JPH031141A - Photosensitive coating liquid containing fluorine surfactant - Google Patents

Abstract

PURPOSE:To improve toxicity and smell and to improve coatability in a stage for application of the photosensitive coating liquid by incorporating 30 to 80wt.% diethylene glycol dimethyl ether and fluorine surfactant into the coating liquid. CONSTITUTION:This coating liquid contains 30 to 80wt.% diethylene glycol dimethyl ether and fluorine surfactant. The ratio of the diethylene glycol dimethyl ether and the remaining solvent to be incorporated into the solvent is preferably a 30 to 80% range of the former and the remaining solvent of the coating solvent to be used preferable contains at least one kind selected from the group of 1 to 5C alcohol, methyl ethyl ketone, ethyl acetate or diethylene glycol monomethyl ether. The toxicity at the time of the production of the photosensitive printing plate is low in this way and smells are relieved; in addition, the coatability is improved.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive coating solution, and more specifically, a photosensitive coating solution that has improved odor, low toxicity, improved coating properties, and has excellent storage stability. The present invention relates to a photosensitive coating liquid, particularly a photosensitive coating liquid used in the production of a photosensitive lithographic printing plate.

[Background of the invention] A photosensitive printing plate is produced by dissolving a photosensitive composition in a suitable solvent,
It is manufactured by coating this on a support and drying it. Conventionally, when manufacturing such photosensitive printing plates, various solvents have been used to dissolve the photosensitive composition, such as methyl cellosolve. (ethylene glycol monomethyl ether), glycol ethers such as ethyl cellosolve, and cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate are mainly used.

However, these coating solvents have the problem of being highly toxic during the production of photosensitive printing plates, as well as having a strong odor.
It is uncomfortable and unfavorable in terms of the working environment.Furthermore, when a photosensitive composition is coated onto a support using the above-mentioned solvent, coating properties are poor, and coating irregularities such as streaks and pinholes often occur, resulting in poor product quality. This has become a problem as it may damage its value.

Furthermore, JP-A-62-14652 describes the use of a propylene compound as a solvent for a photosensitive coating solution, but photosensitive printing plates obtained using this propylene compound have poor storage stability. Improvement in this point is desired.

Furthermore, when using diethylene glycol ether and/or its ester as a coating solvent, improvements in odor, toxicity, and coating properties can be seen compared to conventional solvents such as methyl cellosolve and ethyl cellosolve, but the results are still insufficient. Further improvements are desired.

On the other hand, in the manufacturing method of photosensitive printing plates, in order to cope with the increase in production volume in recent years, one type of product is manufactured continuously for a long time, and the number of units for manufacturing photosensitive liquid is increasing. However, when such photosensitive printing plates are manufactured continuously for a long period of time, the storage stability of the photosensitive liquid becomes a problem, and the conventionally used solvents or dioxane are used as coating solvents. When using a solvent that mainly contains organic solvents such as , tetrahydrofuran or cyclohexanone, fluorine-based surfactants and oil sensitizers such as ocdylphenol, which are added to improve coating properties, are used.
When a compound consisting of a phenolic compound substituted with an alkyl group such as dobutylphenol is used, there is a drawback that the affinity is poor. That is, in the photosensitive coating liquid using these coating solvents, the fluorine-based surfactant and the oil-sensitizing agent separate within one hour at the earliest, and within one day at the latest. Therefore, photosensitive printing plates obtained by applying such photosensitive coating liquids have vertical streaks caused by agglomeration of these substances and pinholes caused by repelling, which significantly reduces the commercial value of the photosensitive printing plates. lower. In addition, when developing a photosensitive printing plate manufactured from a photosensitive liquid in which these substances are separated, the unexposed areas of the photosensitive layer are not completely removed by development, resulting in stains during printing and impairing the performance of the printing plate. was damaging.

As a result of various studies on these problems, the present inventors not only found that adding a fluorine-containing surfactant to at least diethylene glycol dimethyl ether significantly improves odor, toxicity, and especially applicability. When used in combination with certain solvents, it has good affinity with fluorosurfactants and fat-sensitizing agents, and therefore has excellent storage stability of photosensitive solutions and good performance even in long-term continuous manufacturing processes. It was discovered that photosensitive printing plates can be stably produced, and the present invention has now been completed.

[Object of the Invention] The object of the present invention is to provide a photosensitive coating liquid that has low toxicity during the production of photosensitive printing plates, alleviates odor, improves coating properties, and has excellent storage stability. It is in.

[Structure of the Invention] The objects of the present invention are as follows: 1) A photosensitive coating liquid containing 30% to 80% by weight of diethylene glycol dimethyl ether and a fluorosurfactant.

2) The photosensitive coating liquid according to claim 1 contains at least one selected from the group consisting of an alcohol having 1 to 5 carbon atoms, methyl ethyl kene, ethyl acetate, and diethylene glycol methyl ether. This is achieved using a photosensitive coating solution.

The present invention will be explained in more detail below. The solvent containing diethylene glycol dimethyl ether for forming the photosensitive coating liquid used in the present invention is used in the coating process of the photosensitive coating liquid to improve toxicity and odor, and to Improves sex.

The remaining solvent in the coating solvent used in the present invention may contain at least one selected from the group consisting of alcohols having 1 to 5 carbon atoms, methyl edyl ketone, ethyl acetate, and diethylene glycol monomethyl ether. Preferably, this improves the storage stability of the photosensitive coating solution.

The ratio of diethylene glycol dimethyl ether contained in the solvent to the remaining solvent is such that the former is 30% by weight to 30% by weight.
A range of 80% by weight is preferable, and when it is less than 30% by weight, the effects of the present invention cannot be sufficiently obtained. Also 80% by weight
Exceeding this is economically unfavorable. Therefore, in consideration of economic efficiency, a photosensitive coating liquid with good storage stability can be obtained when the amount is in the range of 3% to 80% by weight, more preferably in the range of 50% to 70% by weight.

This mixed solvent can further be used in combination with other solvents, and can also be appropriately mixed with two or more other solvents.

Other solvents include dimethylformamide, dimethyl sulfoxide, acetone, dioxane, tetrahydrofuran, cyclohexane, methylene chloride, methyl propyl ketone, methyl butyl ketone, diethyl ketone, and water.

The fluorine-based surfactant used in the present invention can be added to the photosensitive coating solution containing diethylene glycol dimethyl ether to improve coating properties, such as Marangoni-1 Vertical streaks, pinholes, etc. are improved, and odor and toxicity are also improved.

As the fluorine-based surfactant preferably used in the present invention, for example, a (meth)acrylate polymer having a fluorinated alkyl group in the side chain can be mentioned, and in this case, the number average molecular weight in terms of standard polystyrene is: IO,000 or less preferably 2.000 N10,00
It is in the range of 0.

The number average molecular weight of the (meth)acrylate polymer is 30.0
f) If Q is exceeded, the effect of improving coating properties will not be sufficient.

The acrylate structural unit or methacrylate structural unit of the moiety having a fluorinated alkyl group in the side chain in the (meth)acrylate polymer is, for example, the following formula [
11 or the following formula [II].

-Formula [11%Formula% (In the formula, R is a hydrogen atom or a methyl group, and n is O~
20, a represents an integer of 0 to 2, and b represents an integer of 0 to L. ) General formula [11] %Formula% (In the formula, R is a hydrogen atom or a methyl group, and n is 0-
10, m is (1 to 20.a represents an integer of O to 2) General formula [1] or the following formula [I! ] The structural unit represented by is specifically shown below.

As the fluorine-based surfactant preferably used in the present invention, for example, a (meth)acrylate polymer having a fluorinated alkyl group in the side chain can be mentioned, and in this case, the number average molecular weight in terms of standard polystyrene is 30. (Preferably 100 or less, more preferably 2.000 to io, ooo
It is within the range of

The number average molecular weight of the (meth)acrylate polymer is 30.0
If it exceeds 00, the effect of improving coating properties will not be sufficient.

As the acrylate structural unit or methacrylate structural unit of the portion having a fluorinated alkyl group in the side chain in the (meth)acrylate polymer, for example, the following - formula U
N] or the following formula [If].

Margin below General formula [1] %formula% (In the formula, R is a hydrogen atom or a methyl group, ■ ■ n is O~20, a is O~2, b is an integer between O and 1 show.

General formula [H] -CH□-〇- ! ■ (In the formula, R is a hydrogen atom or a methyl group, n is O~10, m is O~2, a is an integer between O and 2 show.

■ general formula [ ] or below - formula [! ■] represented by The structural unit is Specifically, it is shown below.

! -9 1-1゜ Margin below ! -11 ! -12 ■ ! -14 ■-25 ■ ■ ■ ■-27 ■-28 ■-17 ■ ! -29 ■ ■ ■ =21 ■ ! -31 ■-32 ■ ■ U-1;? 21; 3 υ−(shiF2)2shiF3 ! ■-36 ■-37 -C11, -CII- 0-(CF2)+aCFs ■ ■-39 ■ -40 ■ -41 1! -1 -CH, -CH- ■! -7 -CH, -C11- υ l! -8 -C11□-CH- ! ! -9 -C112-C11- +1-10 - CII 2- CII - -CH2-C)l- υ ! ■-3 -CH2-CH- -C1h-CH- ■! -5 -(:)I, -CH- saliva ! ■-6 -C)1! -CH- l-11 -CH2-CH- CH3 -CH2-C- ” l-13 C.B.

-CI+, -C- ++-14 C) 1° -C112-C- CI1゜ CI+2-C- 1-11i CI+3 - C112-C ++-17 -CI+2-C- ++-18 CI(3 CI2-C- +1-23 C) 13 -CI+2-C- υ C11゜ -CH2-C- 11th throw type [II+] -(:1I2-C- 0-(Cn112no)-11 ! 1l-1 CII 2- CII +1! -2 -C112-CI- C-〇 C stomach 0 OC2II, OII 0 C31! a OII ++-19 -CI+2-C- ++-20 C11゜ -CI+, -C- ++-21 -CI 2- C- ++-22 H3 -CH2-C- +11-3 +11-4 1i6 +11-7 1i8 ! 1l-9 II+-10 II+ -11 1I+-12 II+-13 II+ -14 C1(.

No. -CI+, -C- 0-Cntb. -+ IV-1 IV-2! ■-3 IV-4 IV-5 IV-6 u-+;s■,t ut;6HI3 IV-17 IV-18 IV-19 IV-20 IV-2+ IV-22 IV-23 IV-24 IV -7 IV-8 v-9 IV-10 IV-11 IV-12 IV-13 IV-14 IV-15 IV-16 (Meta) Acrylate unit Structural unit other than the above CaF+y502NIICzt+aN CII 3)
2 C2tl s OS-0202II 5CyF+
5CONHC3HaN”(CH3) 3cIL --C
Il -CH- 0"cVc-.

Fluorine surfactant c, F, 5COJH4 C, F,, 50□N (C21(5) C1l, Coo
CaF I 7S02NIIC3)16N” (CH
s) 2Cfl -CaF ls C0NII (CI
l2) 3N” (CHs) zCJ4COO-CaF
l 7SO2N (C2H8) C2H4(OCsH
a) 50) ICt F 1scONHc311aN”
(CH3) 2 (Ctl□) 2COO-CaF1
7SO2N(CH3)CH2CH202CCH-CH2
These fluorine-based surfactants are used in an amount of 0.011% to 11% by weight, preferably 0.05% to 0.75% by weight, particularly preferably 0.05% to 0.75% by weight, based on the photosensitive composition contained in the photosensitive coating liquid. is 0.08% to 0.5% by weight.

Margin below CaF17S02N-(CH2)sN”(CHs)zC
LCOO - The coating solution obtained by dissolving in the solvent used in the present invention can contain either a positive-working photosensitive composition or a negative-working photosensitive composition, but this positive-working photosensitive composition As such, a polymer compound containing an orthoquinonediazide group is mainly used, and the polymer compound containing an orthoquinonediazide group is a reaction product of a compound containing an orthoquinonediazide group and an alkali-soluble resin, or a polymer compound containing an orthoquinonediazide group. It is used to mean either or both of the cases where it is a mixture of a compound containing the above and an alkali-soluble resin.

Typical examples will be explained below.

As a polymer compound containing an orthoquinonediazide group,
For example, ester compounds of 0-naphthoquinonediazide sulfonic acid and polycondensation resins of phenols and aldehydes or ketones may be mentioned.

Examples of the phenols include phenol, 0
-cresol, l-cresol, p-cresol, 3.
Examples include monohydric phenols such as 5-xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin.

Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde,
Examples include furfural.

Preferred among these aldehydes are formaldehyde and benzaldehyde.

Furthermore, examples of the above-mentioned ketones include acetone, methyl ethyl ketone, and the like.

Specific examples of the polycondensation resin include phenol-formaldehyde resin, layer-cresol-formaldehyde resin, -, O-mixed cresol-formaldehyde resin, resorcinol-benzaldehyde resin, pyrogallol-acetone resin, and the like.

The condensation rate (0) of the O-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol in the O-naphthoquinonediazide compound (reaction rate per group per unit) is 15 to 80.
%, more preferably 20 to 45%.

Further, as the O-quinonediazide compound used in the present invention, compounds described in JP-A-58-43451 can also be used.

Among the above 0-quinonediazide compounds, 0-quinonediazide is obtained by reacting 1,2-benzoquinonediazide sulfonyl chloride or 1,2-naphthoquinonediazide sulfonyl chloride with pyrogallol acetone condensation resin or 2,3,4-trihydroxybenzophenone. Ester compounds are most preferred.

As the O-quinonediazide compound used in the present invention, each of the above compounds may be used alone, or two or more kinds of compounds may be used in combination.

The polymer compound containing 0-quinonediazide used in the present invention preferably has a molecular weight of 1,500 or more, more preferably 2,000 or more, in view of coating properties.

The above-mentioned 0-quinonediazide compound is preferably used in combination with an alkali-soluble resin. Examples of the alkali-soluble resin include novolak resin, a vinyl polymer having a phenolic hydroxyl group, and those described in JP-A-55-57841. Examples include condensation resins of polyhydric phenols and aldehydes or ketones. Examples of the novolac resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-57841, and phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-127553. Examples include copolycondensation resins of p-substituted phenol and phenol or cresol and formaldehyde as described above.

In addition, the vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and is represented by the following general formula [11 to - Formula [
Polymers containing at least one structural unit of V] are preferred.

-Math [I] General formula [! ! ] General formula [III] General formula [IV] General formula [V] [In the formula, R1 and R7 each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R
3 represents a hydrogen atom, a halogen atom or an alkyl group,
R4 preferably represents a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably represents a hydrogen atom. A represents an alkylene group which may have a substituent and which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, T represents an integer from O to 10, and B has a substituent. represents a phenylene group that may have a substituent or a naphthylene group that may have a substituent. ] The polymer used in the photosensitive composition of the present invention preferably has a copolymer-type structure, and can be used in combination with the structural units represented by formulas [1] to [V] above. Examples of monomer units that can be used include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene, p-
Styrenes such as methylstyrene and p-chlorostyrene,
For example, acrylic acids such as acrylic acid and methacrylic acid,
For example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, maleic anhydride, etc., such as methyl acrylate,
Ethyl acrylate, loobyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-acrylic acid
Esters of α-methylene aliphatic monocarboxylic acids such as chloroethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; nitrites such as acrylonitrile and methacrylonitrile; e.g. acrylamide; Amides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc., vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. , vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene,
Ethylene derivatives such as 14-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-ditroethylene, such as N
- N-vinyl monomers such as vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylvirolone, and N-vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above monomers, aliphatic monocarboxylic acid esters and nitriles exhibit excellent performance for the purpose of the present invention and are therefore preferred.

Considering the applicability of these alkali-soluble resins,
Those having a molecular weight of 1,500 or more are preferable, and those having a molecular weight of 2,000 or more are more preferable.

In addition to the above-mentioned materials, these photosensitive compositions may also contain colorants such as dyes and pigments, sensitizing agents, plasticizers, surfactants, organic acids, acid anhydrides, and acids that can be removed by exposure to light. Compounds that may be generated can be added.

There are various types of negative photosensitive materials used in the present invention, and representative ones will be described below.

(1) Photosensitive composition containing diazo resin The diazo resin represented by the condensate of p-diazodiphenylamine and formaldehyde may be water-soluble or water-insoluble, but is preferably
7 and No. 57-43890, etc., which are water-insoluble and soluble in ordinary organic solvents are used. Particularly preferred is a diazo resin represented by the following general formula [11].

General formula [11] [In the formula, R1, R2 and R3 represent a hydrogen atom, an alkyl group or an alkoxy group, and R4 represents a hydrogen atom, an alkyl group or a phenyl group.

X represents ppa or BF4, and Y represents -N! 1--3-
or -O-] The diazo resin is preferably used in combination with a film-forming resin, particularly a lipophilic polymer compound having a hydroxyl group. In addition to the above-mentioned lipophilic polymer compounds, examples of such lipophilic polymer compounds include those having an aliphatic hydroxyl group in the side chain, for example, 2
Examples include copolymers of -hydroxyethyl acrylate or 2-hydroxyethyl methacrylate and other copolymerizable polymers. In addition to these, polyvinyl butyral resins, polyurethane resins, polyamide resins, epoxy resins, novolak resins, natural resins, etc. may be added as necessary.

Various polymeric compounds can be used as the binder used in combination with the diazonium salt, but preferably, JP-A-54-9
Monomers having an aromatic hydroxyl group as described in Japanese Patent No. 8613, such as N-(4-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, o-, m+, or p- Copolymers of hydroxystyrene, o+, m+, or p-hydroxyphenyl methacrylate, etc., with other monomers, hydroxyethyl acrylate units or hydroxy as described in U.S. Pat. No. 4,123,276. Polymers containing ethyl methacrylate units as the main repeating unit Natural resins such as shellac and rosin, polyvinyl alcohol, polyamide resins described in U.S. Pat. No. 3,751,257, U.S. Pat. No. 3,66
0.097, a phthalated polyvinyl alcohol resin, an epoxy resin condensed from bisphenol A and epichlorohydrin, and celluloses such as cellulose acetate and cellulose acetate phthalate.

Examples of the alkali-soluble resin include novolac resin, vinyl polymer having a phenolic hydroxyl group, and JP-A-55-5
Examples include condensation resins of polyhydric phenols and aldehydes or ketones described in Japanese Patent No. 7841. Examples of novolac resins include phenol/formaldehyde resin, cresol/formaldehyde resin, and JP-A-5
Phenol-cresol-formaldehyde copolycondensation resin as described in Japanese Patent Application Laid-Open No. 55-127553,
Examples include copolycondensation resins of -substituted phenol and phenol or cresol and formaldehyde.

In addition to the above-mentioned materials, these photosensitive compositions may also contain colorants such as dyes and pigments, sensitizing agents, plasticizers, surfactants, organic acids, acid anhydrides, and acids that can be removed by exposure to light. Compounds that may be generated can be added.

These binders are present in the solid content of the photosensitive composition in an amount of 40 to 99%.
ii% by weight, preferably 50 to 95% by weight. The diazo resin is 1 to 60% by weight, preferably 3 to 30% by weight.
Contains i amount%.

Other dyes, pigments such as pigments, fat-sensitizing agents, plasticizers, surfactants, etc. can be added to these photosensitive compositions.

(2) A photosensitive composition containing a polymer compound having -C-C)I-C- group in the main chain or side chain of the 11-merged such a polymer compound includes the main daughter or side chain of the polymer The main component is a photosensitive polymer such as polyesters, polyamides, and polycarbonates containing -C-CH-C- as a photosensitive group (for example, U.S. Patent No. 3,0
No. 30,208, No. 3.707.373 and No. 3
, 453, 237)
; Those whose main components are photosensitive polyesters derived from (2-probeliden) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols (for example, U.S. Pat. No. 2,956,878 and U.S. Pat. 3.173.78
7); cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose, and the like (e.g., U.S. Pat. No. 2,690,966); , same No. 2,752,37
2, No. 2,732,301, etc.).

These photosensitive compositions may contain other sensitizers, stabilizers, plasticizers, pigments, dyes, and the like.

(3) Photopolymerizable composition comprising an addition polymerizable unsaturated compound This composition preferably comprises (a) a vinyl monomer having at least two terminal vinyl groups, (b) a photopolymerization initiator, and ( C) Consists of a polymer compound as a binder.

The vinyl monomer of this component (a) is
No. 5093, No. 35-14719, No. 44-2872
It is described in each publication No. 7.

Acrylic or methacrylic acid esters of polyols, such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or methylene bis(meth)acrylamide , bis(meth)acrylamides such as ethylene bis(meth)acrylamide, or unsaturated eastomers containing urethane groups, such as di(2'-methacryloxyethyl)-2,4-tolylene diurethane, di( Examples include reaction products of diol mono(meth)acrylate and diisocyanate such as 2-acryloxethyl)trimethylene diurethane.

As the photopolymerization initiator of component (b), the compound represented by the general formula [I] can be used, but other types can also be used. For example, carbonyl compounds, organic sulfur compounds, perfusates, redox compounds, azo and diazo compounds, as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar, mentioned above;
These include halogen compounds and photoreducible dyes. More specifically, it is disclosed in British Patent No. 1,459,563.

Furthermore, various known polymers can be used as the binder for component (C). Specific binder details are described in US Pat. No. 4,072.527.

These photopolymerizable compositions contain thermal polymerization inhibitors, plasticizers,
It can contain dyes, pigments, etc.

(4) Photosensitive composition containing an azide group As the photosensitive azide compound, an aromatic azide compound in which the azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group is preferably used.

For example, polyazidostyrene, polyvinyl-P as described in U.S. Pat. No. 3,098,311.
-Azidobenzoate, polyvinyl-p-azidobenzal, reaction product of azidoarylsulfonyl chloride and unsaturated hydrocarbon polymer described in Japanese Patent Publication No. 45-9613, and Japanese Patent Publication No. 43-21017, 44
-22.9, 44-22954, 45-249
Examples include polymers containing sulfonyl azide and carbonyl azide, as described in each publication of No. 15.

Sensitizing agents, general surfactants other than fluorine surfactants, sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, pigments such as dyes and pigments, etc. added to the photosensitive composition. The amount of additives added differs depending on the type, but in general, it is added in an amount of 0.01 to 20
% by weight, preferably from 0.05 to 10% by weight, is suitable.

Dyes preferably used in the present invention include basic dyes and oil-soluble dyes. Specifically, Victoria Pure Blue BOH, Victoria Blue BH, Methyl Violet, Eisen Malachite Green (manufactured by Hodogaya Chemical Industry), Patent Pure Blue
Basic dyes such as vx, Rhodamine B, and Methylene Blue (manufactured by Sumitomo Chemical), as well as Sudan Blue II, Victoria Blue F4R (B.

A, S, F), oil blue #603, oil
Oil-soluble dyes such as Blue BOS and Oil Blue II N (all manufactured by Orient Kagaku Kogyo) may be used.

Various types of supports can be used for producing photosensitive printing plates by applying the photosensitive coating solution of the present invention, such as aluminum, zinc, copper, etc.

Metal plates such as steel, metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, etc., paper and plastics treated to make them hydrophilic, paper and plastic films coated with metals, glass plates, resins. Examples include coated paper and paper covered with metal foil such as aluminum.

Among these, aluminum plates are preferred.

In particular, in the case of an aluminum plate support, it is preferable that the support be subjected to surface treatments such as graining, anodizing, and, if necessary, sealing.

As a method for carrying out the above-mentioned graining treatment, commonly used techniques such as brush polishing, ball polishing, chemical polishing, electrolytic etching, etc. are employed after degreasing the surface of the aluminum plate or the like.

The above anodic oxidation treatment is performed using, for example, phosphoric acid, chromic acid, boric acid,
This is carried out by passing an electric current through an aluminum plate or the like as an anode in an aqueous or non-aqueous solution of an inorganic salt such as sulfuric acid, or an organic acid such as oxalic acid or sulfamic acid, or a mixture of two or more of these acids.

Furthermore, the sealing treatment is carried out by immersion in a hot aqueous solution of a sodium silicate solution, hot water, and some inorganic or organic salts, or by a steam bath.

In the present invention, the amount of photosensitive coating liquid applied to the support is as follows:
Depending on the use, - numerically 0.5 to 3 as solid content
．． 5 g/s" is appropriate.

The coating method of the present invention includes dip coating, roll coating, reverse roll coating, air doctor coating, blade coating, rod coating, knife coating, squeeze coating, gravure coating, cast coating, curtain coating, extrusion coating,
The coating film thickness is 0.1 to 5 g/m'.
is preferred. Further, the drying temperature is in the range of 20 to 150°C, preferably 30 to 100°C.

[Examples] The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 A photosensitive solution having the following composition was prepared and coated on a grained aluminum plate using a roll coater to reduce the solid content to 1. I
After coating to a coating weight of 1 g/s2, it was dried to obtain Sample 1 of a photosensitive planographic printing plate.

[Photosensitive liquid] Pyrogallol acetone resin and naphthoquinone (1,2
)-Diazide-4-sulfonic acid chloride ester compound (Mw=2500) 2.3 parts by weight phenol and m+, p- mixed cresol (each molar ratio 4
8:32:20) and formaldehyde (Mw-10000) 6.71 parts by weight Novolac tree I11 synthesized from para-octylphenol and formalin (Mw-1800) 0.9 parts by weight 2-trichloromethyl -5-(β-Benzofuryl vinyl)-1,3,4-oxadiazole 0.05 parts by weight Victoria Pure Blue B OH 0.07 parts by weight Fluorine surfactant rFC-430J (manufactured by 3M) 0.03
Parts by weight Diethylene glycol dimethyl ether 27 parts Ethyl alcohol 18 parts by weight Samples 2 to 1 of photosensitive lithographic printing plates were prepared in the same manner as Sample 1 except that the organic solvent composition in the photosensitive solution was replaced with the compound shown in Table 1.
2 was produced.

For Samples 1 to 12 thus obtained, the coating properties of the printing plates (Marangoni-5 vertical streaks and pinholes) and the storage stability of the photosensitive solutions were compared, and the results are shown in Table 1.

Regarding storage stability, Table 1 shows that after storing the photosensitive solution prepared as described above in a sealed container at 30°C for 7 days,
The presence or absence of precipitation and vertical streaks, marangoni, and pinholes that occur during coating were evaluated. Further, after the entire surface of the printing plate obtained by applying the photosensitive liquid after storage was exposed, the staining of the non-image area of the printing plate obtained by development was evaluated. The conditions are as follows.

Developer: 4% sodium metasilicate aqueous solution with 0.1% sodium benzenesulfonate added (does not contain organic solvent) Automatic developer: Conical S plate automatic processor rPSQ-860 (manufactured by Konica) Development Temperature: 25° C. Development time: 20 seconds The term “marangoni” here refers to hazy, swirl-like coating unevenness that occurs on the coated surface after coating and drying.

The cause of this type of coating unevenness is the Marangoni effect, which is caused by local differences in surface tension of the wet photosensitive layer due to a temperature drop accompanying the volatilization of the solvent.

Pinholes refer to circular white spots in the photosensitive layer that appear on the coating surface, and vertical streaks are unevenness in the thickness of the photosensitive layer that appears in the running direction of the support because the coating solution is not smoothed. be.

The results are shown in Table 1.

As is clear from Table 1 below, samples 7 to 10, which are outside the scope of the present invention, had poor observation results for Marangoni-1 vertical streaks and pinholes.

On the other hand, when the organic solvent used in the present invention was used as a coating solvent, a rating of A was obtained, which was preferable.

Margin Example 2 A photosensitive liquid having the following composition was prepared and coated onto a grained aluminum plate using a roll coater to give a solid content of 1.8.
After coating to a coating amount of g/m 2 , it was dried to obtain Sample 13 of a photosensitive planographic printing plate.

[Photosensitive liquid] Charged monomer molar ratio, N-(4-hydroxyphenyl) methacrylamide: acrylonitrile ethyl acrylate: methacrylic acid: n-butyl acrylate = 8:3
From the raw material 2:40:10:10, JP-A-62-704
Copolymer obtained by the method shown in Synthesis Example 1 of Publication No. 5 (Mww 55000) 8.
Q It Hexafluorophosphate (Mw-2400) of condensation resin of p-diazophenylamine and paraformaldehyde (molar ratio 1:0.9) 0.48
Part by weight Jurimer AC-1OL [manufactured by Nippon Pure Chemical Industries, Ltd.] 0
．． 36 parts by weight Victoria Pure Blue B OHO, 09 parts by weight Fluorine surfactant rFC-430J (manufactured by 3M) 0.03
Parts by weight Diethylene glycol dimethyl ether 27 parts Methyl ethyl ketone 18 parts by weight Samples 14 to 22 of photosensitive lithographic printing plates were prepared in the same manner as Sample 13 except that the organic solvent in the above photosensitive liquid composition was replaced with the compound shown in Table 2. .

Samples 13 to 22 thus obtained were compared in terms of coating properties (Marangoni-1 vertical streaks and pinholes) and storage stability of the photosensitive solution.

Regarding storage stability, Table 2 shows that after putting the photosensitive solution prepared as described above in a sealed container and storing it at 30°C for 5 days,
The presence or absence of precipitation and vertical streaks, marangoni, and pinholes that occur during coating were evaluated. Furthermore, the printing plate obtained by coating the photosensitive liquid after storage was developed without being exposed to light, and the staining of the non-image area of the obtained printing plate was evaluated. The conditions are as follows.

Current situation: Phenyl cellosolve 480g Jetanolamine (80%) 159g Bionin A441
3 (manufactured by Gyousaku Yushi Co., Ltd.) TAOG water
1242 automatic processor: Konica PS plate automatic processor rPSQ-860J (manufactured by Konica) Development temperature: 25°C Development time = 20 seconds The results are shown in Table 2.

As is clear from Table 2 below, samples 16 to 19, which are outside the scope of the present invention, had poor observation results for Marangoni-1 vertical streaks and pinholes.

On the other hand, when the organic solvent used in the present invention was used as a coating solvent, a rating of A was obtained, which was preferable.

[Effect of the invention] Diethylene glycol dimethyl ether is extremely preferable as a coating solvent because it has little odor and toxicity.
The coating properties are not good, but by adding a fluorosurfactant to it, Marangoni-1 vertical streaks, pinholes, etc. are improved, and odor and toxicity are also improved.

Further, the present invention provides a photosensitive coating liquid that can stably produce a photosensitive printing plate having good performance even in a continuous manufacturing process for a long time by having the structure as described in claim 2. .

Claims (1)

[Scope of Claims] 1) A photosensitive coating liquid containing 30% to 80% by weight of diethylene glycol dimethyl ether and a fluorosurfactant. 2) Photosensitivity characterized in that the photosensitive coating liquid according to claim 1 contains at least one member selected from the group consisting of alcohol having 1 to 5 carbon atoms, methyl ethyl ketone, ethyl acetate, and diethylene glycol monomethyl ether. Coating liquid.