JP2001310567A - Thermally sensitive direct type lithographic original printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic original printing plate obtainable in an inexpensive price which dissolves the problems inherent to the ordinary direct type offset printing materials, having the characteristics of a high anti-wearing plate with a high dimensional accuracy in a planographic printing. SOLUTION: A three-dimensionally cross linked binding polymer is employed to make a flat boad type original film from a hydrophilic binding polymer having a formyl group intramolecularly. In this way, a lithographic original printing plate can be provided in a simple way with an inexpensive price, having the characteristics of a high anti-wearing plate with a high dimensional accuracy, further, enabling one to avoid any generation of waste-disposals since no developing process is involved during the plate-making process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive direct lithographic original plate which does not require development and has excellent printing durability.

[0002]

2. Description of the Related Art With the spread of computers, various plate making methods have been proposed along with the plate material composition. From a practical point of view, it is common practice to create a positive or negative film from the block and print it on the lithographic printing plate precursor.However, an electrophotographic plate or a silver halide photographic plate that makes a plate directly from the block without passing through the film , Or electronic typesetting, DTP
A so-called computer-to-plate (CT) that directly prints on a plate material with a laser or thermal head and prints the plate without visualizing the print image information edited and created by
P) type planographic materials are coming. Although these have not yet been put to practical use, the CTP type is particularly expected in fields such as newspaper production where CTP has been completed since the plate making process can be rationalized and shortened, and material costs can be reduced.

As such a CTP plate material, there is known a plate material which is made by photosensitivity, heat sensitivity or electric energy. The photosensitive type plate material is prepared by applying materials such as organic semiconductor, silver salt + photosensitive resin, and high sensitivity photosensitive resin, printing by light irradiation with Ar laser, semiconductor laser, etc., and then developing and making plate. You. However, these plate materials require a large and expensive manufacturing apparatus, and the plate price is higher than conventional PS plates. Therefore, these plate materials and plate making processes have not been put to practical use. In addition, they also have the problem of disposal of the developer. In addition, there is a silver halide photographic plate for light printing, but since printing durability is low, it is used only for light printing.

[0004] Plate materials for plate making using electric energy (European Patent Publication No. 200,488, etc.) are also known, but these require a large-scale plate making device and some of them are generally used for plate making on a printing plate cylinder. Some lacked gender. Some heat-sensitive plate materials have been developed for light printing applications such as in-house printing. JP-A-63-64747 and JP-A-1-113290 disclose that a hot-melt resin and a thermoplastic resin dispersed in a heat-sensitive layer are melted by thermal printing, and the heated portion changes from hydrophilic to lipophilic. The plate material to be used is disclosed in U.S. Pat. Nos. 4,034,183 and 4,063,949.
Discloses plate materials for irradiating a hydrophilic polymer provided on a support with a laser to remove the hydrophilic group and convert the hydrophilic polymer to lipophilic.

A type in which a microencapsulated hot-melt material is applied to a support and the heating portion is changed to lipophilic (Japanese Patent Laid-Open No. 3-108588), a microencapsulated hot-melt material and a silicone resin Apply with
A type in which the heating unit is changed to lipophilic and printing is performed without dampening solution (Japanese Patent Laid-Open No. 5-8575) is known. However, none of the microencapsulated hot melts has reactivity. A type in which a blocked isocyanate is used as a lipophilic component together with an active hydrogen-containing binder polymer on a support having a hydrophilic surface, and after printing, the non-printed portion is washed away (Japanese Patent Application Laid-Open Nos. 62-164596 and 62-164049). Japanese Patent Application Laid-Open No. 3-52991 discloses a plate material in which an upper heat-melting layer is perforated to expose a lower hydrophilic layer (or a lipophilic layer).

On the other hand, a type in which an oily substance is heated on a support and transferred to a hydrophilic surface (US Pat. No. 3,964,964)
389, JP-A-1-209135 and 3-539
In addition, there is also known a plate material in which a sulfonic acid group is introduced into a polyolefin sheet, printing is performed with a thermal head, and the surface concentration of the sulfonic acid group is reduced to form an image area (U.S. Pat. 965, 322).

Further, as one of the direct type lithographic printing materials, there is a direct drawing type lithographic material in which an image portion is formed on the surface of a hydrophilic layer by an external means such as ink jet or toner transfer. There is also known a direct-printing type plate material in which a converted non-reactive heat-fusible substance is applied and a toner receiving layer is provided by heating printing (Japanese Patent Application Laid-Open No. Sho 62-1587). The printing plate is formed only after the lipophilic toner or the like is fixed to the formed toner receiving layer, and the image portion is not formed after printing. These conventional plate materials for heat-sensitive lithographic printing all have poor printing durability or poor oleophilicity, and thus have limited applications. In many cases, wet development is required in the plate making process.

[0008]

As described above, the prior arts have problems in plate performance, plate making equipment, plate making workability, plate materials and plate making, the cost of equipment, and the implementation on a commercial level. there were. Accordingly, an object of the present invention is to solve the above-described problems of the conventional direct offset printing plate material. That is, an object of the present invention is to supply a lithographic printing original plate from which a lithographic printing plate having high printing durability and high dimensional accuracy can be obtained at a low price. Still another object of the present invention is to provide a lithographic printing plate precursor that does not require a developing step that requires waste treatment of a developer or the like in the plate making step, and that can perform plate making without using a dedicated large-scale and expensive plate making apparatus.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and completed the present invention. That is, the present invention provides [1] a lithographic original plate comprising a hydrophilic binder polymer having a formyl group in a molecule, wherein the binder polymer is three-dimensionally crosslinked. [2] The hydrophilic binder polymer having a formyl group is represented by the following formula (1)

[0010]

Embedded image ^{_{CH 2 = CR 1 - (C}} (= O)) p- (O (CH 2) m) nNHCHO (1) ( wherein, R ¹ represents a hydrogen atom or a methyl group, m is 1
To 8 and n and p each represent an integer of 0 or 1. [1] The heat-sensitive direct plate precursor according to [1], wherein the hydrophilic binder polymer having a formyl group is a monomer having a structure represented by the following formula (2): ) [Formula 4]

[0011]

Embedded image wherein a monomer having a structure represented by CH ₂ ＣＲCR ¹ —NHCHO (2) (wherein R ¹ represents a hydrogen atom or a methyl group) is a constituent component. The heat-sensitive direct plate original plate according to [2].

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail. In the present invention, the recording system is laser-based, and the high temperature energy generated at that time causes a part of the polymer chain to be cut, so that the printing portion becomes hydrophobic and printing is performed. The hydrophilic binder polymer having a formyl group in the molecule as referred to in the present invention has a monomer having a structure represented by the formula (1) or (2) as its constituent component. In the formula (1), R ¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Also, m is 1 to 8
Represents an integer of 1 to 3, more preferably 1 to 3. Equation (2)
In the formula, R ¹ represents a hydrogen atom or a methyl group, and a hydrogen atom is more preferable. Therefore, a preferred compound represented by the formula (1) is N-vinylformamide, which is available from Mitsubishi Chemical Corporation.

By using a monomer having a structural formula represented by the above formula (1) or (2) (that is, a compound having a formyl group in a side chain) as a monomer constituting the hydrophilic binder polymer, Even in the printing of the laser-irradiated portion with a low energy, the side chain functional group is sufficiently eliminated, and the printed portion can be made sufficiently hydrophobic. As a result, printing can be performed with high resolution even at the edge portion.

The ratio of the structural units based on the monomers represented by the above formulas (1) and (2) is 5 to 8 in terms of the constituent monomer ratio.
5 mol%. More preferably, it is 10 to 50 mol%. When the proportion is in the range of 5 mol% to 85 mol%, the resolution of the recorded image after recording is preferably high.

Further, the hydrophilic binder polymer of the present invention may be obtained by copolymerizing the monomers represented by the above formulas (1) and (2) with other hydrophilic monomers. As the other hydrophilic monomer to be copolymerized, a conventionally known one can be used. In addition, the ratio may be appropriately determined experimentally by the following method for each sample depending on the type of the hydrophilic functional group used. That is, the hydrophilicity of the hydrophilic binder polymer of the present invention is determined by conducting a printing test described in Examples on a hydrophilic binder polymer cross-linked on a support, and confirming whether or not ink adheres to printing paper, or determining whether or not ink has been printed before and after printing. Difference in reflection density of paper in the image area (for example, reflection density meter DM4 manufactured by Dainippon Screen Mfg. Co., Ltd.)
(Measured at 00).

When the evaluation is performed by this method, the observation is made with the naked eye,
Acceptable if no ink stain is observed, disallowed if accepted, or the difference between the paper reflection density of the non-image area after printing and the paper reflection density before printing is 0.02 or less, and exceeds 0.02 The case is not allowed.

Although the hydrophilic binder polymer of the present invention repels ink and constitutes a non-image portion, it must have a three-dimensional crosslinked structure. By having a three-dimensionally crosslinked structure, the hydrophilic layer does not swell with fountain solution, maintains the adhesive strength with the support and the mechanical properties of the hydrophilic layer, and exhibits high printing durability.

The three-dimensional crosslinked structure may be formed before plate making, or simultaneously with or after printing. From the viewpoint of preventing scratches during handling and printing of the hydrophilic layer component, which has been melted by heat, to the thermal head when printing with a thermal head, it is preferable that the three-dimensional crosslinked structure has been formed before plate making. Those in which the hydrophilic binder polymer does not have a three-dimensional crosslinked structure before plate-making can also be used as a lithographic material.

The hydrophilic binder polymer having a three-dimensional cross-linked structure in the present invention refers to a polymer composed of carbon-carbon bonds, as a side chain, a carboxyl group, an amino group, a phosphoric acid group, a sulfonic acid group, or any of these. A salt, a hydroxyl group, an amide group, a networked polymer containing one or more kinds of hydrophilic functional groups such as polyoxyethylene groups, or a carbon atom, and any one of carbon-carbon bonds is at least one kind or more. Carboxyl group, amino group, phosphoric acid group, sulfonic acid group, or a salt, hydroxyl group, amide group, polyoxyethylene group, etc. of a polymer linked by a hetero atom composed of oxygen, nitrogen, sulfur, and phosphorus or a side chain thereof Is a networked polymer containing one or more kinds of hydrophilic functional groups, and specifically, poly (meth)
Acrylate type, polyoxyalkylene type, polyurethane type, epoxy ring-opening addition polymerization type, poly (meth) acrylic acid type, poly (meth) acrylamide type, polyester type, polyamide type, polyamine type, polyvinyl type, polysaccharide type or the like A polymer such as a composite system can be exemplified.

In particular, a hydroxyl group, a carboxyl group or an alkali metal salt thereof, an amino group or a hydrogen halide salt thereof, a sulfonic acid group or an amine thereof,
Alkali metal salts, alkaline earth metal salts, amide groups or those having repeated combinations thereof, further having a hydrophilic functional group and a polyoxyethylene group partially overlapped with the main chain segment Is preferred because of its high hydrophilicity. In addition to these, those having a urethane bond or a urea bond in the main chain or side chain of the hydrophilic binder polymer are more preferable because not only the hydrophilicity but also the printing durability of the non-printed portion are improved.

The ratio of the hydrophilic functional group in the polymer is as follows:
Depending on the type of the main chain segment and the type of the hydrophilic functional group to be used, each sample may be appropriately determined experimentally by the method described below. That is, the hydrophilicity of the hydrophilic binder polymer of the present invention is determined by conducting a printing test described in Examples on a hydrophilic binder polymer cross-linked on a support, and confirming whether or not ink adheres to printing paper, or determining whether or not ink has been printed before and after printing. The evaluation is made based on the reflection density difference of the printed portion (for example, measured by a reflection densitometer DM400 manufactured by Dainippon Screen Mfg. Co., Ltd.).

In the case of evaluation by this method, observation with the naked eye
Acceptable if no ink stain is observed, disallowed if accepted, or the difference between the paper reflection density of the non-image area after printing and the paper reflection density before printing is 0.02 or less, and exceeds 0.02 The case is not allowed.

The hydrophilic binder polymer of the present invention may contain various other components described below, if necessary. Specific examples of the three-dimensionally crosslinked hydrophilic binder polymer of the present invention are shown below.

(Meth) acrylic acid or its alkali or amine salt, itaconic acid or its alkali or amine salt, 2-hydroxyethyl (meth) acrylate,
(Meth) acrylamide, N-monomethylol (meth)
Acrylamide, N-dimethylol (meth) acrylamide, 3-vinylpropionic acid or its alkali,
Amine salts, vinylsulfonic acid or its alkali,
Amine salt, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, allylamine or halogenated thereof Use at least one of hydrophilic monomers having a hydrophilic group such as a hydroxyl group such as a hydrochloride, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, an amide group, an amino group, and an ether group. To synthesize a hydrophilic homo- or copolymer.

A hydrophilic binder polymer having a functional group such as a hydroxyl group, a carboxyl group, an amino group or a salt thereof, or an epoxy group in the hydrophilic polymer utilizes these functional groups to form a vinyl group, an allyl group, a (meth) acrylic group. An ethylene addition polymerizable unsaturated group such as a group or a cinnamoyl group,
An unsaturated group-containing polymer into which a ring-forming group such as a cinnamylidene group, a cyanosinnamylidene group or a p-phenylenediacrylate group is introduced is obtained. If necessary, a monofunctional or polyfunctional monomer copolymerizable with the unsaturated group, a polymerization initiator described below, and other components described below are added, and the mixture is dissolved in an appropriate solvent to adjust a dope. This is coated on a support and subjected to three-dimensional crosslinking after drying or also as drying.

A hydrophilic binder polymer containing an active hydrogen such as a hydroxyl group, an amino group or a carboxyl group is added to the above active hydrogen-free solvent together with an isocyanate compound or a blocked polyisocyanate compound and other components described below to prepare a dope. Then, it is applied to a support and reacted after drying or while also drying to form a three-dimensional crosslink.

Glycidyl groups such as glycidyl (meth) acrylate are added to the copolymer component of the hydrophilic binder polymer.
A monomer having a carboxyl group such as (meth) acrylic acid can be used in combination. The hydrophilic binder polymer having a glycidyl group is used as a crosslinking agent such as α, ω-alkane or alkenedicarboxylic acid such as 1,2-ethanedicarboxylic acid and adipic acid, 1,2,3-propanetricarboxylic acid, trimellitic acid and the like. Polycarboxylic acid, 1,2-ethanediamine, diethylenediamine, diethylenetriamine, polyamine compounds such as α, ω-bis- (3-aminopropyl) -polyethylene glycol ether, ethylene glycol, propylene glycol, diethylene glycol, tetraethylene glycol, etc. Using a polyhydroxy compound such as oligoalkylene or polyalkylene glycol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, three-dimensional crosslinking can be performed by utilizing a ring opening reaction with these.

The hydrophilic binder polymer having a carboxyl group or an amino group may be used as a crosslinking agent such as ethylene or propylene glycol diglycidyl ether, polyethylene or polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
Three-dimensional crosslinking can be performed by using an epoxy ring-opening reaction using a polyepoxy compound such as 1,6-hexanediol diglycidyl ether or trimethylolpropane triglycidyl ether.

Polysaccharides such as cellulose derivatives, polyvinyl alcohol or partially saponified products thereof, glycidol homo- or copolymers, or hydrophilic binder polymers based on these are used for the above-mentioned functional groups capable of undergoing a cross-linking reaction by utilizing the hydroxyl groups contained therein. Groups can be introduced to provide a three-dimensional crosslinked structure in the manner described above.

Polyols or polyamines containing hydroxyl or amino groups at the polymer terminals, such as polyoxyethylene glycol, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, etc. The three-dimensional crosslinking can be carried out by the above-mentioned method using a polymer obtained by introducing an ethylene addition polymerizable unsaturated group or a ring-forming group into a hydrophilic polyurethane precursor synthesized from the above polyisocyanate.

The synthesized hydrophilic polyurethane precursor is
When it has an isocyanate group terminal, glycerol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylyl Compounds having active hydrogen such as amide, (meth) acrylic acid, cinnamic acid, and cinnamic alcohol, or (meth) acrylic acid, glycidyl (meth) acrylate, 2-isocyanate when they have a hydroxyl group or amino group terminal React with ethyl (meth) acrylate.

After applying a polybasic acid and a polyol or a polybasic acid and a polyamine, a network structure is formed by heating to form a three-dimensional crosslink, or a water-soluble colloid-forming compound such as casein, glue or gelatin is formed to form a three-dimensional crosslink by heating. May be formed.

Furthermore, hydroxyl groups such as homo- or copolymers synthesized from hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate and vinyl alcohol and allylamine, polysaccharides such as partially saponified polyvinyl alcohol and cellulose derivatives, and glycidol homo- or copolymers; There is also a method of forming a three-dimensionally crosslinked hydrophilic binder polymer by reacting a group-containing hydrophilic polymer with a polybasic acid anhydride having two or more acid anhydride groups in one molecule.

Examples of polybasic acid anhydrides include ethylene glycol bis-anhydrotrimellitate, glycerol tris-anhydrotrimellitate, 1,3,3a,
4,5,9b hexahydro-5- (tetrahydro-
2,5-dioxo-3-furanyl) -naphtho [1,2-
C] furan-1,3-dione, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,2,2
3,4-butanetetracarboxylic dianhydride and the like can be exemplified.

Further, urea formalin resin, melamine formalin, dicyandiamide formalin, alkoxymethyl group-containing melamine and the like can be exemplified. In particular,
Alkoxymethyl group-containing melamines are preferred.

The amount of the cross-linking agent in the present invention is preferably 5 to 45 parts by mass with respect to 100 parts by mass of the hydrophilic binder resin. Preferred for optimizing performance. Further, it is preferably 10 to 40 parts by mass.

The degree of cross-linking, such as the average molecular weight between cross-links, varies depending on the type of segment used, the type and amount of associative functional groups, and the like, but may be determined according to the required printing durability. Usually, the average molecular weight between crosslinks is set in the range of 500 to 50,000. If it is shorter than 500, it tends to be brittle, and if it is longer than 50,000, it may be unfavorable because it swells with fountain solution and printing durability is impaired. From the balance of printing durability and hydrophilicity, about 800 to 30,000, and more preferably about 1,000 to 10,000 is practical. The hydrophilic binder polymer of the present invention may be used in combination with the following monofunctional monomers and polyfunctional monomers.

Specifically, Shinzo Yamashita and Tosuke Kaneko, "Handbook of Crosslinking Agents," Taiseisha Publishing Co., Ltd. (1981); Kiyomi Kato, "Ultraviolet Curing System," published by Sogo Gijutsu Center (198).
9), edited by Kiyomi Kato, "UV / EB Curing Handbook (raw material)", Polymer Publishing Association (1985), supervised by Kiyoshi Akamatsu, "Practical technology of new photosensitive resin", CMC, pp. 102-14.
5, (1987), etc., N, N′-methylenebisacrylamide, (meth) acryloylmorpholine, vinylpyridine, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N
-Dimethylaminopropyl (meth) acrylamide,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
N, N-dimethylaminoneopentyl (meth) acrylate, N-vinyl-2-pyrrolidone, diacetone acrylamide, N-methylol (meth) acrylamide,
P-styrenesulfonic acid and its salt, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate (PEG number average molecular weight 400), methoxypolyethylene glycol (meth) acrylate ( Number average molecular weight of PEG 100
0), butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate , Polyethylene glycol di (meth) acrylate (PEG number average molecular weight 4
00), polyethylene glycol di (meth) acrylate (PEG number average molecular weight 600), polyethylene glycol di (meth) acrylate (PEG number average molecular weight 1000), polypropylene glycol di (meth) acrylate (PPG number average molecular weight 400), 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane Or an acrylate thereof, β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxyethyl hadrogen succinate, polyethylene or polypropylene glycol mono (meth) acrylate, 3-chloro- 2-hydroxypropyl (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) ) Acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrafurfuryl (meth) acrylate, benzyl (meth) acrylate, mono (2-acryloyloxyethyl) acid phosphate or its methacrylic body, glycerin mono or di (meth) ) Acrylate,
Tris (2-acryloxyethyl) isocyanurate or its methacrylic product, N-phenylmaleimide, N-
(Meth) acryloxysuccinimide, N-vinylcarbazole, divinylethyleneurea, divinylpropyleneurea and the like.

When the three-dimensional crosslinking reaction of the hydrophilic binder polymer is carried out by using an ethylene addition polymerizable unsaturated group,
Use of a known photopolymerization initiator or thermal polymerization initiator is preferable from the viewpoint of reaction efficiency.

Examples of the photopolymerization initiator include benzoin, benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, Michler's ketone, xanthone, thioxanthone, chloroxanthone, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzyl, 2,2- Dimethyl-2-hydroxyacetophenone, (2-acryloyloxyethyl) (4-
Benzoylbenzyl) dimethyl ammonium bromide, (4
-Benzoylbenzyl) trimethylammonium chloride,
2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9-
On mesochloride, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, thiophenol, 2-benzothiazolethiol, 2-benzoxazolethiol, 2-benzimidazolethiol, diphenylsulfide, decylphenyl Sulfide, di-n-butyl disulfide, dibenzyl sulfide, dibenzoyl disulfide, diacetyl disulfide, dibornyl disulfide dimethoxyxanthogen disulfide, tetramethylthiuram monosulfide, tetramethylthiuram tetrasulfide, benzyldimethyldithiocarbamate quinoxaline, 1,3- Examples thereof include dioxolan, N-laurylpyridinium and the like. From these, what has absorption in the wavelength region of the light source used in the manufacturing process and dissolves or disperses in the solvent used when preparing the dope may be appropriately selected. Usually, those that dissolve in the solvent used are preferred because of their high reaction efficiency.

Examples of the cationic photopolymerization initiator include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts and the like. When this initiator is used, an epoxy group can also be used as a cross-linking reactive species. The aforementioned epoxy group-containing compound may be used as a crosslinking agent or a hydrophilic binder polymer, or an epoxy group may be introduced into the hydrophilic binder polymer. In the case of the photodimerization reaction, various sensitizers generally well known in the reaction, such as 2-nitrofluorene and 5-nitroacenaphthene, can be used. Other than the above, "Sensitizer" by Katsumi Tokumaru et al., Chapter 2, Chapter 4, published by Kodansha (1987), Kiyomi Kato, "Ultraviolet Curing System" (published by Sogo Gijutsu Center), pp. 62-147 (1989). , Fine Chemicals, Vol. 20 No. 4, 16 (199
Known polymerization initiators described in 1) can also be used.

The amount of addition can be in the range of 0.01% to 20% by weight based on the active ingredient excluding the solvent in the dope. If the amount is less than 0.01% by weight, the effect of the photoinitiator is not exerted. If the amount is more than 20% by weight, the self-absorption of the actinic ray by the initiator makes it difficult for light to reach the inside, resulting in a desired printing durability. May not be able to demonstrate. Practically, it is preferable to determine the content in the range of 0.1 to 10% by weight according to the composition in consideration of the balance between the effect as an initiator and the background stain in the non-image area. As the irradiation light source, known light sources such as a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a chemical lamp can be used.

As the polymerization initiator, benzoyl peroxide,
Known materials such as persulfates such as 2,2-azobisisobutylnitrile, potassium persulfate, sodium persulfate and ammonium persulfate can be used.

When a laser is used for recording on the heat-sensitive direct printing plate of the present invention, a light-to-heat conversion material having an absorption band in an emission wavelength region of the laser to be used can be further used. Examples of such a substance include “JOEM Handbook 2 Absorb” written by Ken Matsuoka.
Tion Spectra of Dyes for D
iode Lasers "Bunshin Publishing (1990),
CMC Editorial Department, "Developments and Market Trends of Functional Dyes in the 90s" CMC (1990) Chapter 2, 2.3 Polymethine dyes (cyanine dyes), phthalocyanine dyes, dithiol metal complex dyes, There are dyes, pigments and dyes such as naphthoquinone, anthraquinone dyes, triphenylmethane dyes, aminium, diimmonium dyes, azo disperse dyes, indoaniline metal complex dyes, and intermolecular CT dyes.

Specifically, N- [4- [5- (4-dimethylamino-2-methylphenyl) -2,4-pentadienylidene] -3-methyl-2,5-cyclohexadiene-1 -Ylidene] -N, N-dimethylammonium acetate, N- [4- [5- (4-dimethylaminophenyl) -3-phenyl-2-pentene-4-yne-1-
[Ylidene] -2,5-cyclohexadiene-1-ylidene] -N, N-dimethylammonium perchlorate, N, N-bis (4-dibutylaminophenyl) -N
-[4- [N, N-bis (4-dibutylaminophenyl) amino] phenyl] -aminium hexafluoroantimonate, 5-amino-2,3-dicyano-8-
(4-ethoxyphenylamino) -1,4-naphthoquinone, N'-cyano-N- (4-diethylamino-2-methylphenyl) -1,4-naphthoquinonediimine, 4,
11-diamino-2- (3-methoxybutyl) -1-oxo-3-thioxopyrrolo [3,4-b] anthracene-5,10-dione, 5,16 (5H, 16H) -diaza-2-butylamino -10,11-Dithiazinaphtho [2,3-a: 2′3′-c] -naphthalene-1,4-
Dione, bis (dichlorobenzene-1,2-dithiol) nickel (2: 1) tetrabutylammonium, tetrachlorophthalocyanine aluminum chloride,
Examples thereof include polyvinyl carbazole-2,3-dicyano-5-nitro-1,4-naphthoquinone complex.

In addition, stearic acid, myristic acid,
Room temperature solid lubricants such as dilauryl thiodipropionate, stearic acid amide, and zinc stearate can be added in small amounts to the hydrophilic layer.

The support used in the present invention may be selected from known materials in consideration of the performance and cost required in the printing field. When high dimensional accuracy such as multicolor printing is required, and when used in a printing machine whose mounting method to the plate cylinder is completed according to the metal support, a metal support made of aluminum, steel, or the like is preferable. If high printing durability is required without multicolor printing, plastic support such as polyester is used.In fields where low cost is required, paper, synthetic paper,
A waterproof resin laminate or coated paper support can be used. The support itself may be subjected to a surface treatment in order to improve the adhesiveness to a material that comes into contact with the support. As an example of such surface treatment, in the case of an aluminum sheet, there are various polishing treatments and anodizing treatments, and in the case of a plastic sheet,
There are corona discharge treatment, blast treatment and the like.

An adhesive layer can be provided on the support as required, such as printing durability. Generally, when high printing durability is required, an adhesive layer is provided. The adhesive must be selected and designed according to the hydrophilic layer component and the support used. Acrylics, urethanes, celluloses, epoxies, etc. as described in Yamada Shozaburo's “Encyclopedia of Adhesion and Adhesion”, published by Asakura Shoten (1986), Japan Adhesion Association, “Adhesion Handbook”, published by Nihon Kogyo Shimbun (1980). An adhesive can be used.

The heat-sensitive lithographic original plate of the present invention can be produced by the following method. The above-mentioned components are well dispersed in a paint shaker, a ball mill, an ultrasonic homogenizer or the like together with the type thereof and a solvent selected according to a method of crosslinking a hydrophilic binder polymer, and the obtained coating solution (dope) is subjected to a doctor blade method, a bar coating method, It is coated on a support by a roll coating method or the like and dried to obtain a heat-sensitive lithographic printing material. When a component containing an ethylene addition-polymerizable unsaturated group is used, if necessary for storage stability, the above-mentioned known heat stabilizer is added to the dope at 0.0%.
You may add in the range of 1-5%.

Examples of the dope solvent include water, alcohols such as ethanol, isopropanol and n-butanol; ketones such as acetone and methyl ethyl ketone;
Diethylene glycol diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethers such as diethylene glycol, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane and decalin, dimethylformamide , Dimethyl sulfoxide, acetonitrile, or a mixed solvent thereof can be used.

The thickness of the coating film may be arbitrarily set between several μm and 100 μm. Normally, 1 from the relationship between performance and cost
A thickness of from 10 to 10 μm is preferred. If it is necessary to enhance the surface smoothness, calendering may be performed after coating and drying or after the three-dimensional crosslinking reaction of the hydrophilic binder polymer. In particular, if a high degree of smoothness is required, it is preferable to carry out after coating and drying.

In order to make a heat-sensitive lithographic original plate according to the present invention, a document / image created and edited by an electronic typesetting machine, a DTP, a word processor, a personal computer or the like is drawn and printed with a laser, and then irradiated with actinic rays. And the development process is completed without any process. A known light source can be used for the type of actinic ray, and it may be selected according to the wavelength characteristics of the photoreaction initiator or the sensitizer for the initiator used in combination.
Specific examples include chemical lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, germicidal lamps, and metal halide lamps. When mounting on an offset printing machine and printing,
If necessary, printing can be performed as it is after performing a normal etching process.

[0053]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
In the following description, parts are parts by mass unless otherwise specified. (1) Production example 1 of hydrophilic binder polymer [P-1] 200 g of water was placed in a separable flask having a size of 500 ml.
And heated to 80 ° C. in a nitrogen atmosphere. Then, mixed solution 1 (2-hydroxyethyl acrylate 6.85)
g, acrylamide 25.16 g, N-vinylformamide (manufactured by Mitsubishi Chemical Corporation) 14.25 g, water 50 g) and a mixed solution 2 (potassium persulfate 0.25 g, water 50 g) in a separable flask while stirring. For 2 hours. Thereafter, polymerization was continued at the same temperature for 2 hours to form a hydrophilic binder polymer P-1 (number average molecular weight by GPC: 1.5 × 10 ⁴ , contact angle of water-kerosene oil-in-water method: 160 ° or more). Obtained.

Hydrophilic binder polymer P-2 to 12
About the production example 1 (P) in the amount shown in Table 1 [Table 1].
Polymerization was carried out in the same manner as in -1).

[0055]

AAm; acrylamide 2-HEA; 2-hydroxyethyl acrylate Monomer 1; CH ₂ ＣＨCH—NHCHO (N-vinylformamide) Monomer 2; CH ₂ ＣC (CH ₃ ) —NHCHO (N -Methacrylformamide) monomer 3; CH ₂ ＣＨCHC (＝ O) OCH ₂ NHCHO monomer 4; CH ₂ ＣC (CH ₃ ) C (＝ O) OCH ₂ NHCHO monomer 5; CH ₂ ＣＨCH -C (= O) OCH ₂ CH ₂ NHCHO AAm 2-HEA Other (mol%) Production Example 2 P-2 60 10 Monomer 2 30 Example 2 Production Example 3 P-360 10 Monomer 3 30 Example 3 Production Example 4 P-4 6010 Monomer 4 30 Example 4 Production Example 5 P-5 60 10 Monomer 5 30 Example 5 Production Example 6 P-6 60 10 Monomer 10 Comparative Example 1 Production Example 7 P-7 88 10 Monomer 1 2 Example 6 Production Example 8 P-8 75 10 Monomer 1 15 Example 7 Production Example 9 P-9 15 10 Monomer 1 75 Example 8 Production Example 10 P-100 Body 1 100 Comparative Example 2 Production Example 11 P-11 88 10 Monomer 4 2 Example 9 Production Example 12 P-12 60 10 Acrylic acid 30 Comparative Example 3 Example 1 On a polyethylene terephthalate support having a thickness of 180 μm, A well-dispersed dope having the following composition was dispersed in a paint shaker at room temperature for 30 minutes in advance, and then applied with a blade coater.

Hydrophilic binder polymer; P-1 (15% solid content) 85.0 parts Cymel 385 (manufactured by Mitsui Cytec; 80% solid content) 15.0 parts NK5078 (Dye made by Nippon Sensitive Dye) 5.0 parts Then, it is air-dried for 30 minutes, and dried at 120 ° C. for 2 minutes in a vacuum dryer.
The film was dried for 0 minutes to form a film to obtain a lithographic printing original plate.

This original is connected to an electronic typesetting machine and
The printed image was thermally printed by a printing device equipped with a W semiconductor laser element. This plate is trimmed to a predetermined size, and an offset printing machine (HAMADA61, manufactured by Hamada Printing Machine Co., Ltd.)
1XL, using a hard blanket) and printing on high-quality paper (the used ink was a commercially available offset ink (manufactured by Dainippon Ink Co., Ltd.).
A one-fold dilution was used). Even after passing 20,000 copies, there was no background stain and the image portion could be printed clearly. Example 2 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-2, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was colored black, and plate inspection was easy. As a result of printing, printing was possible without background smear even after 30,000 copies. Example 3 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-3, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was colored black, and plate inspection was easy. As a result of printing, printing was possible without background smear even after 30,000 copies. Example 4 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-4, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was colored black, and plate inspection was easy. As a result of printing, printing was possible without background smear even after 30,000 copies. Example 5 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-5, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was colored black, and plate inspection was easy. As a result of printing, printing was possible without background smear even after 30,000 copies. Example 6 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-7, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was colored black, and plate inspection was easy. As a result of printing, printing was possible without background smear even after 20,000 copies. Example 7 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-8, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was colored black, and plate inspection was easy. As a result of printing, printing was possible without background smear even after 30,000 copies. Example 8 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-9, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was colored black, and plate inspection was easy. As a result of printing, printing was possible without background smearing even after passing 24,000 copies. Example 9 A lithographic printing plate precursor was obtained in the same manner as in Example 1, except that the hydrophilic polymer P-1 was changed to P-11, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was colored black, and plate inspection was easy. As a result of printing, printing was possible without background smear even after 20,000 copies. Example 10 Instead of a polyethylene terephthalate support, one side of a 200 μm thick aluminum sheet degreased with an alkali was
Apply acryloxypropyltrimethoxysilane and apply 50
Coating was carried out in the same manner as in Example 1 except that a support cured at 1 ° C. for 1 hour, air-dried for 30 minutes, and dried in a vacuum dryer at 120 ° C.
The mixture was allowed to react at 20 ° C. for 20 minutes to produce a lithographic original plate. The plate obtained without the development step had good visibility of the image area, and a clear printed matter without background smear was obtained even after exceeding 50,000 parts. Comparative Example 1 A lithographic printing original plate was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-6, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the entire image portion of the printing plate was colored black, and the background was very dirty and could not be used at all. Comparative Example 2 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-10, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate had high water repellency and was not printed on paper. Comparative Example 3 A lithographic printing plate precursor was obtained in the same manner as in Example 1 except that the hydrophilic polymer P-1 was changed to P-12, and plate making and printing were performed. After printing, printing was performed in the same manner as in Example 1. As a result of printing, the image portion of the printing plate was thinly colored in black over the entire surface, and the background was stained, which was not satisfactory. Further, as a result of printing, the entire background was stained after 10,000 copies.

[0058]

According to the present invention, since the non-image area is formed of a hydrophilic binder polymer, development is not required in the plate making process, and work such as management of a developing solution and appropriate treatment of waste liquid is not required, thereby improving work efficiency. , And cost reduction.
As a matter of course, the plate-making apparatus is smaller in size and requires higher accuracy than a plate material requiring development, and the mechanism is simpler, but the apparatus price can be designed lower. In addition, the image and non-image areas are three-dimensionally cross-linked, and the strength is considerably solid, so the printing durability is much better than the existing CTP plate. In addition, it has become practically usable as a plate material for full-scale printing such as newspaper rotary printing and form printing.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) G03F 7/033 G03F 7/033 (72) Inventor Yuko Suzuki 580-32 Takuji Nagaura, Sodegaura-shi, Chiba 580-32 Mitsui Chemicals Co., Ltd. (72) Inventor Takayuki Sanada No. 580-32, Takuji Nagaura, Sodegaura City, Chiba Pref. BA16 BA20 EA04 2H114 AA04 AA24 BA01 BA06 BA10 DA27 DA32 DA34 DA41 DA43 DA44 DA47 DA51 DA53 DA55 DA56 DA59 DA60 EA01 EA02 EA03 EA08

Claims (3)

[Claims] 1. A lithographic original plate comprising a hydrophilic binder polymer having a formyl group in a molecule, wherein the hydrophilic binder polymer is three-dimensionally crosslinked. 2. A hydrophilic binder polymer having a formyl group is represented by the following formula (1): ## STR1 ## CH ₂ ＣＲCR ^1- (C (−O)) p- (O (CH ₂ ) m) nNHCHO (1) (wherein, R ¹ represents a hydrogen atom or a methyl group, and m represents 1
To 8 and n and p each represent an integer of 0 or 1. 2. The direct heat plate precursor according to claim 1, comprising a monomer having a structure represented by the formula (1). 3. A hydrophilic binder polymer having a formyl group is represented by the following formula (2): CH ₂ ＣＲCR ¹ —NHCHO (2) (wherein R ¹ represents a hydrogen atom or a methyl group) The heat-sensitive direct plate precursor according to claim 1, comprising a monomer having a structure represented by the following formula: