JPH08234426A - Negative type image recording material - Google Patents

Abstract

PURPOSE: To enable recording independently of the wavelength of light emitted from a light source for exposure by incorporating a radiation absorbing material, a compd. having specified enol ether groups in each molecule and a linear polymer having acid groups and reacting thermally with the enol ether groups. CONSTITUTION: A radiation absorbing material, a compd. having at least two enol ether groups represented by the formula in each molecule and a linear polymer having acid groups and reacting thermally with the enol ether groups are incorporated. In the formula, each of R1 -R3 is H, an alkyl or aryl and two of them may bond to each other to form a satd. or olefinically unsatd. ring. The linear polymer is required only to have at least acid groups and may have acid and hydroxyl groups.

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 an offset printing master, and more particularly to a lithographic printing plate for so-called direct plate making which can be made directly from digital signals of a computer or the like.

[0002]

2. Description of the Related Art The development of lasers in recent years has been remarkable, and particularly solid-state lasers having an emission region from near infrared to infrared.
High-power and small-sized semiconductor lasers are easily available. These lasers are very useful as an exposure light source when making a plate directly from digital data of a computer or the like.

Conventionally, as a lithographic printing plate which can be directly drawn from digital data of a computer, a printing plate used in an electrophotographic system, a photopolymerization type printing plate in which exposure by an argon laser or a YAG laser and, if necessary, post-heating are combined,
It is known that a silver salt sensitive material is laminated on a photosensitive resin, a silver salt diffusion transfer type, a printing plate of a type in which a silicone rubber layer is destroyed by discharge or laser light.

In the case of using the electrophotographic method, charging, exposure and development processing are complicated, and the apparatus is complicated and large.
The photopolymerizable printing plate originally has a limited sensitivity, and it is difficult to use a small laser and it is difficult to handle in a bright room. The one in which the silver salt sensitive material is laminated and the one in which the silver salt diffusion transfer type is used have the drawbacks that the processing is complicated and the cost is high. Also,
The type in which the silicone rubber layer is destroyed by a laser has a problem in removing the silicone residue remaining on the plate surface.

As a technique capable of forming an image using these light sources, Japanese Patent Application Laid-Open No. 52-113219 discloses a compound (for example, a diazonium compound) which decomposes with light and heat and absorbs light to convert it into heat. A positive type recording material composed of substance particles capable of forming and a binder is disclosed. Further, JP-A-58-148792 discloses a positive type photosensitive and heat-sensitive recording material containing thermoplastic resin particles, a light-heat converting substance and a photo-crosslinking substance (for example, a diazonium compound) as main components. There is.

However, the recording material which can use the above laser as a light source has low sensitivity, and in the case of direct plate making,
Since the digital data of a computer or the like is directly written on the plate material by scanning the laser beam, the positive type material requires a considerable writing time. Therefore, there has been a demand for the development of a high-sensitivity negative type material capable of shortening the writing time and capable of solid-state laser / semiconductor laser (thermal mode) having an emission region from near infrared to infrared.

As described above, the lithographic printing plate capable of directly drawing from the digital data of the conventional computer is not sufficiently satisfactory. On the other hand, vinyl ether group-containing compounds are generally known as one type of polymerizable compounds. This vinyl ether group-containing compound is being developed mainly as a cationically polymerizable compound. Cationic polymerization is characterized in that it has no effect of inhibiting the polymerization of oxygen during polymerization and has a small volume contraction, as compared with radical polymerization. Therefore, the vinyl ether group-containing compound can be used as a UV curable resin in combination with a photo acid generator to form an ink, a paint,
Recently, it has been used to create 3D stereoscopic images.

This photoacid generator (photocationic polymerization initiator)
Known examples thereof include diazonium salts, sulfonium salts, iodonium salts, pyrilinium salts, thiopyrrinium salts, and the like. None of these combinations of cationic polymerization monomer and photoacid initiator have sufficient sensitivity. See Stephen C.
Lapin, Polymers Paint Color Journal, 179 (4237),
321 (1989) describes a highly sensitive photo-cationic polymerizable monomer.

Further, recently, by utilizing the property that a vinyl ether group is hydrolyzed in the presence of an acid, it can be used as a chemically amplified positive material also in combination with a photo-acid generator, as disclosed in JP-A-6-230574. JP-A-62-
It is disclosed in Japanese Patent No. 45971. Most of the practically effective photoacid generators used in this technology are 450 nm.
As the exposure light source is 450 n
Only those that emit light with a wavelength of m or less can be used.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a negative type image recording material capable of recording without depending on the emission wavelength of an exposure light source, and particularly from near infrared light to infrared light ( It is to provide a negative image recording material capable of recording by heat rays).

[0011]

Various negative-type image recording materials (hereinafter sometimes referred to as light-sensitive materials or photosensitive compositions) have been searched for in order to achieve the above-mentioned goals. A film prepared by dissolving a compound having two or more ether groups in the molecule and a linear polymer having an acid group in a solvent and dry-coating it on a support at a relatively low temperature effectively thermally crosslinks at a high temperature, The present invention has been reached by finding the fact that it is insoluble in an alkaline aqueous solution.

That is, the present invention includes (1) a substance that absorbs radiation, a compound having at least two enol ether groups represented by the following general formula (I) in the molecule, and an acid group having an enol ether group. A negative-type image recording material comprising a linear polymer that thermally reacts with a base.

[0013]

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In the formula, R ₁ , R ₂ and R ₃ represent hydrogen, an alkyl group or an aryl group, and may be the same or different. Also, two of them may combine to form a saturated or olefinically unsaturated ring. (2) On a support, a substance that absorbs infrared light or near infrared light, a compound having at least two enol ether groups represented by the general formula (I) in the molecule, and a line having an acid group A negative type image recording material which is a negative lithographic printing plate for direct plate making in the heat mode writing type characterized by containing a macromolecule. The present invention can achieve the above objects.

Preferred embodiments of the present invention include the following (3) to (10). (3) A substance that absorbs infrared light or near infrared light, a compound having at least two enol ether groups of the following general formula (I) in the molecule, and a line having an acid group and a hydroxyl group, on a support And a layer containing a macromolecule. (4) The image recording material according to (3) above, which uses a dye as a substance that absorbs infrared light or near infrared light. (5) The image recording material according to the above (3), which uses a pigment as a substance that absorbs infrared light or near infrared light. (6) The image recording material according to (3), wherein carbon black is used as a substance that absorbs infrared light or near infrared light. (7) The image recording material according to (3) above, which uses a polyester film as a support. (8) The image recording material according to (3) above, which uses an aluminum plate as a support. (9) A substance that absorbs infrared light or near infrared light, a compound having at least two enol ether groups of the general formula (I) in the molecule, and a line having an acid group and a hydroxyl group component, on a support. Negative image recording method, which comprises providing a layer containing a macromolecule, exposing a negative image recording material using a laser emitting near infrared light or infrared light, and then developing with alkaline water. (10) The negative image recording material as described in (3) above, which is a negative heat-sensitive lithographic printing plate.

The present invention thermally crosslinks a linear polymer having an acid group and a compound having two or more enol ether groups by heat energy obtained by absorbing radiation to form a negative image. It is a thing. The linear polymer used in the present invention may have at least an acid group,
Further, the linear polymer may have an acid group and a hydroxyl group.

Particularly, when the radiation is infrared light or near-infrared light, recording in the thermal mode can be made good, which is preferable. In the present invention, the substance that absorbs infrared light or near infrared light is preferably a dye from the viewpoint of developability after exposure, and is preferably a pigment because sensitivity is good. Carbon black is preferable because it has a wide absorption wavelength range and high sensitivity.

In the present invention, the use of polyester as the support is preferable in that it is light in weight and can form a light-transmitting image, and the use of an aluminum plate is excellent in dimensional stability and durability. The image recording material of the present invention is preferably a recording method in which the image recording material is exposed using a laser emitting infrared light or near infrared light and then developed with alkaline water.

When the image recording material of the present invention is a lithographic printing plate, it is preferably a heat mode writing type lithographic printing plate for direct plate making. The heat mode writing is to record on the image recording material by using an appropriate heat ray source, controlling the heat ray source based on digital data. The heat ray source at this time is a thermal head used in a facsimile machine or a thermal copying machine, or a laser emitting infrared light or near infrared light. For direct plate making, infrared light or near infrared light is used. Lasers that emit light are preferred.

The preferred light used in the present invention is near-infrared rays and infrared rays, of which infrared rays are also generally called heat rays, and when the recording of the present invention is carried out by infrared rays, the present invention can be said to be heat-sensitive.

The present invention will be described in detail below. In the present invention, a substance that absorbs radiation is a substance that absorbs light (radiation) and generates heat. Various pigments or dyes are used as such substances. As the pigment, commercially available pigments and color index (CI) handbooks,
Pigments recorded in "Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" (CMC Publishing, 1984) are used. it can.

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Examples include blue pigments, green pigments, fluorescent pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacrid pigments, dioxazine pigments, isoindolinone pigments. ,
Quinophthalone pigment, dyed lake pigment, azine pigment,
Nitroso pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic pigment, carbon black and the like can be used.

These pigments may be used without surface treatment or may be used after surface treatment. Surface treatment methods include resin or wack surface coating, surfactant attachment, reactive substances (eg, silane coupling agents, epoxy compounds, polyisocyanates, etc.)
It is possible to consider a method of binding the pigment to the surface of the pigment. The above surface treatment method is "property and application of metal soap" (Koushobo),
"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, and more preferably in the range of 0.05 μm to 1 μm. As a method of dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. As the disperser, ultrasonic disperser, sand mill, attritor, pearl mill, super mill, ball mill, impeller, disperser, KD
Mill, colloid mill, dynatron, three roll mill,
A pressure kneader and the like can be mentioned. Details are described in "Latest Pigment Application Technology" (CMC Publishing, 1986).

As the dye, commercially available dyes and literatures (for example, "Handbook of Dyes" edited by the Society of Synthetic Organic Chemistry, Showa 4)
The publicly known thing described in the 5-year publication can be used. Specific examples thereof include dyes such as azo dyes, metal chain salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes.

Among these pigments or dyes, those absorbing infrared light or near infrared light are particularly preferable.
Carbon black is preferably used as a pigment that absorbs infrared light or near infrared light. Examples of the dye that absorbs infrared light or near infrared light include, for example, JP-A-58-12.
No. 5246, No. 59-84356, No. 59-2028.
29, 60-78787 and the like, cyanine dyes described in JP-A Nos. 58-173696 and 58-18.
1690, 58-194595 and the like, methine dyes described in JP-A-58-112793 and 58-
224793, 59-48187, 59-73
No. 996, No. 60-52940, No. 60-63744.
Naphthoquinone dyes described in JP-A-58-
Examples thereof include squarylium dyes described in 112792, cyanine dyes described in British Patent 434,875, and the like.

Further, the near infrared absorbing agent described in US Pat. No. 5,156,938 is also preferably used. Further, a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, a trimethine thiapyrylium salt described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-181051, 5
8-220143, 59-41363, 59-
84248, 59-84249, 59-146.
Nos. 063 and 59-146061, pyranium compounds described in JP-A-59-216146, pentamethinethiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fair 5-135
The pyrylium compounds disclosed in JP-A-14 and JP-A-5-19702 are particularly preferably used.

Another particularly preferable example is the near infrared absorbing dyes described as the formulas (I) and (II) in US Pat. No. 4,756,993. These pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 2% by weight based on the total solid content of the image recording material.
It can be added to the image recording material in an amount of 0% by weight, more preferably 0.5 to 15% by weight. Addition amount is 0.
If it is less than 01% by weight, an image cannot be obtained, and if it is more than 50% by weight, stains are generated on the non-image portion during printing.

Next, the compound having two or more enol ether groups represented by the general formula (I) used in the present invention will be explained. Here, if the number of enol ether groups is one, crosslinking cannot be achieved and the effect of the present invention cannot be effectively obtained. In the enol ether group of the general formula (I), when R ₁ , R ₂ and R ₃ are aryl groups, they are generally 4
Having from 20 carbon atoms, an alkyl group, an aryl group,
It may be substituted with an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylmercapto group, an aminoacyl group, a carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom.

When R ₁ , R ₂ and R ₃ represent an aryl group, it represents a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, a halogen atom, a cyano group,
It may be substituted with an ester group, an oxy group, an alkoxy group, an aryloxy group or an aryl group. Also,
When any _{two of} R ₁ , R ₂ and R ₃ are combined to form a cycloalkyl group or a cycloalkenyl group, it usually represents 3 to 8, preferably 5 or 6 ring members.

In the present invention, among the enol ether groups represented by the general formula (I), it is preferable that _one of R ₁ , R ₂ and R ₃ is a methyl group or an ethyl group.
The remainder is an enol ether group having hydrogen atoms, and more preferred is a vinyl ether group in which R ₁ , R ₂ and R ₃ are all hydrogen. Although various compounds containing two or more enol ether groups can be used in the present invention,
These are compounds having a boiling point of 60 ° C. or higher under atmospheric pressure, and preferable compounds having a vinyl ether group include vinyl ether compounds represented by the following general formula (II) or (III).

[0032] A - _{[- O- (R 4 -O) n} -CH = CH 2 ] _m (II) A - _{[- B-R 4 -O-CH} = CH 2 ] _m (III) wherein, A Is an m-valent alkyl group, an aryl group or a heterocyclic group, B is -CO-O-, -NHCOO- or -NHCONH-, and R ₄ is a linear or branched alkylene group having 1 to 10 carbon atoms. , N is an integer of 0 or 1 to 10, and m is an integer of 2 to 6.

The compound represented by the general formula (II) is, for example,
Stephen. C. Lapin, Polymers Paint Color Journal,
179 (4237), 321 (1988), i.e., a reaction between a polyhydric alcohol or a polyhydric phenol and acetylene, or a reaction between a polyhydric alcohol or a polyhydric phenol and a halogenated alkyl vinyl ether. You can

Specific examples include ethylene glycol divinyl ether, triethylene glycol divinyl ether,
1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol Divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene Recall diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether,
Pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether,
1,2-di (vinyl ether methoxy) benzene, 1,
Examples thereof include 2-di (vinyl ether ethoxy) benzene and compounds represented by the following general formulas (II-1) to (II-41), but the compounds are not limited thereto.

[0035]

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[0036]

[Chemical 4]

[0037]

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[0038]

[Chemical 6]

[0039]

[Chemical 7]

[0040]

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[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

On the other hand, in the general formula (III) (B = CO-O-
In the case of) can be produced by reacting a polycarboxylic acid with a halogenated alkyl vinyl ether. Specifically, terephthalic acid diethylene vinyl ether, phthalic acid diethylene vinyl ether, isophthalic acid diethylene vinyl ether, phthalic acid dipropylene vinyl ether, terephthalic acid dipropylene vinyl ether, isophthalic acid dipropylene vinyl ether, maleic acid diethylene vinyl ether, fumaric acid diethylene vinyl ether, itaconic acid diethylene. Examples thereof include vinyl ether, but are not limited thereto.

Further, as the enol ether group-containing compound preferably used in the present invention, the following general formula (I
Examples thereof include enol ether group-containing compounds synthesized by reacting an enol ether compound having active hydrogen represented by V), (V) or (VI) with a compound having an isocyanate group. _{CH 2 = CH-X-R} 5 -OH (IV) CH 2 = CH-X-R 5 -COOH (V) CH 2 = CH-X-R 5 -NH 2 (VI) wherein R ₅ is the number of carbon atoms 1-10 linear or branched alkylene groups are shown. X represents an oxygen atom or a sulfur atom. As the compound having an isocyanate group, for example, the compounds described in Crosslinking Agent Handbook (Taisei-sha, 1981) can be used.

Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, O- Polyisocyanate type such as tolylene diisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylol propane, adduct of hexamethylene diisocyanate and water, xylene di Examples thereof include polyisocyanate adduct types such as adducts of isocyanate and trimethylolpropane.

By reacting the above-mentioned isocyanate group-containing compound with the active hydrogen-containing enol ether group-containing compound, various compounds having an enol ether group at the terminal can be prepared. Examples of compounds having an enol ether group used in the present invention are listed below, but the scope of the present invention is not limited thereto.

[0048]

[Chemical 12]

[0049]

[Chemical 13]

[0050]

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The compounds containing at least two enol ether groups in the molecule described above can be used alone, but may be used as a mixture of several kinds. The addition amount of the compound containing an enol ether group in the photosensitive composition is generally 1 to 80 relative to the total solid content of the photosensitive composition.
%, Preferably 5 to 50% by weight. Within this range, thermal cross-linking is efficiently performed, and a negative image film having high film strength can be obtained.

Next, the linear polymer having an acid group, which is used in the present invention, and which reacts thermally with an enol ether group-containing compound will be described. This linear polymer thermally crosslinks with a compound having at least two enol ether groups,
Any three-dimensional cross-linking resin can be selected and used.

The above linear polymer can be generally synthesized by a known method for obtaining a linear polymer. For example, vinyl having an acid group, preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, etc. It can be obtained by copolymerizing monomers with other vinyl monomers copolymerizable therewith. Examples of the acid group-containing vinyl monomer used in the present invention include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, isocrotonic acid, p-vinylbenzoic acid, p-vinylbenzenesulfonic acid, p- Examples thereof include, but are not limited to, vinyl cinnamic acid, maleic acid monomethyl ether, and maleic acid monoethyl ether.

Other monomers copolymerizable with the above monomers include, for example, acrylonitrile, acryloamide,
Methacrylamide, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, vinyl benzoate, vinyl chloride, vinylidene chloride, styrene, vinyl acetate, N- ( 4-sulfamoylphenyl)
Methacrylamide, N-phenylphosphonylmethacrylamide, butadiene, chloroprene, isoprene, 2-
Hydroxyethylstyrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, p-
Examples thereof include 2-hydroxyethylstyrene, p-hydroxystyrene, 3-mercaptoethyl acrylate, and 2-mercaptoethyl methacrylate, but are not limited thereto.

The vinyl monomer containing an acid group and the other copolymerizable monomer can be copolymerized in any combination and in any number, but the vinyl monomer containing an acid group can be copolymerized with another monomer. The proportion of the polymerizable monomer is, by weight, in the range of 2 to 80:90 to 20, and the preferable range is 5 to 70:95 to 30,
A more preferable range is 5 to 30:95 to 70.

The linear polymer having an acid group and a hydroxyl group is
It can be obtained by cocondensation of a dihydroxy compound having an acid group and a dicarboxylic acid compound. For example 3,5-
Dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid ,
Dihydroxy compounds having an acid group such as bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, 2,4-tolylene diisocyanate, and 2,4-tolylene diisocyanate Dimer of nato, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), etc. By reacting the diisocyanate compound (1) in an equivalent amount, a linear polyurethane resin containing a carboxyl group can be obtained. Further, a diol compound which does not have a carboxyl group and may have another substituent which does not react with isocyanate may be used in combination. For example, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,3
-Butylene glycol, bisphenol A, hydrogenated bisphenol A, hydrogenated bisphenol F, bisphenol A
Examples of the ethylene oxide adduct thereof include, but are not limited to, these.

Further, the linear polymer is a diol having the above-mentioned acid group, and, if necessary, the above-mentioned other diol and a difunctional carboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, itaconic acid, It can be obtained by co-condensing with adipic acid or the like. The ratio of the diol having an acid group to the other monomer unit is 2 to 8% by weight.
A range of 0:98 to 20 is suitable, a preferable range is 5 to 70:95 to 30, and a more preferable range is 5 to 30:95 to 70.

Examples of the linear polymer having an acid group and a hydroxyl group used in the present invention include a resin having a phenolic hydroxyl group. Specifically, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, novolak resin such as phenol / cresol formaldehyde resin, and resol type phenol. Resins, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene,
Examples thereof include acrylic resins having a phenolic hydroxyl group, but are not limited thereto.

The molecular weight of the linear polymer having an acid group of the present invention is 1,000 to 1,000,000, preferably 1,
500 to 200,000, more preferably 2,000 to
It is 100,000. Among these, the linear polymer preferably used includes a copolymer containing a monomer containing an acid group and a monomer containing a hydroxyl group in a fixed ratio. The content of the monomer containing an acid group in the copolymer is 5 to 50% by weight, preferably 5 to 4
0% by weight, more preferably 10 to 30% by weight, and the content of the hydroxyl group-containing monomer is 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight. Particularly preferably used.

The linear polymer used in the present invention can be used alone, but may be used as a mixture of several kinds. The amount of linear polymer added to the photosensitive composition is generally 1 to 95% by weight, preferably 20% by weight, based on the total solid content of the photosensitive composition.
To 90% by weight, more preferably 30 to 80% by weight. Within this range, thermal cross-linking is efficiently performed, and a negative image film having high film strength can be obtained.

The image recording material of the present invention is coated on a support using a solvent that dissolves or disperses the above-mentioned components. As the solvent used here, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- There are methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, ethyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, etc. , These solvents are used alone or as a mixture.

A mixed solvent obtained by adding a small amount of water or a solvent which does not dissolve the diazo resin or polymer compound such as toluene to these solvents or mixed solvent is also suitable. The concentration (solid content) of the above components in the solvent is 1 to 50% by weight.
A liquid dissolved or dispersed in these solvents is applied and dried to form a film, but when a negative image recording material is produced, it is desirable to dry at 50 ° C to 100 ° C.

Alkyl ethers (eg ethyl cellulose, methyl cellulose) for improving coating properties, surfactants (eg fluorine-containing surfactants), plasticizers for imparting film flexibility and abrasion resistance. (For example, tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added.
The amount of these additives added varies depending on the purpose for which they are used, but is generally 0.5 to 0.5 based on the total solid content of the image recording material.
It is 30% by weight.

Further, as a printing-out agent for obtaining a visible image immediately after absorption of radiation, a combination of a compound which releases an acid by heat of exposure and an organic dye capable of forming a salt can be mentioned as a representative. Specifically, JP-A-50-362
No. 09, JP-A-53-8128 and combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye, and JP-A-53-362.
The combination of a trihalomethyl compound and a salt-forming organic dye described in JP-A No. 23, JP-A-54-74728 can be mentioned. As the image colorant, dyes other than the above-mentioned salt-forming organic dyes can be used.
Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue B.
OS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above,
Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B
(CI45170B), Malachite Green (CI42
000), methylene blue (CI52015) and the like.

These print-out agents and dyes are used in an amount of 0 to 30% by weight in the image recording material. When a visible image having a sufficient density can be obtained by the substance that absorbs radiation according to the present invention, it is not necessary to add such a dye.
Although the coating amount varies depending on the use, for example, in the case of a photosensitive lithographic printing plate (heat-sensitive lithographic printing plate), generally, the solid content is preferably 0.5 to 3.0 g / m ² . Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate. Further, if necessary, a mat or a mat layer may be provided on the photosensitive film.

The support to which the image recording material of the present invention is applied is, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), such as aluminum (including aluminum alloy), zinc, Plates of metal such as copper, for example, plastics such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Film of
It includes paper or plastic film on which the above metal is laminated or vapor deposited. Of these supports, a polyester film or an aluminum plate is preferably used, and an aluminum plate is particularly preferable because it is remarkably dimensionally stable. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Further, in the case of a support having a surface of metal, especially aluminum, it is desirable to carry out an appropriate hydrophilic treatment. Examples of such a hydrophilic treatment include a mechanical method such as wire brush graining, brush graining in which a surface of an aluminum surface is roughened with a nylon brush while pouring a slurry of abrasive particles, ball graining, HF or AlCl ₃ , Graining the surface by chemical graining using HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or complex graining performed by combining these surface roughening methods, and then acidifying as necessary. It is possible to form a strong passivation film on the aluminum surface by etching treatment with alkali, and subsequently by anodizing with sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulphamic acid or mixed acid of these with direct current or alternating current power supply. preferable. The aluminum surface is hydrophilized by such a passivation film itself, but if necessary, US Patent 2,714,
Silicate treatment (sodium silicate, potassium silicate) described in US Pat. No. 066 and US Pat. No. 3,181,461, potassium zirconium fluoride treatment described in US Pat. No. 2,946,638, US patent 3,201,24
Phosphomolybdate treatment described in No. 7,
Alkyl titanate treatment described in British Patent No. 1,108,559, polyacrylic acid treatment described in German Patent No. 1,091,433, described in German Patent Nos. 1,134,093 and British Patent No. 1,230,447 Polyvinylphosphonic acid treatment described in JP-B-44-6409, U.S. Patent No. 3,307,
Phytic acid treatment described in Japanese Patent No. 951 and a composite of a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-16893 and JP-A-58-18291. Those treated with a hydrophilizing treatment by undercoating a water-soluble polymer having a sulfonic acid group described in JP-A-59-101651 are particularly preferable.
Other hydrophilic treatment methods include U.S. Pat. No. 3,658,662.
The silicate electrodeposition described in the specification can be mentioned.

Examples of the light source of actinic rays used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
Radiation includes electron beams, X-rays, ion beams, far infrared rays, and the like. Also, g-line, i-line, Deep-UV light, and high-density energy beam (laser beam) are used. Examples of the laser beam include helium / neon laser, argon laser, krypton laser, helium / cadmium laser, and KrF excimer laser. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser and a semiconductor laser are particularly preferable.

As the developing solution and replenishing solution for the image recording material of the present invention, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium silicate, third
Sodium phosphate, potassium, ammonium, second
Sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. Inorganic alkali salts such as 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 may be used alone or in combination of two or more.

Various surfactants and organic solvents can be added to the developing solution and the replenishing solution, if necessary, for the purpose of promoting or suppressing the developing property, dispersing the development residue and enhancing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. If necessary, the developer and replenisher
It is also possible to add a reducing agent such as sodium salt or potassium salt of an inorganic acid such as hydroquinone, resorcin, sulfurous acid or bisulfite, and further an organic carboxylic acid, an antifoaming agent or a water softener.

Among these developing solutions, particularly preferable ones are, for example, JP-A-54-62004 and JP-B-57-.
Those described in Japanese Patent No. 7427 and Japanese Patent Laid-Open No.
No. 1-77401, a developer composition comprising benzyl alcohol, an anionic surfactant, an alkaline agent and water, and benzyl alcohol, an anionic surfactant described in JP-A-53-44202. Developer, a developer composition comprising an aqueous solution containing a water-soluble sulfite, an organic solvent having a solubility in water of 10% by weight or less at room temperature, an alkaline agent, and water, as described in JP-A-55-155355. And a developer composition containing the same.

When the image recording material of the present invention is used as a printing plate, it is washed with the above-mentioned developing solution and replenishing solution and then rinsed with water, a rinse solution containing a surfactant, gum arabic and a starch derivative. It is preferably post-treated with a desensitizing solution. Various combinations of these treatments can be used for the post-treatment.

In recent years, automatic developing machines for printing plates have been widely used in the plate making / printing industry in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate, each processing liquid tank and a spraying device, which conveys an exposed printing plate horizontally while pumping it up with each pump. The processing liquid is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid for processing. In such automatic processing, it is possible to perform processing while supplementing each processing solution with a replenishing solution according to the processing amount, operating time, and the like.

Further, a so-called disposable processing method of processing with a substantially unused processing liquid can be applied.

The photosensitive lithographic printing plate using the image recording material of the present invention is subjected to imagewise exposure, development, washing with water and / or rinsing and / or gumming. For example, if there is a film edge mark of the original image film), the unnecessary image portion is erased. Such erasing can be carried out, for example, by applying an erasing liquid to an unnecessary image portion as described in Japanese Patent Publication No. 2-13293, leaving it as it is for a predetermined time, and then rinsing with water.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitizing gum, if desired.

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EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 [Production of Substrate] A substrate was produced by the method disclosed in JP-A-56-28893. That is, the thickness is 0.24 m
The aluminum plate of m was washed with water after the surface of the aluminum plate was grained using a nylon brush and an aqueous suspension of 400 mesh pumice. Then, it is immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, and then neutralized and washed with 20% HNO 3.
Washed with water. Next, this plate was subjected to 16% in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current under the conditions that the voltage at the anode was 12.7 V and the ratio of the electricity at the cathode to the electricity at the anode was 0.8.
The electrolytic surface-roughening treatment was performed with an electric quantity at the anode of 0 coulomb / dm @ 2. The surface roughness at this time was measured to be 0.6μ.
(Ra indication). Subsequently, it was immersed in 30% sulfuric acid and desmutted at 55 ° C. for 2 minutes, and then, in 20% sulfuric acid, at a current density of 2 A / dm 2, the thickness was 2.7 g / m 2.
Anodizing treatment was performed for 2 minutes so as to be 2. Then 70 ° C
Was immersed in a 2.5% aqueous solution of sodium silicate for 1 minute, washed with water and dried.

[Preparation of Carbon Black Dispersion] A composition having the following weight ratio was dispersed with glass beads for 10 minutes to obtain a carbon black dispersion. Carbon black 1 part by weight Copolymer of benzyl methacrylate and methacrylic acid 1.6 parts by weight (molar ratio 72:28, weight average molecular weight 70,000) Cyclohexanone 1.6 parts by weight Methoxypropyl acetate 3.8 parts by weight

[Preparation of negative photosensitive lithographic printing plate] The aluminum plate obtained above was coated with the following photosensitive solution, and 8
It was dried at 0 ° C for 2 minutes to obtain a negative photosensitive lithographic printing plate. The weight after drying was 2.0 g / m 2. Photosensitive solution Carbon black dispersion 10 g Compound II-11 3 in the text Benzyl methacrylate / 2-hydroxymethyl 10 g Methacrylate / methacrylic acid 60/20/20 molar ratio copolymer, weight average molecular weight 30,000 FC-430 (US 3M Fluorine-based surfactant) 0.1 g Methyl ethyl ketone 50 g After exposing the obtained negative-type photosensitive lithographic printing plate with a YAG laser adjusted to a plate surface output of 2 W, a developing solution manufactured by Fuji Photo Film Co., Ltd., DN- 3C (1: 1), gum solution FN-
When processed through an automatic processor equipped with 2 (1: 1), a negative image was obtained. When this lithographic printing plate was printed on a Heidel SOR-KZ machine, good printed matter was about 3
I got 10,000 copies. Comparative Example 1 In the photosensitive liquid composition of Example 1, an oil-soluble dye (Victoria Pure Blue BOH) was used instead of the carbon black dispersion.
A negative photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that 0.3 g was used. When this photosensitive lithographic printing plate was exposed and developed in the same manner as in Example 1, all the photosensitive film was dissolved in the developing solution, and no image was obtained.

Examples 2 to 4 Samples were prepared in the same manner as in Example 1 except that the compound of Table 1 was used in place of 3 g of the compound (II-11) in the composition of the photosensitive solution of Example 1, and the same procedure was carried out. Write with YAG laser,
After development, a negative image was obtained. When this printing plate was used and printed under the same conditions as in Example 1, the number of sheets shown in Table 1 and good printed matter were obtained.

[0083]

[Table 1]

Example 5 A negative photosensitive lithographic printing plate was obtained in exactly the same manner as in the photosensitive liquid composition of Example 1, except that the linear polymer was changed to the following resin.

[0085]

[Chemical 15]

The negative-working photosensitive lithographic printing plate thus obtained was exposed with a YAG laser adjusted to a plate surface output of 2 W, and then developed by Fuji Photo Film Co., Ltd., DN-3C (1: 1), gum solution FN-. When processed through an automatic processor equipped with 2 (1: 1), a negative image was obtained. When this lithographic printing plate was printed with a Heidel SOR-KZ machine, about 50,000 good prints were obtained.

Example 6 A negative photosensitive lithographic printing plate was obtained in the same manner as in Example 1 except that the following dye was used in place of the carbon black dispersion used in Example 1. Dye 2,6-di-t-butyl-4- {5- (2,6-di-t-0.02g butyl-4H-thiopyran-4-ylidene) -penta-1,3-dienyl} thiopyrylium Tetrafluoroborate (Compound described in U.S. Pat. No. 4,283,475) The obtained negative-type photosensitive lithographic printing plate was used with a semiconductor laser (wavelength 825 nm, spot diameter: 1 / e ² = 11.9 μ). , The plate surface output was adjusted to 110 mW at a linear velocity of 8 m / sec, and exposure was performed. Next, when the same developing treatment as in Example 1 was performed, a fine line having a line width of 10 μ could be formed.

Next, the beam diameter is adjusted to 6 μ (1 / e ² ) and similarly, the writing resolution of 4000 dpi is set to 20 μm.
After the exposure of the dot image of 0 lpi, the same process was performed to form a dot image. When the obtained lithographic printing plate was used to print on high-quality paper with a commercially available ink using a SOR-KZ type printer manufactured by Heidelberg, excellent printing durability was obtained as in Example 1. Comparative Example 2 A negative photosensitive lithographic printing plate was prepared in the same manner as in Example 6 except that 0.2 g of an oil-soluble dye (Victoria Pure Blue BOH) was used in place of the dye in the photosensitive liquid composition of Example 6. did. When this photosensitive lithographic printing plate was exposed and developed in the same manner as in Example 6, all the photosensitive film was dissolved in the developing solution, and no image was obtained.

[0089]

INDUSTRIAL APPLICABILITY The present invention can provide a negative image recording material capable of recording without depending on the emission wavelength of the exposure light source.
In particular, it is possible to obtain a negative image recording material capable of recording from near infrared to infrared (heat rays).

Claims (1)

[Claims] 1. A substance which absorbs radiation, a compound having at least two enol ether groups represented by the following general formula (I) in a molecule, and an acid group, which reacts thermally with an enol ether group. A negative image recording material containing a linear polymer. Embedded image In the formula, R ₁ , R ₂ and R ₃ each independently represent hydrogen, an alkyl group or an aryl group. Also, two of them may combine to form a saturated or olefinically unsaturated ring.