JPH02134636A - Lithographic printing plate material that does not require dampening water - Google Patents

Abstract

PURPOSE:To obtain the printing plate which does not generate scumming of the printing surface by incorporating the functional group of a compd. incorporated into a photosensitive compsn. forming a photosensitive layer and fluoroplastic having the functional group which can be bound by exposing into a fluoroplastic layer. CONSTITUTION:The fluoroplastic layer contains the functional group of the compd. incorporated into the photosensitive compsn. forming the photosensitive layer and the fluoroplastic having the functional group which can be bound by exposing. The functional group of the compd. incorporated into the non-image part of the photosensitive layer, therefore, forms crosslinking by reacting with the functional group in the fluoroplastic and the fluoroplastic layer and the photosensitive layer are securely bound. Developing latitude is widened in this way and the printing plate obtd. by this printing material is excellent in plate wear and the reproducibility of shadow parts and small dots. The generation of the scumming of the plate surface is obviated.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a lithographic printing plate material that does not require dampening water, and more specifically, has a wide development latitude, is hard to scratch the plate surface, and furthermore, when used for printing. The present invention relates to a lithographic printing plate material that does not require dampening water and can form a lithographic printing plate with good stiffness resistance.

[Background of the invention]

Conventionally, lithographic printing plate materials that do not require dampening water (hereinafter simply referred to as "plate materials") include those in which a photosensitive layer and an ink repulsion layer are coated on a support in order from the support side. This is known, and by exposing and developing this plate material, a lithographic printing plate (hereinafter also simply referred to as "printing plate J" for short) that does not require dampening water can be obtained.

A technique using a fluororesin as a material for forming the above-mentioned ink repellent layer is known, for example, in Japanese Patent Application Laid-Open No. 58-215
No. 411 discloses a plate material in which a copolymer formed from a specific fluorine-containing acrylic monomer and a monomer having a photosensitive group is used as an ink-repellent layer.

However, printing plates obtained from this plate material do not have sufficient printing durability and have the disadvantage of poor reproducibility of shadow areas and small dots.

Furthermore, although the above plate material can be developed with a developer containing a fluorine-based solvent such as Freon-113, perfluorohexane, and meta-xylene hexafluoride, it can be developed with a developer containing a solvent other than a fluorine-based solvent. Can not do it. As a result, it is difficult to select a developing solution9, and since the reaction activity of fluorine is strong, it is not easy to handle, and there are problems in waste liquid treatment. Furthermore, since fluorine-based solvents are generally very volatile, there is also the problem that developing solutions containing them cannot be used in automatic processors.

In addition, when the content of photosensitive groups in the plate material is increased in an attempt to improve the printing durability and reproducibility of the printing plate obtained from this plate material, the ink repellency of the obtained printing plate decreases. There is also the problem that background stains are more likely to occur.

On the other hand, with the conventional plate material in which a photosensitive layer and a fluororesin layer are coated on a support in order from the support side, the adhesion between the photosensitive layer and the fluororesin layer is insufficient, and no image is formed during development. It has the disadvantage that the fluororesin layer in the line portion is easily peeled off and the development latitude is narrow. Therefore, in order to improve the adhesion between the photosensitive layer and the fluororesin layer in such a plate material, for example, perfluoroalkyl having a metal atom and a functional group bonded to the metal atom in the ink repellent layer can be used. A plate material using an ink repellent layer formed from a compound is disclosed in WO 33-02175, and in this plate material, the presence of metal atoms can improve adhesion, and the thickness of the ink repellent layer can be reduced. The printing plate obtained from this plate material can be made extremely thin, with a thickness of less than 10 mm.
Although this printing plate has the characteristic of having high resolution, it also has the problem of insufficient printing durability and the occurrence of streak-like stains on the entire plate surface.

Therefore, the present inventors have conducted various studies in view of the above-mentioned circumstances, and have developed a lithographic printing plate material that does not require dampening water and has a photosensitive layer and a fluororesin layer on a support in this order from the support side. In this step, the functional groups of the compound contained in the photosensitive composition forming the photosensitive layer and the functional groups of the fluororesin forming the fluororesin layer are crosslinked by a photopolymerization reaction caused by exposure to light. This significantly improves the adhesion between the non-image areas of the photosensitive layer and the fluororesin layer, which widens the development latitude during development, and improves stiffness, shadow areas, and small dot reproducibility. We have discovered that it is possible to obtain a printing plate that has excellent properties and does not cause scumming on the plate surface.

[Object of the invention and structure of the invention]

The present invention was invented based on the above knowledge, and allows the use of a developer containing a solvent other than fluorine-based solvents, widens the development latitude during development processing, and improves printing durability and shadow areas. The purpose is to provide a lithographic printing plate material that does not require dampening water and can form a printing plate that has excellent reproducibility of small dots and does not cause scumming on the plate surface. , in a lithographic printing plate material that does not require dampening water and has a fluororesin layer, the fluororesin layer is bonded to a functional group of a compound contained in the photosensitive composition forming the photosensitive layer by exposure to light. This invention relates to a lithographic printing plate material that does not require dampening water and is characterized by containing a fluororesin having a functional group capable of forming a functional group.

[Effect]

In the plate material of the present invention, the plate material is formed by utilizing changes in the solubility or degree of swelling of the photosensitive layer in the developer, or changes in the degree of adhesion of the photosensitive layer to the fluororesin layer. Developing can be carried out using solvents other than fluorine-based as long as the solvent dissolves or swells.

In addition, in the plate material of the present invention, the functional groups of the compound contained in the non-image area of the photosensitive layer react with the functional groups in the fluororesin upon exposure to form a crosslink, thereby forming a bond between the fluororesin layer and the photosensitive layer. Since the layers are strongly bonded, the development latitude is widened, and the printing plate obtained from this plate material has excellent stiffness resistance and reproducibility of shadow areas and small dots, and does not cause scumming on the plate surface.

[Detailed description of the invention] The present invention will be explained in more detail below.

The lithographic printing plate material of the present invention that does not require dampening water has a
A photosensitive layer is sequentially provided from the support side, followed by a fluororesin layer, and this fluororesin layer reacts with a compound having a functional group among the compounds in the photosensitive layer.
It is preferable that the resin contains a fluororesin having a functional group capable of forming a bond with this functional group, and further contains a crosslinking agent.

First, to explain the fluororesin layer used in the present invention, this fluororesin layer acts as an ink repellent layer. It has a functional group that can form a bond with a functional group, and the following are used for this purpose.

(1) It has the following structural unit in the molecule, CFz--cr;'2--CF-1CF! −〇−CF
, -0- -CF-0 (the fluorine content is 30% arsenic or more, preferably 50% arsenic or less) and is capable of forming a bond with a compound in the photosensitive layer by exposure to light in the molecule. Fluororesin with functional groups that can be used.

Examples of the above-mentioned functional groups include addition-polymerizable unsaturated double bonds and epoxy groups, and these unsaturated double bonds and epoxy groups may be present in either the side chain or the main chain of the fluororesin; Of these, it is preferable that
Unsaturated double bonds are preferred.

This unsaturated double bond can be introduced into the fluororesin by, for example, the following method.

a. Copolymerizing a fluorine-containing acrylic monomer and allyl (meth)acrylate.

b, the fluororesin is -OH, -COOH, -NH,

When it has an active hydrogen functional group such as -N l-1-,
A compound having both a functional group and an unsaturated double bond capable of reacting with the above fluororesin, such as glycidyl methacrylate-1., m-isopropenyl-α, α-dimethylbenzyl isocyanate or 2-methacryloyloxyethyl isocyanate, is Make it react.

-OH, -COOH when it has both a functional group capable of reacting with active hydrogen and an unsaturated double bond.

A compound having an active hydrogen functional group such as NHZ, NH-, etc., such as pentaerythritol triacrylate, acrylic acid, 2-hydroxyethyl methacrylate, allylamine, is reacted with the fluororesin.

-OH or -NH when containing a group such as.

A compound having both an unsaturated double bond and an unsaturated double bond, such as pentaerythryl-1-monyl acrylate, 2-hydroxyethyl acrylate, and allylamine, is reacted with the above-mentioned fluororesin.

e. When the fluororesin has -OH or -NH2, -C-O-C- or a compound having both -COOH and an unsaturated double bond, such as tetrahydrophthalic anhydride, acrylic acid, maleic acid. is reacted with the above fluororesin. Further, the epoxy group can be introduced by copolymerizing a fluorine-containing acrylic monomer and glycidyl (meth)acrylate.

(2) have the structural units described in item (1) above in the molecule, and preferably react with each other directly or via a crosslinking agent to form bonds, thereby mutually Two or more fluororesins each having, for example, the following functional groups, forming a crosslinked fluororesin layer.

(3) It has a structural unit as described in the above item (1) in its molecule, and is preferably bonded by reaction with a functional group of a compound in the photosensitive layer directly or via a crosslinking agent. form,
For example, a fluororesin having the following functional groups, namely:

Either or both of the fluororesin layer and the photosensitive layer in the present invention optionally contain the crosslinking agent, and when this crosslinking agent is present, the functional groups are crosslinked with each other via this crosslinking agent, and the functional groups are crosslinked with each other via this crosslinking agent. The formation of a bond across the interface of the two layers results in improved adhesion between the two layers.

When the fluororesin used in the present invention contains a copolymer resin of a fluorine-containing monomer and a fluorine-free monomer, the fluororesin does not have the following functional groups in the molecule of the fluorine-containing monomer. Alternatively, the fluorine-free monomer may contain the fluorine in its molecule.

Specifically, the polymers exemplified below are preferably used as the copolymer resin.

■ Copolymer resin of perfluoroalkyl (meth)acrylate and allyl methacrylate■ Resin in which (meth)acrylic acid is added to the product obtained by copolymerizing perfluoroalkyl (meth)acrylate with glycidyl methacrylate■ Perfluoropolymer A resin in which glycidyl methacrylate is added to the product obtained by copolymerizing ether (meth)acrylate with (meth)acrylic acid■ Perfluoroalkyl (meth)acrylate is added to 2-
A resin in which 2-methacryloyl oxyneethyl isocyanate is added to a product obtained by copolymerizing with hydroxyethyl (meth)acrylate■ Perfluoropolyether (
Copolymer resin of meth)acrylate and allyl methacrylate ■ Resin obtained by adding 2-hydroxyethyl methacrylate to the product obtained by copolymerizing perfluoroalkyl (meth)acrylate with maleic anhydride Fluororesin used in the present invention is preferably a combination of a fluorine-containing acrylic monomer and a monomer having a functional group that can form a bond directly or via a crosslinking agent with a functional group of a compound contained in the photosensitive composition forming the photosensitive layer. This is a resin in which unsaturated double bonds are introduced into a copolymer resin or a fluororesin described in item (3) above by methods a to e.

The fluorine-containing acrylic monomer is preferably a monomer represented by the following general formula.

It is a fluorine polyether group, and R is a hydrogen atom or an alkyl group. ] As such a fluorine-containing acrylic monomer, the following monomers are further preferred.

C11z-8CII-C-0-C1l□(CF2)41
1 [wherein, Rf is a substituted fluoroalkyl group or substituted CF]
* (CF Z)? SO□N(Czlh) (C11
ri zOcOcH=cHzCF z (CF z) i
, 0cOcH=clI□ It is also preferable that the third monomer is copolymerized. Here, as the third monomer,
For example, styrene, methyl methacrylate (MMA),
Examples include butyl acrylate, acrylonitrile and ethyl acrylate.

When the third monomer is copolymerized with the fluorine-containing resin used in the present invention, the third monomer has the following functional group in the molecule, i.e., the functional group of the compound in the photosensitive layer. Preferred examples of monomers having functional groups capable of reacting with groups or crosslinking agents include glycidyl methacrylate, methacrylic acid, maleic anhydride, and 2-hydroxy methacrylate.

The fluorine-containing resin used in the present invention is a copolymer resin of the above-mentioned fluorine-containing acrylic monomer and a monomer having a functional group capable of reacting with the functional group of the compound in the photosensitive layer or the crosslinking agent. You may stay for a while.

(1) In the present invention, when the fluororesin and the compound in the photosensitive layer form a direct bond, for example, the following fluororesin and the compound in the photosensitive layer are used in combination, and each of them is used in combination. In this case, the following crosslinking agents may be added to the fluororesin layer.

■Fluororesin: 011. C0OH, NHz
.

Fluororesin with Crosslinking agent: -OH, -COOH in the molecule.

Active hydrogen reactive groups such as -NH2, -NH- or -NGO
Compounds having a functional group capable of reacting with active hydrogen, such as compounds having a functional group capable of reacting with active hydrogen, such as Compounds in the fluororesin photosensitive layer having a functional group capable of reacting with active hydrogen: -OH in the molecule.

-COOH, -NH□, -NH-, etc. compounds in the fluororesin photosensitive layer having active hydrogen ash: Compounds having -OH or -NH2 in the molecule Crosslinking agent having -OH or -NH in two molecules Compound ■ Compound in the fluororesin photosensitive layer having fluororesin 011 or -NH: Compound having 1000H111 or -C-O-C- in the molecule Crosslinking agent: -COOH or -NH in the molecule (2) In the present invention, when a fluororesin and a compound in the photosensitive layer form a bond via a crosslinking agent, for example, the following fluororesin, compound in the photosensitive layer, and crosslinking agent are each combined. used.

■Fluororesin: OH, C00H, NHt.

Fluororesin with -OH in two molecules of the compound in the photosensitive layer.

A non-point resin that has active hydrogen such as -COOH, -NH2, -NH-, and a functional group that can react with active hydrogen.A compound that has a functional group that can react with active hydrogen, such as NGO.Crosslinking agent: -OH, - in the molecule COOH.

A compound in a fluororesin photosensitive layer having an active hydrogen-reactive group such as N Hz or N tl-: A compound having a functional group capable of reacting with active hydrogen, such as -COOH, in the molecule. Compound containing II or -NH, ■ Fluororesin: Compound in a fluororesin photosensitive layer containing -OH or -NH: -OH or -N II in the molecule
Compound crosslinking agent having t: -COOH in the molecule or mutually corresponding functional groups contained in the above two layers, a particularly preferred combination of functional groups is an isocyanate group or an acid anhydride for a hydroxyl group .

As the crosslinking agent, for example, the following are used.

(1) Hexamethylene diisocyanate (CHz) &
NC0 υ (4) Toluylene-2,4-diisocyanate (5) Pentaerythritol polyglycidyl ether (6) Bisphenol A diglycidyl ether (7) Pentaerythritol (8) Pentaerythritol diacrylate (9) Diethylenetriamine (1O) Anhydrous Hexahydrophthalic anhydride (11) Pyromellitic anhydride (12) Metaxylene diamine (13) 1,3-bis(α,α-dimethylisocyanato-methyl)benzene The fluororesin of the present invention is activated with an active hydrogen functional group. H2(J
U N l-1 (CII RI AN C0) When it has both hydrogen and a functional group that can react, or when a fluororesin that has an active hydrogen functional group and a fluororesin that has a functional group that can react with active hydrogen are mixed. When used, a crosslinking agent may or may not be used.

The amount of the fluororesin used in the fluororesin layer of the present invention is generally 60 to 100%, preferably 8%.
It is 0 to 98% by weight.

The bonding between the fluororesin layer and the photosensitive layer according to the present invention is achieved by dissolving the fluororesin and an optionally added crosslinking agent in a suitable solvent, coating it on the photosensitive layer, drying it, and then subjecting it to heat treatment. As a result, the fluororesin and the compound in the photosensitive layer are crosslinked via a crosslinking agent or directly.

In the present invention, the fluororesins in the fluororesin layer may or may not be crosslinked with each other, but preferably they are crosslinked.

In the present invention, in addition to the above components, a crosslinking reaction catalyst,
For example, a small amount of an organic tin compound such as diptyltin laurate, or a quaternary or tertiary amine compound such as triethylbenzylammonium chloride or benzyldimethylamine may be contained in either or both of the photosensitive layer and the fluororesin layer.

Next, the photosensitive layer used in the present invention will be explained.

A feature of the photosensitive layer, which is a constituent component of the plate material of the present invention, is that the functional groups of the compounds in the photosensitive layer can react with the functional groups in the fluororesin or crosslinking agent by exposure to light. It contains a photosensitive substance and a binder added as necessary, and at least either the photosensitive substance or the binder has a functional group that can form a bond with the fluororesin layer by exposure to light.

Photosensitive substances having such functional groups are not particularly limited, and specific examples include the following.

Diazo resins represented by condensates of aromatic diazonium salts and formaldehyde, especially salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphates, tetrafluoroborates, perchlorates Or a diazo resin inorganic salt which is a reaction product of periodate and the above condensate, or a reaction between the above condensate and sulfonic acids as described in U.S. Pat. No. 3,300.309. The product diazo resin organic salt and the like are preferably used.

Furthermore, the diazo resin is preferably used together with a binder, and various polymeric compounds can be used as the binder, but suitable examples include novolac resins that are soluble in aqueous alkaline solutions. Typical examples of such novolac resins include phenol-formaldehyde resin, cresol-formaldehyde resin, p-tert-butylphenol-formaldehyde resin, phenol-modified xylene resin, etc. is preferably a monomer having an aromatic hydroxyl group, such as N-(4-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacryl, as described in JP-A-54-98613. Amide, 0-1m-1 or ρ-
Copolymers of hydroxystyrene, 0, m-1 or p-hydroxyphenyl methacrylate, etc. and other monomers,
and polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as a main repeating unit, natural resins such as shellac and rosin, polyvinyl alcohol, and US Pat. Patent tube 3,75
1,257, linear polyurethane resins as described in U.S. Pat. No. 3,660,097, polyvinyl alcohol phthalate resins, bisphenol A and epichlorohydrin, cellulose derivatives such as cellulose acetate and cellulose acetate phthalate are included.

Furthermore, a -CH group is added to the main chain or side chain of the polymer as a photosensitive group.
= Polyesters containing CH-C-, polyamides,
Also included are those whose main component is a photosensitive polymer such as polycarbonates. For example, JP-A-55-40415
A photosensitive polyester obtained by condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol as described in US Pat. No. 2,956,878 (2-
Examples include photosensitive polyesters derived from malonic acid compounds (properidene) and difunctional glycols.

Further examples include aromatic azide compounds in which an azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group. For example, U.S. Patent No. 3,096,3
Polyazidostyrene, polyvinyl-p-azidobenzal 1-, polyvinyl-p-azidobenzal as described in No. 11, azidoarylsulfanyl chloride as described in Japanese Patent Publication No. 45-9613 and reaction products of unsaturated hydrocarbon polymers, and Japanese Patent Publication Nos. 43-21067 and 44-2295.
Polymers having sulfonyl azide or carbonyl azide as described in Japanese Patent No. 4 and Japanese Patent No. 45-24915 can be mentioned.

Preferably, a photopolymerizable composition containing an addition polymerizable unsaturated compound and a photopolymerization initiator is also mentioned.

Examples of addition-polymerizable unsaturated monomers include alcohols (for example, ethanol, propatool, hexanol, octatool, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol,
Acrylic acid or methacrylic acid esters of polyethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), and amines (such as methylamine, ethylamine, butylamine, benzylamine, ethylenediamine, diethylenetriamine, hexamethylenediamine, xylylenediamine, dimethyl amine, diethylamine, ethanolamine, jetanolamine, aniline, etc.) and glycidyl acrylate or glycidyl methacrylate.

Carboxylic acids (e.g. acetic acid, propionic acid, benzoic acid,
acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.) and glycidyl acrylate or glycidyl methacrylate, amide derivatives (e.g. acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, etc.), and a reaction product of an epoxy compound with acrylic acid or methacrylic acid, etc. can also be used.

Also, JP-A-53-120799, JP-A-62-21
150, JP-A No. 63-17840, etc., photocationic polymerization initiators such as Schiff 1J luyodonium salts, triallylsulfonium salts, metallocene compounds, etc., and bisphenol A-based epoxy resins, alicyclic polyepoxides, etc. It is also possible to use photosensitive compositions containing epoxy resins, in which case a fluororesin layer having epoxy groups is used.

In the photosensitive layer or further the fluororesin layer in the present invention,
A photopolymerization initiator is added to cause a photopolymerization reaction, and the following can be used as the photopolymerization initiator, for example.

Benzoin M'J monoliths such as benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy α-phenylacetophenone, benzophenone, 2,
Benzophenone derivatives such as 4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4.4'-bis(dimethylamino)benzophenone, 4.4'bis(diethylamino)benzophenone, 2-chlorothioxanthone, 2-isopropylthioxanthone, etc. Thioxanthone derivatives, anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone, acridone derivatives such as N-methylacridone and N-butylacridone, α
, α-jethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compound, halogen compound, etc.

Further, a binder is preferably added to the photopolymerizable composition containing the photosensitive polymer having a photosensitive group or an addition polymerizable unsaturated compound as described above. This binder can be used in combination with a diazo resin, and more preferably,
Photo-crosslinkable copolymers having ethylenically unsaturated bonds in their side chains, which are described in publications such as No. 643 and JP-A-57-71048, are used. For example, copolymers of allyl methacrylate and methacrylic acid are used. Examples include polymer resins, carboxylic acid half ester polymers made by reacting styrene/maleic anhydride copolymer with pentaerythritol triacrylate, and polymers made by adding glycidyl methacrylate to styrene/acrylonitrile/acrylic acid copolymer. .

The combination of the functional group of the compound in the photosensitive layer used in the present invention and the fluororesin or crosslinking agent having a functional group that can react with the functional group of the compound in the photosensitive layer is the combination of the above-mentioned components in the photosensitive layer and the fluororesin or crosslinking agent. It can be appropriately selected from crosslinking agents.

In addition to the above, the photosensitive layer used in the present invention may contain pigments for visualizing images after exposure or development (for example, Victoria Pure Blue BOH' (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue'603 (manufactured by Orient Chemical Co., Ltd.)). triphenylmethane-based, diphenylmethane-based dyes, etc.)
, alkyl ethers (e.g., ethyl cellulose, methyl cellulose, etc.) to improve coating properties, fluorine-based surfactants, nonionic surfactants (e.g., Pluronic L64 (manufactured by Jiryuka Co., Ltd.), etc.), and coating film flexibility. plasticizers (e.g., polyethylene glycol, tricresyl phosphate, acrylic acid or methacrylic acid polymers, etc.), stabilizers (e.g., phosphoric acid, oxalic acid, tartaric acid, etc.) to impart properties.
can be contained.

In the present invention, a photosensitive composition comprising the above-mentioned components is applied to a support for plate material.

The support is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the load applied during printing, such as metal plates such as aluminum, zinc, copper, and steel, as well as chromium, zinc, copper, etc. , metal plates plated or vapor-deposited with nickel, aluminum, iron, etc., paper,
plastic films and glass plates, resin coated paper,
and paper covered with metal foil such as aluminum.

Among these, aluminum plates are particularly preferred.

In order to improve the adhesion between the support and the photosensitive layer, various surface roughening treatments and the like are performed as necessary.

Further, a primer layer may be provided on the support, and examples of materials constituting this primer layer include polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin. , epoxy resin, acrylate copolymer,
Examples include vinyl acetate copolymers, phenoxy resins, polyurethane resins, polycarbonate resins, polyacrylonitrile butadiene, and polyvinyl acetate. This primer layer may contain an ultraviolet absorber to prevent halation.

Further, as the anchor agent constituting the primer layer, for example, a silane coupling agent, a silicone primer, etc. can be used, and organic titanates and the like are also effective.

The thickness of each layer constituting the plate material of the present invention is as follows. That is, the support has a thickness of 50 to 400 μm, preferably 1
00 to 300 μm, photosensitive layer 0.05 to 10 μm, preferably 0.5 to 5 μm, fluororesin layer 0.01 to 10 μm
m, preferably 0.1 to lam.

The plate material of the present invention may have a protective layer on the upper surface of the fluororesin layer, if necessary.

The plate material of the present invention that does not require dampening water is manufactured, for example, as follows.

A composition solution to form a photosensitive layer is coated onto the support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary coater such as a Whaler, and then dried and heated if necessary. I'm excited.

Note that, if necessary, a primer layer may be provided between the support and the photosensitive layer in the same manner as in the case of the photosensitive layer. Next, a fluororesin and a crosslinking agent are applied on the photosensitive layer in the same manner,
The fluororesin layer is usually formed by heat treatment at a temperature of 100 to 120° C. for several minutes to sufficiently cure the resin. If necessary, a protective film can be provided on this fluororesin layer using a laminator.

Next, a method for manufacturing a printing plate that does not require dampening water using the plate material that does not require dampening water of the present invention will be explained.

A positive film, which is an original, is vacuum-adhered to the surface of a positive plate material and exposed. The light sources for this exposure include mercury lamps, carbon arc lamps, xenon lamps, and
Metal halide lamps, fluorescent lamps, etc. are used.

Then, the positive film is peeled off and developed using a developer. As the developer, a known developer for plate materials that does not require dampening water can be used. For example, aliphatic hydrocarbons (hexane, heptane, "°isopar E, H, G" (trade name of aliphatic hydrocarbons, manufactured by Esso Chemical Co., Ltd.), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, Xylene, etc.) or halogenated hydrocarbons (trichloroethylene, etc.) to which the following polar solvents are added are suitable.

Alcohols (methanol, ethanol, etc.), water, ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carpitol, ethyl carpitol, butyl carpitol, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters ( ethyl acetate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.).

It is also possible to dye the image area simultaneously with development by adding a dye such as crystal violet or astrazone red to the developer.

Development can be carried out by a known method, for example, by using a developing pad containing the developer as described above, or by pouring the developer onto the printing plate and then rubbing it with a developing brush.

By the above development, the fluororesin in the unexposed area is removed and the photosensitive layer, in some cases the primer layer or the support, is exposed.
A printing plate is obtained in which the fluororesin layer remains in the exposed areas.

〔Example〕

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

In the following description, "parts" means parts by weight unless otherwise specified.

Example 1 A photosensitive composition having the following composition was coated on a degreased aluminum plate having a thickness of 0.24 mm, and was dried at 100° C. for 2 minutes to form a photosensitive layer having a thickness of 2 μm.

[Photosensitive composition]

(1) 100 parts of a resin in which glycidyl methacrylate is added to the carboxyl group of a copolymer resin of styrene, acrylonitrile, butyl acrylate, and acrylic acid in a molar ratio of 49.10.4.37 (Japanese Patent Publication No. 49-17874
(2-1) 70 parts of a 4:l adduct of glycidyl methacrylate and metaxylene diamine (2-2)) Limethylolpropane triethoxy triacrylate
30 parts (3) 2,4-diethylthioxanthone 10
Part (4) p-dimethylaminobenzoic acid isoamyl ester 3 parts (5) Victoria Pure Blue B OH 1.0 parts (manufactured by Hodogaya Chemical Co., Ltd., dye) (6) Methyl cellosolve 500 parts Next, the following was applied to the surface of the photosensitive layer. Fluororesin composition-1 having the composition is applied and heated at 90°C for 3 minutes to crosslink the fluororesin and form a hardened fluororesin layer with a thickness of 1.0 μm, eliminating the need for dampening water. A lithographic printing plate material was obtained.

[Fluororesin composition-1] (1) Summer 1. Ill, 211.211-hebutadecafluorodecyl methacrylate-2-hydroxyethyl methacrylate, methyl methacrylate, 50% of the hydroxyl groups in the copolymer resin with a molar ratio of 80, 10, 10, 2-methacryloyloxyethyl Isocyanate [C11□・C(CH:+)COOCHzCH
zNCO) added resin 5
0 parts (2) Coronate EH (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate) 3.5 parts (3) Dibutyl tin dilaure) 0.05 parts (
4) Freon - 113,500 parts (5) Methyl ethyl ketone 20 parts After a positive film was vacuum-adhered to the upper surface of the above plate material, it was exposed to light using a metal highland lamp as a light source. By this exposure, the photosensitive layer in the exposed area is crosslinked, and the photosensitive layer and the fluororesin layer in this area are crosslinked, so that these layers are firmly bonded to each other.

Next, the exposed plate material was developed using the following developer. During development, only the unexposed portions of the fluororesin layer were easily removed by rubbing the surface of the plate material with a development bat. A lithographic printing plate was obtained in which the fluororesin layer in the exposed areas was firmly adhered and did not require dampening water.

[Developer composition]

Isopar H 20 parts Toluene 80 parts Tulfite (manufactured by Clarei Soprene Chemical Co., Ltd.) 3 parts Then,
The above printing plate was attached to a Heidenberg GTO printing machine with the dampening water supply device removed, and the printing plate was manufactured by Osaka Ink Mfg. Co., Ltd.
When printed using PROCfiSS RED H, 20,000 prints with good small dot reproducibility and shadow area reproducibility were obtained.

Example 2 A plate material was prepared and developed to obtain a printing plate in the same manner as in Example 1 except that fluororesin composition-1 of Example 1 was replaced with fluororesin composition-2 having the following composition. Ta.

The fluororesin layer in the exposed areas of this printing plate was firmly adhered, and when printed in the same manner as in Example 1, 20,000 prints with good dot reproducibility and shadow area reproducibility were obtained.

[Fluororesin composition-2] F, L;? , υ and the molar ratio of It3 methyl methacrylate, methacrylic acid, and 2-hydroxyethyl methacrylate is 70
．． 10. A resin in which glycidyl methacrylate is added to 50% of the carboxyl groups in the copolymer resin of 10.10.
50 parts (2) Coronate EH (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate) 3.5 parts (3) Dibutyltin dilaurate 0.05 part (4
) Freon - 113,500 parts (5) Acetone 20 parts Comparative Example 1 A printing plate was prepared according to the method of Example 2 of WO83-02175. When printing was carried out in the same manner as in Example 1, streak-like stains were observed over the entire plate surface as the amount of printing increased.

Comparative Example 2 A printing plate was prepared according to the method of Example 1 of JP-A-58-215411. When printing was carried out in the same manner as in Example 1, light scumming was observed on the entire plate surface as the amount of printing increased.

Further, this printing plate could be developed with meta-xylene hexafluoride, but could not be developed with the developer of Example 1. Further, the reproducibility of shadow parts and small dots was also better in Examples 1 and 2.

Examples 3 to 6 Plate materials were prepared and developed in the same manner as in Example 1, except that fluororesin composition-2 of Example 2 was replaced with fluororesin compositions-3 to 6 having the following compositions. A printed version was obtained. All of these printing plates had a fluororesin layer firmly attached to the exposed areas, and when used for printing in the same manner as in Example 1, it was possible to produce printed matter similar to that of Example 2. did it.

[Fluororesin composition-3] (1) The molar ratio of hebutadecafluorodecyl methacrylate, methyl methacrylate, methacrylic acid, and 2-hydroxyethyl methacrylate is 75
:10:10:5 copolymer resin with glycidyl methacrylate added to the carboxyl group
50 parts (2) Coronate E) I (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate) 3.5 parts (3) Dibutyltin dilaurate 0.05 part (4
) Freon - 113,500 parts (5) m-xylene hexafluoride 20 parts [Fluororesin composition-4] (1) Moles of hebutadecafluorodecyl methacrylate, methyl methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate The ratio is 75
:10:10:5 copolymer resin 50 parts (2) Coronate EH (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate) 3.5 parts (3) Dibutyltin dilaurate 0.05 part (4
) Freon-113,500 parts (5) m-xylene hexafluoride 20 parts [Fluororesin composition-5] (1) Hebutadecafluorodecyl methacrylate, maleic anhydride, methyl methacrylate, molar ratio is so: 50 parts of a resin in which 2-hydroxyethyl methacrylate is added as a half ester to the carboxylic anhydride group of a to:to copolymer resin (2) Coronate EH (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate) 3.5 parts (3) Dibutyltindi Laure) 0.05 part (
4) Freon-113,500 parts (5) m-xylene hexafluoride 20 parts [Fluororesin composition-6] (1) Hebutadecafluorodecyl methacrylate, 2-
50 parts of a resin obtained by adding m-isopropenyl-α,α-dimethylbenzylisocyanate to 70% of the hydroxyl groups of a copolymer resin of hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 85:15:5 (2) Coronate EH (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate) 3.5 parts (3) Dibutyltin dilaurate 0.05 part (4
) Freon - 113,500 parts (5) m-xylene hexafluoride 20 parts [Effects of the invention] As is clear from the above explanation, according to the present invention, development is performed with a developer containing a solvent other than a fluorine-based solvent. Lithographic printing that does not require dampening water and can form a printing plate that has a wider development latitude during development processing, has excellent rigidity and reproducibility of shadow areas and small dots, and does not cause scumming on the plate surface. Plate materials will be provided.

Claims (1)

[Claims] In a lithographic printing plate material that does not require dampening water and has a photosensitive layer and a fluororesin layer on a support in order from the support side, the fluororesin layer is contained in the photosensitive composition forming the photosensitive layer. A lithographic printing plate material that does not require dampening water and is characterized by containing a fluororesin having a functional group of a compound described above and a functional group that can be bonded by exposure to light.