _m indicates -R ^8, wherein R ⁷ represents a divalent hydrocarbon group having not more than 12 carbon atoms, R ⁸ represents a hydrocarbon group having not more than several 12 hydrogen atoms or carbon, m is 0
Indicates an integer of 3. R ³ and R ⁶ both represent-(R ⁷ O) _m-
For R ^8, each other R ^7, R ^8, m each independently. k1 and k2 each independently represent an integer of 2 to 4.
n1 and n2 each independently represent an integer of 1 to 3.

Since the negative type image recording material of the present invention has the above-mentioned constitution, it can be directly made from digital data of a computer or the like by recording using a solid-state laser or a semiconductor laser emitting infrared rays. Direct plate making is possible, and further, there is an effect such as high sensitivity to laser during recording.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [(A) Binuclear phenol derivative represented by general formula (I) (compound capable of being crosslinked by acid)] In the present invention, the phenol derivative represented by general formula (I) is used as a crosslinking agent. In the general formula (I), Ar ₁ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent. From the availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Preferred substituents include a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms,
Examples include a cyano group, a nitro group, and a trifluoromethyl group. Because of high sensitivity, Ar ¹ and Ar ² may be the same as each other and have no substituent, such as a benzene ring and a naphthalene ring, or a halogen atom, a hydrocarbon group having 6 or less carbon atoms, A benzene ring and a naphthalene ring having as substituents an alkoxy group having a number of 6 or less, an alkylthio group having 6 or less carbon atoms, a nitro group, and the like are particularly preferable. X represents a linking group consisting of three or more nonmetallic elements containing at least one carbon atom. This linking group may contain an oxygen atom, a sulfur atom and the like in addition to the carbon atom and the hydrogen atom. If this linking group is a long chain, 2
Two phenol nuclei are present at a sufficient distance, which is preferable from the viewpoint of sensitivity and film strength of the image area. X
Examples of the following include, for example, the following linking groups.

[0012]

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R¹, R^Two, R^FourAnd R^FiveAnd R_TwoIs
Each may be the same or different and may be a hydrogen atom or
Shows an aliphatic hydrocarbon group having 12 or less carbon atoms.
For ease, a hydrogen atom or a methyl group is preferred.
Good. R^Three, R⁶Are each independently a hydrogen atom or
− (R⁷O)_m-R⁸Where R⁷Is 12 carbon atoms
Or less divalent hydrocarbon groups;⁸Is a hydrogen atom or
Represents a hydrocarbon group having 12 or less carbon atoms, and m represents 0 to 3
Indicates an integer. Where R ^Three, R⁶Are both-(R
⁷O)_m-R⁸, Each R⁷, R⁸, M
Are independent and may be different from each other. Sensitivity
From the viewpoint of the film strength of the^Three, R⁶Is a hydrogen atom
Or a 2-hydroxyethyl group,
Tylethyl group, 2-methoxyethyl group, 2-methoxy-
A 1-methylethyl group is preferred. k1 and k2 are respectively
Independently represent an integer of 2 to 4, indicating that synthesis is easy.
For this reason, it is preferably 2. n1 and n2 are each
Each independently represent an integer of 1 to 3, indicating that raw materials are readily available
For that reason, it is preferably 1 or 2.

The dinuclear phenol derivatives (crosslinking agents [KZ-1] to [KZ-5]) represented by formula (I) which are preferably used in the present invention are shown below.

[0015]

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[0016]

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These phenol derivatives can be synthesized by a conventionally known method. For example, [KZ-1] is obtained by reacting 4-hydroxythiophenol with 1,2-bis (2-iodoethoxy) ethane in the presence of a base such as potassium carbonate as shown in the following reaction formula (1). 2-bis @ 2-
It can be synthesized by synthesizing (4-hydroxyphenylthio) ethoxydiethane and further reacting it with formaldehyde or parahiraldehyde in the presence of a base such as potassium hydroxide.

[0018]

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These phenol derivatives may be used alone or in combination of two or more. When synthesizing these phenol derivatives,
In some cases, phenol derivatives are condensed with each other to produce by-products such as trimers, but they may be used while containing these impurities. Note that this impurity is preferably at most 30%, more preferably at most 20%.

In the present invention, these phenol derivatives are used in an amount of 5 to 70% by weight, preferably 10 to 50% by weight, based on the total solid content of the image recording material. If the addition amount of the phenol derivative (thermal crosslinking agent) is less than 5% by weight, the film strength of the image portion at the time of image recording will be deteriorated, and if it exceeds 70% by weight, the storage stability will be poor. Not preferred.

The use of these phenol derivatives improves the sensitivity of the image recording material, but the reason is not clear. For example, JP-A-7-206
No. 29, JP-A-8-27.
The specific phenol derivative having 4 to 8 benzene nuclei in the molecule described in No. 6558 is a compound having a large molecular weight. Generally, it is considered that the larger the molecular weight of the crosslinking agent, the higher the crosslinking efficiency, and as a result, the higher the sensitivity. However, the phenol derivative of the present invention is a compound having a molecular weight not so large,
The presence of a long-chain linking group between the two phenol nuclei enhances the flexibility of the membrane, and allows specific interaction with an acid generator described later or an acid generated from the acid generator, In the recording material coating, acid is selectively captured,
It is thought that the crosslinking efficiency was improved.

[(B) Binder polymer] In the present invention, various alkali-soluble polymers can be used as the binder polymer. Specific examples include novolak resins such as phenol novolak and cresol novolak, resol resins such as bisphenol A resol resin, styrene-based polymers such as poly (p-hydroxystyrene), and carboxyl group-containing polyurethane.

As the binder polymer suitably used in the present invention, a polymer having an aromatic hydrocarbon ring directly bonded to a hydroxy group or an alkoxy group in a main chain or a side chain is exemplified. As the alkoxy group,
From the viewpoint of sensitivity, those having 20 or less carbon atoms are preferred.
Also, as the aromatic hydrocarbon ring, from the availability of raw materials,
A benzene ring, a naphthalene ring or an anthracene ring is preferred. These aromatic hydrocarbon rings may have a substituent, but preferably have no substituent other than a hydroxy group or an alkoxy group in terms of sensitivity.

In the present invention, a binder polymer that can be particularly preferably used is a novolak resin or
It is a polymer having a structural unit represented by the following general formula (II).

[0025]

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Where Ar_TwoIs a benzene ring, naphthalene
A ring or an anthracene ring. R ⁹Is a hydrogen atom or
Represents a methyl group. R^TenIs a hydrogen atom or carbon number 20
Represents up to alkoxy groups. X¹Is a single bond or
Containing one or more atoms selected from C, H, N, O, S
And a divalent linking group having 0 to 20 carbon atoms. j
Represents an integer of 1 to 4.

In the present invention, examples of the structural unit represented by the general formula (II) which is preferably used are shown below.

[0028]

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[0029]

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The polymer having these structural units can be obtained by radical polymerization using a corresponding monomer by a conventionally known method.

In the present invention, as the binder polymer,
A homopolymer composed of only the structural unit represented by the general formula (II) may be used, or a copolymer having a structural unit derived from another known monomer may be used. Other known monomers used at this time, for example,
Acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl Methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, methacrylates such as benzyl methacrylate, styrene, acrylonitrile, and acrylic acid, monomers having an acidic group such as methacrylic acid,
Further, a monomer containing a salt of a strong acid such as a sodium salt of p-styrenesulfonic acid, an alkali metal salt of 2-acrylamido-2-methylpropanesulfonic acid, a tetraalkylammonium salt, and a potassium salt of 3-sulfopropylacrylate are exemplified. Can be

The proportion of the structural unit represented by the general formula (II) contained in the copolymer using the above compound is 50 to 10
0% by weight, more preferably 60% by weight.
１００100% by weight. The weight average molecular weight of the polymer used in the present invention is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, more preferably 2,000 to 3,000. The range is 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably in the range of 1.1 to 10.

These copolymers may be random copolymers, block copolymers, graft copolymers, etc., but are preferably random copolymers.

The solvent used in synthesizing the polymer used in the present invention includes, 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 when synthesizing the polymer used in the present invention, for example, known compounds such as an azo initiator and a peroxide initiator can be used.

The binder polymer used in the present invention may be used alone or as a mixture. These polymers are added to the image recording material at a ratio of 20 to 95% by weight, preferably 40 to 90% by weight, based on the total solid content of the image recording material. 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.

[(C) Compound that Generates Acid by Heat] In the present invention, the compound that generates an acid by heat (hereinafter, simply referred to as an acid generator) is, for example, decomposed by heating at 100 ° C. or more to convert the acid. It is a compound that is generated. 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. Specifically, US Patent No. 4,708,92
No. 5 and 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. Examples of the diazonium salt include diazonium compounds described in U.S. Pat. No. 3,867,147, diazonium compounds described in U.S. Pat. No. 2,632,703, and JP-A-1-102456 and JP-A-1-1024.
The diazo resin described in JP-A-57-57 is also preferable. Also, benzyl sulfonates described in U.S. Pat. No. 5,135,838 and U.S. Pat. No. 5,200,544 are preferable. Further, Japanese Unexamined Patent Application Publication No.
4, JP-A-2-100055 and Japanese Patent Application No. 8-944.
The active sulfonic acid esters and disulfonyl compounds described in No. 4 are also preferable. In addition, JP-A-7-271
No. 029, haloalkyl-substituted S
-Triazines are also preferred.

These compounds are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 40% by weight based on the total solid content of the image recording material.
%, More preferably 0.5 to 30% 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,
Also, two or more kinds may be used in combination. Since these acid generators can be decomposed by irradiation with ultraviolet rays, the image recording material of the present invention can record images not only with infrared rays but also with ultraviolet rays.

[(D) Infrared ray absorbent] The main object of the present invention is to record an image with a laser emitting infrared rays.
For this purpose, it is necessary to use an infrared absorber in combination. The infrared absorbent has a function of converting the absorbed infrared light into heat. At this time, the generated heat decomposes the acid generator to generate an acid. The infrared absorber used in the present invention is a dye or pigment that effectively absorbs infrared rays having a wavelength of 760 nm to 1200 nm. Preferably,
It is a dye or 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 such as “Dye Handbook” (edited by the Society of Synthetic Organic Chemistry, Japan, 1970) can be used. Specifically, for example, 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,
Dyes such as pyrylium salts, for example, metal thiolate complexes such as nickel thiolate complexes.

Preferred dyes include, for example, those described in
Cyanine dyes described in JP-A-8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, etc .;
No. 96, JP-A-58-181690, JP-A-58-1
No. 94595, etc., methine dyes described in
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940 and JP-A-60-63744;
Squarylium dyes described in No. 12792, etc.,
Cyanine dyes described in British Patent No. 434,875 and the like can be mentioned.

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 a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993.

Among these dyes, particularly preferred are, for example, 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), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" CMC Publishing, 1984)
Can be used.

Examples of the type of pigment include black pigment, yellow pigment, orange pigment, brown pigment, red pigment, purple pigment, blue pigment, green pigment, fluorescent pigment, metal powder pigment, and polymer-bound pigment. . Specifically, for example, 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 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. 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 (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Is mentioned. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably 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 preferable in terms of stability in the coating solution for the image recording layer, and when it exceeds 10 μm, it is not preferable 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. See “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% by weight, based on the total solid content of the image recording material.
To 10% by weight, particularly preferably 0.5 to 10% in the case of a dye.
% By weight, particularly preferably 1.0 to 10% by weight in the case of a pigment.
In the image recording material. 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, various compounds other than these may be further added, if necessary.
For example, a dye having a large absorption in the visible light region can be used as a colorant for an image. Specifically, for example, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY,
Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Ethyl Violet, Rhodamine B (CI145170B), Malachite Green (CI42000) , Methylene blue (CI5
2015) and the dyes described in JP-A-62-293247.

It is preferable to add these dyes since the image area and the non-image area can be easily distinguished after image formation. The addition amount is based on the total solid content of the image recording material.
The ratio is 0.01 to 10% by weight.

In the image recording material of the present invention, a nonionic interface as described in JP-A-62-251740 and JP-A-3-208514 is used in order to widen the stability of processing under development conditions. Activator, JP-A-59
An amphoteric surfactant as described in JP-A-121044 and JP-A-4-13149 can be added.

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

Specific examples of amphoteric surfactants include, for example, alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl- N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and the like.

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

Further, a plasticizer is 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.

In the image recording material of the present invention, each of the above components is usually dissolved in a solvent and applied on a suitable support. Examples of the solvent used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol,
2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, Sulfolane, γ-
Examples thereof include, but are not limited to, butyl lactone, toluene, and water. 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. Various methods can be used as the method of coating, and examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the image recording film deteriorate.

In the image recording material of the present invention, a surfactant for improving coating properties, for example, JP-A-62-1
No. 70950 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.

[Support] The support on which the image recording material of the present invention can be applied is a dimensionally stable plate, for example, paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.). Laminated paper,
Metal plates (eg, aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate,
Cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited.

Preferred examples of the support include a polyester film and an aluminum plate. Among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in aluminum alloys include silicon, iron, manganese,
Copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The total content of foreign elements in the alloy is 10% by weight or less. 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 is performed to remove the rolling oil on the surface.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically roughening the surface. Is selectively dissolved. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. Further, as an electrochemical surface roughening method, there is a method of performing an alternating current or a direct current in a hydrochloric acid or nitric acid electrolyte.
Further, 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, if necessary, and then subjected to an anodic oxidation treatment if necessary to increase the water retention and abrasion resistance of the surface. You. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes 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 anodizing treatment conditions 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.
Current density 5 to 60 A / dm ^2, voltage 1 to 100 V, which is an electrolyzing time of 10 seconds to 5 minutes.

When the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient, and the non-image area of the lithographic printing plate is easily damaged, and the scratched area may be damaged during printing. 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. U.S. Pat. No. 2,714,075 discloses a hydrophilic treatment that can be used in the present invention.
No. 66, No. 3,181,461, No. 3,280,
There is an alkali metal silicate (for example, sodium silicate aqueous solution) method as disclosed in U.S. Pat. Nos. 734 and 3,902,734. In this method, the support is immersed or electrolytically treated with an aqueous solution of sodium silicate. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063, U.S. Pat.
No. 76,868, No. 4,153,461, No. 4,
No. 689,272, a method of treating with polyvinyl phosphonic acid or the like is used.

[Others] Before applying the image recording material of the present invention, an undercoat layer may be provided on the support, if necessary.

Various organic compounds are used as components of the undercoat layer. Examples thereof include 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, naphthylphosphoric acid, alkylphosphoric acid which may have a substituent and Organic phosphoric acids such as glycerophosphoric acid; organic phosphinic acids such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent; amino acids such as glycine and β-alanine; and triethanol Hydroxyl groups such as amine hydrochloride Selected from hydrochloride of the amine to be, but may be used by mixing two or more. It is also preferable to undercoat the aforementioned diazonium compound.

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

As described above, a planographic printing plate using the image recording material of the present invention can be prepared. This lithographic printing plate can be recorded with an infrared laser. Also,
Thermal recording with an ultraviolet lamp or a thermal head is also possible. In the present invention, the wavelength from 760 nm to 120
It is preferable that the image is exposed by a solid-state laser and a semiconductor laser that emit 0-nm infrared light. In the present invention, the developing treatment may be performed immediately after the exposure, or a heat treatment may be performed between the exposure step and the developing step. When performing the heat treatment, it is preferable that the heat treatment is performed within a range of 60 ° C. to 150 ° C. for 5 seconds to 5 minutes. As a heating method, various conventionally known methods can be used. For example, a method using a panel heater or a ceramic heater, a method using a lamp, and the like are included. Specifically, Japanese Patent Application No. Hei 8-
No. 94197. 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 preferably developed with water or an aqueous alkaline solution.

When an alkaline aqueous solution is used, a conventionally known alkaline aqueous solution can be used as a developer and a replenisher for the image recording material of the present invention. For example, sodium silicate, potassium silicate, tribasic sodium phosphate,
Potassium tertiary phosphate, ammonium tertiary phosphate, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate And inorganic alkali salts such as sodium borate, potassium borate, 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. An example of a particularly preferable developer among these alkaline agents is an aqueous solution of a silicate such as sodium silicate and potassium silicate. The reason is that the developability can be adjusted by the ratio and the concentration of the silicon oxide SiO ₂ and the alkali metal oxide M ₂ O, which are the components of the silicate. An alkali metal silicate described in JP-B-57-7427 is effectively used.

When developing using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is added to the developing solution to replace the developing solution in the developing tank for a long time. It is known that a large amount of lithographic printing plate material can be processed without the need. This replenishment system is also preferably applied in the present invention.

To the developing solution and the replenishing solution, various surfactants and organic solvents can be added as necessary 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. Preferred organic solvents include benzyl alcohol and the like. It is also preferable to add polyethylene glycol or a derivative thereof, or polypropylene glycol or a derivative thereof.

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

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

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

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

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitized gum if desired, but when it is desired to obtain a lithographic printing plate having higher printing durability. Is subjected to a burning process.

In the case of burning a lithographic printing plate, prior to burning, Japanese Patent Publication 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.

[0086] 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 liquid to apply the printing plate, an application using an automatic coater, or the like is applied. Further, it is preferable to make the application amount uniform with a squeegee or a squeegee roller after the application.

The application 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 burned by a burning processor (for example,
It is heated to a high temperature by a burning processor (BP-1300) sold by Fuji Photo Film Co., Ltd. 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 a conventional treatment such as washing with water or gumming, if necessary. When a liquid is used, a so-called desensitizing treatment such as gumming can be omitted.

The planographic 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.

[0091]

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 Crosslinking Agent [KZ-1] 1,2-bis (2-iodoethoxy) ethane and 4-hydroxythiophenol were reacted with N, N in the presence of potassium carbonate.
Dimethylformamide as a solvent,
-Bis {2- (4-hydroxyphenylthio) ethoxy} ethane was synthesized. Subsequently, the resultant was reacted with paraformaldehyde in an aqueous potassium hydroxide solution, and further purified by column chromatography to obtain a crosslinking agent [KZ-1] having the following structure.

Crosslinking agent [KZ-1]

Embedded image

Synthesis of Crosslinking Agent [KZ-2] Using 1,6-dibromohexane in place of 1,2-bis (2-iodoethoxy) ethane, the following structure was obtained in the same manner as in the synthesis of [KZ-1]. (KZ-2) was obtained.

Crosslinking agent [KZ-2]

Embedded image

Synthesis of Crosslinking Agent [KZ-3] p-Hydroxybenzaldehyde is reacted with acetone in the presence of methanesulfonic acid to give 1,5-bis (p-hydroxyphenyl) penta-1,4-dien-3-one Was synthesized. Next, hydrogenation using palladium-carbon,
1,5-bis (p-hydroxyphenyl) pentane-3
-One was synthesized. Furthermore, it is reacted with paraformaldehyde under alkaline conditions to form a crosslinking agent [KZ-
3] was obtained.

Crosslinking agent [KZ-3]

Embedded image

Obtainment of Binder Polymer [BP-1] Poly (p-hydroxystyrene) and Marca Linker MS-4P (trade name) manufactured by Maruzen Petrochemical Co., Ltd. were obtained and designated as [BP-1].

Binder polymer [BP-1]

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Synthesis of Binder Polymer [BP-2] m-Cresol and formalin were polycondensed under an acid catalyst to obtain a novolak resin having a weight average molecular weight of 3,000.
And

Binder polymer [BP-2]

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Synthesis of Binder Polymer [BP-3] 2- (p-Hydroxyphenyl) ethanol and methacrylic acid were subjected to a dehydration reaction under an acid catalyst to synthesize 2- (p-hydroxyphenyl) ethyl methacrylate. Furthermore, radical polymerization was carried out using 2-methoxyethanol as a solvent and an azo-based polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), followed by reprecipitation of water to obtain a polymer [BP-3]. . The weight average molecular weight was 56,000 (polyhydroxystyrene standard). The structure of [BP-3] is shown below.

Binder polymer [BP-3]

Embedded image

Synthesis of Binder Polymer [BP-4] The sodium salt of p-styrenesulfonic acid was reacted with thionyl chloride to give p-styrenesulfonyl chloride.
Subsequently, it was reacted with 3,5-dimethoxyaniline in the presence of pyridine to synthesize p- (N- (3,5-dimethoxyphenyl) aminosulfonyl) styrene. further,
Furthermore, radical polymerization was carried out using 2-methoxyethanol as a solvent and an azo-based polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), followed by reprecipitation of water to obtain a polymer [BP-4]. . The weight average molecular weight was 72,000 (polyhydroxystyrene standard). The structure of [BP-4] is shown below.

Binder polymer [BP-4]

Embedded image

(Examples 1 to 6) 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 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, etched, washed with water, and 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, this 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 with water 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], six types of solutions [P-1] to [P-6] were prepared by changing the types of the crosslinking agent and the binder polymer of the present invention. This solution was applied to the above-mentioned primed aluminum plate,
Dried at 0 ° C for 1 minute to form a negative type lithographic printing plate [P-1]
To [P-6] were obtained. The weight after drying was 1.4 g / m ² .

Solution [P] Crosslinker 0.5 g Binder polymer 1.5 g Acid generator [SH-1] 0.3 g Infrared absorber [IK-1] 0.1 g Colorant [AIZEN SPILON BLUE C-RH Hodogaya Chemical Co., Ltd.] 0.035 g Fluorosurfactant [Megafac F-177, manufactured by Dainippon Ink and Chemicals, Inc.] 0.01 g Methyl ethyl ketone 14 g Methyl alcohol 4 g 1-methoxy-2-propanol 10 g

Table 1 shows the crosslinking agents and binder polymers used in the solutions [P-1] to [P-6]. The acid generator [SH-1] and the infrared absorber [IK-
1] is shown below.

[0109]

Embedded image

[0110]

Embedded image

The obtained negative type lithographic printing plate material [P-1]
To [P-6] were scanned and exposed with a semiconductor laser emitting infrared light having a wavelength of about 830 to 850 nm. After the exposure, the film was subjected to a heat treatment at 110 ° C. for 15 seconds with a panel heater, and then developed with a developer manufactured by Fuji Photo Film Co., Ltd., DP-4 (1: 8 water diluent). The amount of energy required for recording was calculated based on the line width and laser output of the obtained image, the loss in the optical system, and the scanning speed. Table 1 shows the results.
In each case, recording was possible with an energy amount of 200 mJ / cm ² or less.

[0112]

[Table 1]

(Comparative Example 1) The solution [P-
1], instead of the phenol derivative of the present invention,
Solution [Q-1] was prepared using compound [HR-1] having the following structure. This solution was applied to the undercoated aluminum plate used in Example 1 and dried at 100 ° C. for 1 minute to obtain a negative type lithographic printing plate [Q-1]. The weight after drying was 1.4 g / m ² . An image was formed on the obtained lithographic printing plate material [Q-1] in the same manner as in Example 1. When the amount of energy required for recording at this time was calculated, 230 mJ / cm ² of energy was required.

[0114]

Embedded image

From Examples 1 to 6 and Comparative Example 1, it is found that the negative image recording material of the present invention requires a low energy amount for laser recording and has high sensitivity. Example 7 Using the negative type lithographic printing plate [P-1] obtained in Example 1, printing was performed with a Heidel KOR-Z machine, and the number of obtained good printed matters was observed. Good prints were obtained up to 40,000 sheets or more from the beginning of printing. (Comparative Example 2) Using the negative type lithographic printing plate [Q-1] obtained in Comparative Example 1, printing was performed by a Heidel KOR-Z machine, and the number of obtained good printed matters was observed. Good prints were obtained only up to 40,000 sheets from the beginning of printing.

[0116]

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 having excellent recording sensitivity.

Claims (1)

[Claims] (A) a compound which is cross-linked by an acid,
(B) a binder polymer, (C) a compound that generates an acid by heat, and (D) an infrared absorber, wherein the (A) compound that is crosslinked by an acid is represented by the following general formula (I). A negative-type image recording material comprising at least one binuclear phenol derivative. Embedded image In the formula, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent. X represents a linking group consisting of three or more nonmetallic elements containing at least one carbon atom. R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms;
R ³ and R ⁶ are each independently a hydrogen atom or — (R ⁷
O) shows the _m -R ^8, wherein R ⁷ represents a divalent hydrocarbon group having not more than 12 carbon atoms, R ⁸ represents a hydrogen atom or a hydrocarbon group having 12 or less carbon, m is 0 Represents an integer of 1 to 3. When both R ³ and R ⁶ are-(R ⁷ O) _m -R ⁸ ,
R ⁷ , R ⁸ and m are independent of each other. k1, k
2 independently represents an integer of 2 to 4; n1 and n2 each independently represent an integer of 1 to 3.