JPH036560A - Developing solution for damping waterless planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain excellent developability and dot reproducibility by incorporating one or >=2 kinds of alkyl benzenes having >=9 carbon atoms as a whole into the developing soln. CONSTITUTION:One or >=2 kinds of the alkyl benzenes which are expressed by formula I and have >=9 carbon atoms as a whole I, R denotes an alkyl group having 1 to 4C; n denotes 1 to 4 integer. The more specific examples of the alkyl benzenes include, for example, n-butyl; benzene, 1, 4-n-butyl benzene and 1, 3-di-sec-butyl benzene, etc. These compds. may be used alone or in combination of >=2 kinds. The developing soln. which has the excellent developability suitable for the development of the damping waterless planographic printing plate material and has the good dot reproducibility is obtd. in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a developer for lithographic printing plate materials that does not require dampening water, and more specifically, a developer that can be used to develop lithographic printing plate materials that do not require dampening water. The present invention relates to a developer that can improve the developability of the lithographic printing plate material and also improve the halftone reproducibility, that is, the reproducibility of shadow areas and the reproducibility of small dots, of the lithographic printing plate formed by the development.

[Background of the invention]

Conventionally, a lithographic printing plate material (hereinafter also simply referred to as "plate material") that does not require dampening water, which is made by coating a support with a photosensitive layer and an ink-repellent layer in order from the support side, is exposed to light. In order to obtain a lithographic printing plate (hereinafter simply referred to as a "printing plate") that does not require dampening water by development, for example, aliphatic hydrocarbons (hexane, heptane, "Isopar E,"
H, G” (manufactured by Esso Chemical Co., Ltd., a trade name for aliphatic hydrocarbons) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, meta-xylene hexafluoride, etc.)
, or halogenated hydrocarbons (trichlorethylene,
(perfluorohexane, etc.) and the following polar solvents, namely alcohols (methanol, ethanol, etc.), water, ethers (methyl cellosolve, ethyl cellosolve,
butyl cellosolve, methyl carpitol, ethyl carbitol, butyl carpitol, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters (
Ethyl acetate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.) are used, and for example, a plate material in which a photosensitive layer and a silicone rubber layer are provided on a support in this order from the support side. As a developer for developing
No. 448 discloses a developer containing a propylene oxide derivative, JP-A-61-275759 discloses a developer containing an organic solvent, a surfactant, and water, and JP-A-59
JP-A-146054 discloses a developer containing 0.05 to 5% water and a hydrocarbon.

However, developing plate materials with conventional developers containing the above-mentioned solvents generally takes time, and the resulting printing plates do not have sufficient dot reproducibility. In an attempt to shorten this time, if a developer containing a solvent that is highly soluble in the photosensitive layer is used, the reproducibility of the shadow areas of the printing plate will be poor. It is necessary to use a large amount of solvent to swell the plate material, and if the plate material is rubbed too hard in an attempt to shorten the development time, the silicone rubber layer will be damaged, and conventional developers generally do not provide sufficient developability. Not yet.

In particular, the developer disclosed in JP-A-57-13448 and the like is applicable to a developing method that removes only the silicone rubber layer by utilizing photoadhesion between the photosensitive layer and the silicone rubber layer caused by exposure. However, for development methods in which both the silicone rubber layer and the photosensitive layer are removed by development, the adhesion between the exposed photosensitive layer and the support, the primer layer or the silicone rubber layer, especially the silicone rubber layer, is suitable. Because it weakens it more than necessary, it was not possible to obtain satisfactory results.

Furthermore, although the developer disclosed in JP-A No. 61-275759 has improved safety by containing 30% by weight of water, it does not give satisfactory results in terms of developability, especially development speed. is not obtained.

Therefore, as a result of various studies in view of the above-mentioned situation, the present inventors have found that the following general formula [I], that is, the following general formula [I] is expressed in % color %, and the overall A developer for lithographic printing plate materials that does not require dampening water and contains one or more types of alkylbenzenes having 9 or more carbon atoms, [wherein R is an alkyl group having 1 to 4 carbon atoms] , and n represents an integer from 1 to 4], and contains one or more alkylbenzenes having 9 or more carbon atoms as a whole, and does not require dampening water. It has been found that when developing a printing plate material, not only excellent developability is exhibited, but also a printing plate with improved halftone dot reproducibility can be produced in a relatively short time.

[Object and structure of the invention]

The present invention was invented based on the above findings, and an object of the present invention is to provide a developer that exhibits excellent developability and halftone dot reproducibility when used for developing lithographic printing plate materials that do not require dampening water. [wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4].

[Detailed description of the invention]

The present invention will be explained in more detail below.

As mentioned above, the developer of the present invention has the following general formula [I]
It is expressed as % color % and contains one or more alkylbenzenes having 9 or more carbon atoms as a whole, [wherein R has 1 to 4 carbon atoms] represents an alkyl group, and n represents an integer of 1 to 4] Specific examples of this alkylbenzene include n-butylbenzene, 5eC-butylbenzene, t
ert-butylbenzene, m-cymene, 0-cymene, p
-cymene, m-diethylbenzene, 0-diethylbenzene, p-diethylbenzene, 2-ethyl-p-xylene, 3-ethyl-〇-xylene, 4-ethyl-m-xylene, 4-ethyl-〇-xylene, 5-ethyl -m-xylene, is.

-butylbenzene, 2-n-propyltoluene, 3-n
-propyltoluene, 4-n-propyltoluene, i,
2.3.4-tetramethylbenzene, 1.2.3.5-
Tetramethylbenzene, n-propylbenzene, 1.3
．． 5-) Limethylbenzene, tert-propylbenzene, ■-methyl-4-n-butylbenzene, 1,3-di-n-butylbenzene, 3-butyl-0-xylene, l
-n-butyl-3-ethylbenzene, 1-ethyl-2-
Methylbenzene, 1,2.3-trimethylbenzene, 1
, 4-di-n-butylbenzene and 1゜3-di5e
Examples include c-butylbeny/yne, and these compounds may be used alone or in combination of two or more.

Commercial products corresponding to the above-mentioned compounds or mixtures thereof, such as 5S-1800 (mixture of alkylbenzenes having 10 carbon atoms, manufactured by Mitsubishi Oil Corporation) and 5
S-1500 (mixture of alkylbenzenes having 9 carbon atoms, manufactured by Mitsubishi Oil Corporation) can also be used.

Among alkylbenzenes, those having 10 carbon atoms are preferably used.

The developer of the present invention generally contains 1 to 10% of the alkylbenzene described above.
90% by weight, preferably 5-80% by weight, more preferably 10-50% by weight, the remainder being components used in conventional developers, such as optionally methanol, ethanol, 1-butoxy- 2-Proper Tools, 3-
Alcohols such as methyl-3-methoxybutanol and benzyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve,
Methyl carpitol, ethyl carpitol, butyl carpitol, dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol shifthyl ether, propylene glycol ether, dipropylene glycol butyl ether, tripropylene glycol methyl ether and polypropylene glycol methyl ether ethers such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone, ethyl acetate, propyl acetate, hexyl acetate, methyl butyrate, propyl butyrate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzoic acid Esters such as benzyl, cellosolve acetate, methyl cellosolve acetate and carpitol acetate, and polar solvents such as water, as well as hexane, heptane, “Isopar E, H, G” (manufactured by Esso Chemical Co., Ltd., for aliphatic hydrocarbons) (product name), gasoline, aliphatic hydrocarbons such as kerosene, aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as trichloroethylene.
It can contain more than one species.

The developer of the present invention can contain a surfactant, and examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene Nonionic surfactants such as sorbitan fatty acid ester, glycerin fatty acid ester, oxyethylene oxypropylene block polymer, fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfo(acid ester, alkyl Anionic surfactants such as phosphoric acid ester salts, naphthalene sulfonic acid-formalin condensates, polyoxyethylene alkyl sulfate salts, cationic surfactants such as alkyl amine salts, quaternary ammonium salts, polyoxyethylene alkyl amines, and alkyl betaines. Among them, anionic surfactants are suitable.

These surfactants can be used alone or in combination of two or more, and when a surfactant is used in the present invention, it is generally added in a concentration of 0.5 to 6
It is appropriate to contain 0% by weight, preferably 1 to 50% by weight.

Here, specific examples of the developer of the present invention are as follows.

[I]% Color% Isopar H1-99% by weight Nocimene 1-99% by weight (2) Isopar H5
-85% by weight 1-Methyl-4-n-butylbenzene 5-85% by weight Tripropylene glycol monomethyl ether 5-85% by weight (3) 3-Methyl-3-methoxybutanol 2-80% by weight Isopar M
1-50% by weight 33-1800
2-60% water by weight 30-
95% by weight (4) Surfactant 1 to 30% by weight Diethylene glycol dimethyl ether 5S-1500 Water (5) Isopar H n-Butylbenzene tripropylene glycol monomethyl ether 5 to 85% by weight Diethyl succinate 1 to 10% by weight of the present invention The developer can generally be used for any of the conventional lithographic printing plate materials that do not require dampening water, but it is preferable to apply a fluororesin layer as a photosensitive layer and a 18-layer layer on the support in order from the support side. or a silicone rubber layer, particularly preferably a fluororesin layer as an ink repellent layer, and the ink repulsion of such a plate material is 1 to 80% by weight 2 to 50% by weight 30 -950-9 5% by weight 5% by weight 5-85% by weight As the fluororesin constituting the layer, for example, JP-A-52-7
No. 4404, No. 52-74405, No. 55-8301
No. 1, No. 5B-88750, and No. 5B-90
It is disclosed in various publications such as No. 524 and is conventionally known, or it is disclosed in Japanese Patent Application No. 63-182466 and No. 63-2376.
It is possible to use any of the fluororesins that the present applicant had already proposed by the time of filing this application in applications such as No. 80 and No. 63-288129.

Preferably, Japanese Patent Application Nos. 63-182466 and 63-2
The fluororesins described in the specifications of No. 37680 and No. 63-288129 are used, and for example, the following can be used.

[I]%Color%Has the following structural unit in the molecule, CF s
CF t CF-1CF, -〇--CF
, -0--CF-0- (fluorine content is 30% by weight or more, preferably 50% by weight or more) and fluorine resins are bonded to each other and/or in the photosensitive layer within the molecule, directly or via a crosslinking agent. A fluororesin that has a functional group that can react with other compounds to form a bond.

Examples of the above-mentioned functional groups include the following functional groups.

OH, -COOH, NHs, NH- The above fluororesin can be obtained by copolymerization of a fluorine-containing monomer and a monomer having the above functional group.

Specifically, the fluororesins exemplified below are preferably used.

■ Copolymer resin of perfluoroalkyl (meth)acrylate and allyl methacrylate ■ Copolymer resin of perfluoroalkyl (meth)acrylate and (meth)acrylic acid ■ Perfluoropolyether (meth)acrylate and (meth)acrylic acid Glycidyl (
Resin with added meth)acrylate■ Perfluoroalkyl(meth)acrylate and 2-hydroxyethyl(
Copolymer resin of meth)acrylate, alkyl(meth)acrylate, and acrylonitrile■ Perfluoroalkyl(meth)acrylate and 2-
The bond between the resin fluororesin layer and the photosensitive layer is formed by adding 2-methacroyloxyethyl isocyanate to the product obtained by copolymerizing hydroxyethyl (meth)acrylate, alkyl (meth)acrylate, and acrylonitrile. Fluororesin and
After dissolving the optionally added crosslinking agent in a suitable solvent,
By applying the solution onto the photosensitive layer, drying it, and then subjecting it to heat treatment, the fluororesin and the compound in the photosensitive layer are crosslinked via a crosslinking agent or directly.

The fluororesin layer is preferably crosslinked, and the crosslinking agent used with the fluororesin has two or more functional groups in the molecule that can react with the functional groups described in the above [I] % color %. Preferably, a polyisocyanate compound such as hexamethylene diisocyanate, toluylene-2,4-diisocyanate, etc. is used in combination with a fluororesin having a hydroxyl group.

Next, silicone rubber, which is another material constituting the ink repellent layer in the plate material, will be explained.

The above-mentioned silicone rubber is a linear organic rubber having several thousand to hundreds of thousands of repeating units represented by the following general formula (2) on the molecule, with a hydroxyl group bonded in the main chain or at the end of the main chain. Those containing polysiloxane as a main component are preferably used.

General formula ■ -←5i-0-)r where n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkoxyl group, a vinyl group, an aryl group, a silanol group (OH group) ), and 60% or more of R is preferably a methyl group.The above silanol group (OH group) may be located either in the main chain or at the end of the main chain, but the one at the end is preferable.

The silicone rubber used in plate materials is obtained by a condensation reaction between such a silicone base polymer and a silicone crosslinking agent as listed below.

[I]%Color%R-3i-←OR'): 1(2)R-3i
-←0AcL (3) R-3t-←ON = CR' z)s where R
has the same meaning as R, which is a substituent of the polymer represented by the general formula (2), R' is an alkyl group such as a methyl group or an ethyl group, and Ac is an acetyl group.

These silicone rubbers are also available as commercial products, such as YE-3085 manufactured by Toshiba Silicone Corporation.

Other useful silicone rubbers are produced by the reaction of the above-mentioned base polymer with a silicone oil having the following general repeating units, or silicone rubbers in which about 3% of R is vinyl groups. It can also be obtained by an addition reaction with a base polymer or a reaction between the above silicone oils.

General 2 (wherein, R has the same meaning as R, which is a substituent of the polymer represented by the above general formula 2, m is an integer of 2 or more, and n is an integer of 0 or 1 or more.) To obtain silicone rubber by crosslinking reaction, the crosslinking reaction is carried out in the presence of a catalyst. As this catalyst, organic carboxylates of metals such as tin, zinc, cobalt, lead, calcium, manganese, etc., such as dibutyltin laurate, tin(n) octoate, cobalt naphthenate, etc., or chloroauric acid, etc. are used. .

In addition, in order to improve the strength of silicone rubber and obtain silicone rubber that can withstand the frictional forces generated during printing operations,
Fillers can also be mixed. Silicone rubber mixed with filler in advance is commercially available as silicone rubber stock or silicone rubber dispersion, and when it is preferable to obtain a silicone rubber film by coating as in the present invention, RT
V or LTV silicone rubber dispersions are preferably used. An example of this is Sy10ff 23.5RX-257,5H manufactured by Toray Silicone.
There are silicone rubber dispersions for vapor coating such as 237.

In general, it is preferable to use condensation and crosslinking type silicone rubber for plate materials.

The silicone rubber layer preferably contains a silane coupling agent having an amino group in order to further improve adhesiveness.

Examples of preferable silane coupling agents include the following.

(a) 1lJcHzcllzNIl (C1h)
3si (OCH3) 3(b) IhNCf1□C
H□N11(CI+□)+5i(OCtl+)z(CI
! +)(C) HJ(C1lt)+5i(OEt)s Next, the material constituting the photosensitive layer is not particularly limited, and specifically, the following are exemplified.

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 a 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.

Further, the diazo resin is preferably used together with a binder, and various polymeric compounds can be used as the binder, but preferably one such as that described in JP-A-54-98613 is used. Monomers having aromatic hydroxyl groups, such as N-(4-hydroxyphenyl)acrylamide, N-(4-hydroxyethyl)methacrylamide, 〇-m-1 or p-hydroxystyrene, o-
1m, or copolymers of p-hydroxyphenyl methacrylate, etc. and other monomers, and U.S. Patent No. 4,12
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as a main repeating unit as described in US Pat. No. 3.276, natural resins such as shellac and rosin, polyvinyl alcohol, and polyvinyl alcohol; Polyamide resins such as those described in No. 257, U.S. Pat.
60,097, linear polyurethane resins, polyvinyl alcohol phthalate resins, epoxy resins condensed from bisphenol A and epichlorohydrin, cellulose derivatives such as cellulose acetate and cellulose acetate phthalate. be done.

Furthermore, there are also those whose main component is a photosensitive polymer such as polyesters, polyamides, and polycarbonates containing one group -CH=CH-C- as a photosensitive group in the polymer main chain or side chain. . For example, JP-A-55-40
Photosensitive polyesters obtained by condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol as described in U.S. Pat. No. 415, as described in U.S. Pat. Examples include photosensitive polyesters derived from (2-properidene)malonic acid compounds such as cinnamylidenemalonic acid 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,
Polyazidostyrene, polyvinyl-ρ-azidobenzoate, polyvinyl-ρ-azidobenzal as described in No. 311, azidoarylsulfanylflora ide as described in Japanese Patent Publication No. 45-9613. reaction product with an unsaturated hydrocarbon polymer,
and Japanese Patent Publication No. 43-21067, I4-22
Examples include polymers having sulfonyl azide or carbonyl azide, as described in Japanese Patent No. 954 and Japanese Patent No. 45-24915.

Photopolymerizable compositions of plate materials suitable for development with the developer of the present invention are disclosed in JP-A-50-50102 and JP-A-55.
-124149, JP-A-61-67864, and JP-A-63-280250, photopolymerizable compositions containing an addition polymerizable unsaturated compound and a photopolymerization initiator are also preferred. It is the material.

Also, JP-A-53-120799, JP-A-62-21
Photo-cationic polymerization initiators such as diallyliodonium salts, triallylsulfonium salts, and metallocene compounds described in publications such as No. 150 and JP-A-63-17840, and epoxy resins such as bisphenol A-based epoxy resins and alicyclic polyepoxides. It is also possible to use photosensitive compositions containing.

Further, a binder is preferably added to the photopolymerizable composition containing the photosensitive polymer or addition polymerizable unsaturated compound having a photosensitive group as described above. As this binder, the binders mentioned above as those used in combination with the diazo resin can be used, and more preferably, JP-B-49-17874, JP-A-59-46643, JP-A-57- Photocrosslinkable copolymers having ethylenically unsaturated bonds in side chains, which are described in publications such as No. 71048, are used, such as copolymer resins of allyl methacrylate and methacrylic acid, styrene/maleic anhydride, etc. Examples include a carboxylic acid half ester polymer obtained by reacting a copolymer with pentaerythritol triacrylate, and a polymer obtained by adding glycidyl meccrylate to a styrene/acrylonitrile/acrylic acid copolymer.

The photosensitive composition of the plate material suitable for development with the developer of the present invention is a photosensitive composition containing a binder as described above, such as a composition containing a diazo resin and a binder, and addition polymerization. Examples include compositions containing a sexually unsaturated compound, a photopolymerization initiator, and a binder.

The photosensitive composition comprising the above-mentioned components is applied to a support for plate material, and this support must be flexible enough to be set in a normal lithographic printing machine and capable of withstanding the load applied during printing. Preferably, metal plates such as aluminum, zinc, copper, steel, etc., metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper, plastic films, and glass plates, Examples include 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 as described above is as follows. That is, the support has a thickness of 50 to 400 μm, preferably 100 to 300 μm, and the photosensitive layer has a thickness of 0.05 to IO μm.
Preferably 0.2 to 5 μm, ink anti-ta layer 0.1 to 5 μm
10 μm, preferably 0.3 to 3 μm.

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

Next, a method for producing a printing plate that does not require dampening water using a plate material that does not require dampening water will be described.

A positive film l, which is an original, is vacuum-adhered to the surface of a positive plate material and exposed. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet rays, are used.

Then, the positive film is peeled off and developed using the developer of the present invention. In this case, dyes such as crystal violet and astrazone red can be added to the developer to dye the image area at the same time as development.

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

By the above development, the ink-repellent layer in the unexposed areas is removed and the photosensitive layer, optionally the primer layer or the support, is exposed, resulting in a printing plate in which the ink-repellent layer remains in the exposed areas.

When silicone rubber is used as the ink repellent layer, the developer of the present invention can ink the unexposed area 1a by development.
It is particularly preferably applied to development processes in which the layer and the photosensitive layer are removed, so that the primer layer or the support is exposed.

〔Example〕

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

Note that "parts" described in the examples mean "parts by weight" unless otherwise specified.

Manufacturing thickness Q of aluminum plate a,! mm aluminum plate was immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then soaked in hydrochloric acid with a concentration of 1%.
and at a temperature of 25°C in an aqueous solution with a boric acid concentration of 1%.
Electrolytic etching was performed for 5 minutes at 3A/dm'',
After washing with water, 1.
Anodize for 2 minutes at 5A/dm, wash with water,
37 in a 1% sodium metasilicate aqueous solution at a temperature of 85°C.
Dip for 2 seconds, then soak in water (pH 8.5) at a temperature of 90°C for 25 minutes.
It was immersed for seconds, washed with water, and dried to obtain aluminum plate a.

Next, a photosensitive composition having the following composition was applied to the aluminum plate a produced as described above, and dried at 100° C. for 2 minutes to form a photosensitive layer with a thickness of 2 μm.

[Photosensitive composition]

[I]% Color% Molar ratio of styrene, acrylonitrile, butyl acrylate, and acrylic acid is 49 = IO = 4:3
50 parts of a resin obtained by adding glycidyl methacrylate to the carboxyl group of the copolymer resin 7 (synthesized by the method described in Japanese Patent Publication No. 17874/1987) (2-1) 4 of glycidyl methacrylate and metaxylene diamine =1 adduct 25 parts (2-2)
Trimethylolpropane triethoxy triacrylate 10 parts (2-3) Tetramethylolmethane tetraacrylate
5 parts (2-4)) Limethylolpropane triacrylate
25 parts (3) 2,4-diethylthioxanthone 12
．． 5 parts (4) p-dimethylaminobenzoic acid inamyl ester 3 parts (5) Victoria Pure Blue BOH 0.2 parts (6) Methyl cellosolve 500 parts Next, a fluororesin composition having the following composition was applied to the surface of the photosensitive layer. Apply 9
The fluororesin was crosslinked by heating to 0°C for 30 minutes, and as a result, a cured fluororesin layer with a thickness of 1.0 μm was formed on the photosensitive layer, thereby obtaining a lithographic printing plate material that did not require dampening water. Ta.

[Fluororesin composition l] [I]% Color% IH, IH, 2H, 2H-hebutadecafluorodecyl acrylate [CH*=CHCOO(=CH
C00(CHz)], ]2-hydroxyethyl methacrylate and methyl methacrylate, 50 parts of copolymer resin with a molar ratio of 50:10:40 (2) Coronate EH (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate 3.5 Part (3) Dibutyltin dilaurate 0.05 part (4) Freon-
113,500 parts (5) Methyl ethyl ketone 20 parts After vacuum-adhering a positive film to the top surface of the above plate material, it was exposed to light using a metal halide lamp as a light source, and the exposed plate material was immersed in the following developer for 30 seconds. The surface of the plate material was developed by rubbing it with a development pad for 60 seconds.

Only the unexposed portions of the fluororesin layer were removed, yielding a printing plate in which halftone dots of 2 to 98% were well reproduced.

[Developer composition]

Isopar H5 parts 5S-180080 parts Tulphyte (manufactured by Clarei Soprene Chemical Co., Ltd.) 15 parts Then, when the above printing plate was attached to a Komori Sprint printing machine with the dampening water supply device removed and printed, the printed matter had good halftone reproducibility. 15,000 copies were obtained.

Comparative Example 1 The same procedure as in Example 1 was repeated except that a developer was used in which 5S-1800 in the developer in Example 1 was replaced with toluene. The halftone reproducibility of the obtained printing plate was poor at 5 to 90%.

Example 2 Synthesis of diazo resin [I]% color p-diazodiphenylamine sulfate 14.5 g (50
mmol) was dissolved in 40.9 g of concentrated sulfuric acid under water cooling. 1.5 g (50 mmol) of paraformaldehyde was slowly added dropwise to this reaction solution. At this time, the reaction temperature is 1
The mixture was added so as not to exceed 0''C. Thereafter, stirring was continued for 2 hours under water cooling.

This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100 mf of pure water, and 6.8 mf was added to this solution.
A cold concentrated aqueous solution of 1 g of zinc chloride was added. After filtering the settled precipitate, it was washed with ethanol, and this was washed with 150 m
Dissolved in 1 liter of pure water. A cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved was added to this solution. The resulting precipitate was collected by filtration, washed with water, and dried at 30°C for a day and night to reduce the color of diazo resin [I]%. I got %.

Synthesis of polymer compound [I]% color% N-(4-hydroxyphenyl) methacrylamide 53
．． 2g, acrylonitrile 15.9g, ethyl acrylate 36.5g, methyl methacrylate 3.5g and azobisisobutyronitrile 1.642g in acetone-ethanol 1:l (volume ratio) mixed solvent 112mj! After dissolving the mixture in the solution and purging it with nitrogen, it was heated at 60°C for 8 hours.

After the reaction is complete, add 51.5% of the reaction solution to water. Pour into the mixture while stirring.
The resulting white precipitate was filtered and dried to obtain the lipophilic polymer compound [I
]90 parts of %color% were obtained.

The molecular weight of this lipophilic polymer compound [I]% color is determined by GPC.
As a result of measurement, the weight average molecular weight was 52,000.

Next, using the diazo resin [I] % color % and the polymer compound [I] % color % produced as described above, a photosensitive [photosensitive layer composition] having the following composition was prepared on the aluminum plate a. Resin [I]% Color% 40
Part High molecular compound [I]% Color% 6
0 parts Victoria Pure Blue BOH 1 part (manufactured by Odugaya Kagaku Co., Ltd., dye) 900 parts of methyl cellosolve Next, 2 parts of the following silicone rubber composition was applied to the photosensitive layer by dry weight.
．． 0 g/m'' and dried at 90°C for 10 minutes to obtain a lithographic printing plate material that does not require dampening water.

[Silicone rubber layer composition]

Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 52.000) 100 parts triacetoxymethylsilane 10 parts dibutyltin laurate 0.8 parts Isopar G (
After vacuum-adhering a positive film to the upper surface of a 900-part (manufactured by Esso Chemical) board material, it was exposed to light using a metal halide lamp as a light source, and then developed using the following developer.

During development, the unexposed portions of the photosensitive layer and silicone rubber layer were removed by rubbing the surface of the plate material with a development pad.

[Developer composition]

Isopar H 30 parts Tulphyte (manufactured by Clarei Soprene Chemical Co., Ltd.) 50 parts 5S-180020 parts Diethyl succinate 5 parts Then,
When printing was carried out in the same manner as in Example 1, 17,000 prints with good dot reproducibility were obtained.

Comparative Example 2 The same procedure as in Example 1 was repeated except that a developer was used in which 5S-1800 in the developer in Example 1 was replaced with tripropylene glycol monomethyl etherel. The halftone reproducibility of the obtained printing plate was poor at 5 to 90%.

〔Effect of the invention〕

As is clear from the above description, according to the present invention,
Provided is a developer suitable for developing lithographic printing plate materials that do not require dampening water, has excellent developability, and has good halftone dot reproducibility.

Claims (1)

[Claims] A lithographic printing plate material that does not require dampening water and contains one or more alkylbenzenes represented by the following general formula [I] and having 9 or more carbon atoms as a whole. Developer, General Formula [I] % Color % In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4.