JPH03255446A - Photosensitive coating solution - Google Patents

Abstract

PURPOSE:To reduce toxicity and foul odor and to improve the suitability of a photosensitive soln. to coating and the shelf stability by incorporating at least one kind of compd. having ketone and alcoholic hydroxyl groups as a coating solvent. CONSTITUTION:At least one kind of compd. having ketone and alcoholic hydroxyl groups is incorporated as a coating solvent. The compd. may be 3-8C chain compd. or 5-9C cyclic compd., preferably 4-hydroxy-2-butanone or 3- methylolcyclohexanone. The compd. may be mixed with one or more kinds of other solvents. In this case, the compd. is used by >=20 wt.%, preferably 30-70 wt.% of the total amt. Foul odor and toxicity are reduced and a photosensitive coating soln. having superior suitability to coating and superior shelf stability can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive coating liquid, and more specifically, it has improved odor, low toxicity, improved coating properties, and improved material solubility of the photosensitive liquid. This invention relates to a photosensitive coating solution which provides an improved photosensitive solution with excellent storage stability, and which also provides a lithographic printing plate with no diazo residue when a diazo resin is used as the photosensitive material.

[Background of the Invention] A photosensitive lithographic printing plate is produced by dissolving a photosensitive composition in a suitable solvent, applying the solution to a support, and drying it. Conventionally, such a photosensitive lithographic printing plate During the production of
Various solvents are used to dissolve the photosensitive composition, such as methyl cellosolve (ethylene glycol monomethyl ether), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monomethyl ether acetate.

However, although these coating solvents have good storage stability and solubility, they have a problem in that they are highly toxic during the production of photosensitive printing plates, and they also have a strong odor and are unpleasant, making them 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, which impairs the value as a product, which is a problem. It has become.

Furthermore, as disclosed in JP-A No. 61-6648, a propylene glycol compound is used as a solvent for a photosensitive coating solution.
Although it is described in Japanese Patent Application Laid-open No. 14652/1983,
The photosensitive coating solution obtained using this propylene glycol compound not only has poor storage stability (precipitate formation), but also
A so-called dilute coating solution with poor material solubility and an increased amount of tt solvent are used, resulting in an increase in drying load and an increase in solvent cost, which is undesirable. Therefore, improvements in these points are desired.

Therefore, the inventors of the present invention have conducted various studies regarding the above-mentioned problems, and have discovered that the problems with photosensitive liquids can be improved by using a certain type of organic solvent, and have hereby completed the present invention. reached.

[Objectives of the Invention] The objects of the present invention are to improve odor, have low toxicity, improve coating properties, have excellent material solubility and storage stability of photosensitive liquids, and use diazo resin as a photosensitive material. It is an object of the present invention to provide a photosensitive coating solution containing a coating solvent that does not leave diazo residue when exposed to water.

[Structure of the Invention] The above object of the present invention is achieved by a photosensitive coating liquid characterized by containing at least one of a compound having a ketone group and an alcoholic hydroxyl group as a coating solvent.

The present invention will be explained in more detail below.

The photosensitive coating liquid used in the present invention includes, as a coating solvent,
It contains at least one of compounds having a ketone group and an alcoholic hydroxyl group, and specifically, these include a chain compound having 3 to 8 carbon atoms, a compound containing a cyclic structure having 5 to 9 carbon atoms, In the process of applying a photosensitive coating liquid, toxicity and odor are improved (the coating properties of the photosensitive liquid are improved), and storage stability is improved, and these solvents improve the material solubility of the photosensitive coating liquid.

The compound having a ketone group and an alcoholic hydroxyl group used in the present invention is preferably 4-hydroxy-2-butanone, 3-hydroxy-2-butanone, 1-hydroxy-2-butanone, 3-hydroxy-2-pentanone. , 4
-Hydroxy-2-pentanone, 5-hydroxy-2-
Pentanone, 4-hydroxy-3-pentanone, 5-hydroxy-3-pentanone, 3-hydroxy-2-hexanone, 4-hydroxy-2-hexanone, 6-hydroxy-2-hexanone, 5-hydroxy-3-hexanone, 6-hydroxy-3-hexanone, 3-methyl-3
-Hydroxy-2-pentanone, 4-methyl-4-hydroxy-2-pentanone, 3-hydroxycyclopentanone, 3-hydroxycyclohexanone, 4-hydroxycyclohexanone, 3-methylolcyclohexanone, and the like.

These compounds having a ketone group and an alcoholic hydroxyl group can be used alone or in combination of two or more.

In the compound having a ketone group and an alcoholic hydroxyl group used in the present invention, other solvents are used in an amount of 20% by weight or more, preferably 30% to 70% by weight of the total solvent, and one or more of these are mixed. It can be used as

Other solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butanol, 5eC-butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol, 1-hexanol, etc. alcohol, acetone,
Methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-〇-butyl ketone,
Ketones such as methyl isobutyl ketone, cyclopentanone, cyclohexanone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether,
Diethylene glycols such as diethylene glycol monoethyl ether, diethylene glycol isopropyl ether, diethylene glycol monophenyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, ethyl acetate,
Acetate esters such as n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoaryl acetate, n-hexyl acetate, other water, methyl lactate, ethyl lactate, lactic acid Propyl, diethyl ether, dioxane, dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, 3-methoxy-
Examples include 1-butanol, 3-methyl-3-methoxy-1-butanol, tetrahydrofuran, methylene chloride, and the like. Among these, the diethylene glycols, lactic acid esters, γ-butyrolactone, 3-methoxy-1-butanol and 3-methyl-3-methoxy-1-butanol are preferably used.

In particular, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, methyl lactate, ethyl lactate, and 3-methoxy-1-butanol have low toxicity, mild odor, appropriate boiling point, and appropriate drying load. It is particularly preferably used because it provides an excellent appearance of the coated product.

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 as this positive-working photosensitive composition, , a polymer compound containing an orthoquinonediazide group is mainly used. Here, the polymer compound containing an orthoquinonediazide group refers to 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 the compound containing the compound and the 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, organ-cresol, p-cresol, 3,
Examples include m-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, l-cresol/formaldehyde resin, (1)-10-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, pyrogallol/acetone resin, and the like.

The condensation rate of 0-naphthoquinonediazide sulfonic acid with respect to the O)I group of the phenol of the 0-naphthoquinonediazide compound (reaction rate per 1 group) is 15 to 8.
It is preferably 0%, more preferably 20-45%.

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 types 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 alkali-soluble resins include novolac resins, vinyl polymers having phenolic hydroxyl groups, and condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-57-57841. 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.

Moreover, 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 a polymer having the following general formula [I] to -numerical formula [
Polymers containing at least one structural unit of V] are preferred.

- Numerical formula [I General formula [II] General formula [ml General formula [rV] H General formula [V H [In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R
5 represents a hydrogen atom, a halogen atom or an alkyl group,
Preferably, it 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, preferably a hydrogen atom. A represents an alkylene group optionally having a substituent that connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, Peng represents an integer from 0 to 1O, 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 shown in the formulas [1] to [EV] above. Examples of monomer units 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, 1it-n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, acrylic acid-
Esters of α-methylene aliphatic monocarboxylic acids such as 2-chloroethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; nitriles such as acrylonitrile and methacrylonitrile; For example, amides such as acrylamide, e.g. acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m
- Anilides such as methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, chloride Vinyl, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1
- Ethylene derivatives such as methyl-1-nitroethylene,
For example, N-vinylvirol, N-vinylcarbazole,
There are N-vinyl-based polymers such as N-vinylindole, N-vinylpyrrolidene, and N-vinylpyrodone. 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 [I].

General Formula [I] [In the formula, RI 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 PF6 or BF4, and Y represents -NH--5- or -0-. ] 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 those listed above, such lipophilic polymer compounds include monomers having an aliphatic hydroxyl group in the side chain, such as 2
Copolymers of -hydroxyethyl acrylate or 2-hydroxyethyl methacrylate and other copolymerizable monomers can be mentioned. 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
A monomer having an aromatic hydroxyl group as described in Japanese Patent No. 8613, such as N-(4-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylic acid, o+, m-, or Copolymers of p-hydroxystyrene, o+, m-, or p-hydroxyphenyl methacrylate, etc., with other monomers, hydroxyethyl acrylate as described in U.S. Pat. No. 4,123,276. Polymers containing units or hydroxyethyl methacrylate units as main repeating units Shellac, natural resins such as 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 JP-A No. 5-57841, p as described in JP-A-55-127553
Examples include copolycondensation s1 fats 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%.
It is contained in an amount of 50 to 95% by weight. The diazo resin is contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

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

1 (2) Photosensitive composition containing a polymer compound having a -C-CH-C- group in the main chain or side chain of the polymer. Those whose main component is a photosensitive polymer such as polyesters, polyamides, and polycarbonates containing -C-CH-C- as a photosensitive group (for example, U.S. Pat. No. 3,030,208, U.S. Patent No. 3) 707.373 and 3,453.237); photosensitive compounds derived from (2-probelidene) malonic acid compounds such as cinnamylidene-7a acid and difunctional glycols; polyesters as the main component (for example, U.S. Patent Nos. 2,956,878 and 3,17)
3.787):
Cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose and their analogs (
For example, U.S. Patent Rate No. 2.690.966, U.S. Patent No. 2,75
2,372, 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 caramers 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 above general formula [1] can be used, but other types can also be used. For example, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar, cited above;
These include halogen compounds and photoreducible dyes. Further C is specifically disclosed in British Patent No. 3i81,459,563.

Furthermore, various known polymers can be used as the binder for component (e). Details of four-body binders 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. 3,096,311;
-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
No.-229, No. 44-22954, No. 45-2491
Polymers having sulfonyl azide or carbonyl azide as described in each publication of No. 5 can be mentioned.

A liposensitizing agent and a surfactant added to the photosensitive composition,
The amount of additives such as sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, and pigments such as dyes and pigments varies depending on the type, but in general, they are included in the photosensitive composition contained in the photosensitive coating solution. 0.01 to 201% by weight, preferably 0.05 to 201% based on the substance
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 vx10-Damine B5 Methylene Blue (manufactured by Sumitomo Chemical), Sudan Blue II, Victoria Blue F4R (B.

A, S, F), oil blue #603, oil
Oil-soluble dyes such as Blue BO3 and Oil Blue IIN (manufactured by Orient Kagaku Kogyo Co., Ltd.) include oil-soluble dyes.

To produce a photosensitive printing plate by applying the photosensitive coating solution of the present invention (a variety of suitable supports can be used, for example, metal plates such as aluminum, zinc, copper, steel, etc., and chromium , metal plates plated or vapor-deposited with zinc, copper, nickel, aluminum, etc., paper and plastics treated to make them hydrophilic, paper and plastic films coated with metals, glass plates, resin-coated paper, metal foils such as aluminum, etc. For example, paper covered with

Among these, aluminum plates are preferred.

In particular, in the case of an aluminum plate support, surface treatments such as graining, anodizing, and, if necessary, sealing are preferably applied.

As a method for 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 IA filling is carried out by immersion in a hot aqueous solution of a sodium silicate aqueous solution, a mineral salt, 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/m'' is appropriate.

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

[Examples] The present invention will be explained below using Examples, but the present invention is not limited thereto.

Example 1 [Preparation of WA photolithographic printing plate] An aluminum plate with a thickness of 0.24 mm was degreased in a 5 wt % aqueous sodium hydroxide solution at 60° C. for 1 minute, and then treated with 0.5 molar hydrochloric acid of 11. In aqueous solution, temperature 25
The electrolytic etching process was performed under the following conditions: °C, current density: 60 A/dI, 112 seconds, and processing time: 30 seconds.

Then, in a 5 wt % sodium hydroxide aqueous solution at a temperature of 60
After desmutting for 10 seconds at °C, anodizing was performed in a 20% by weight sulfuric acid solution at a temperature of 20 °C, a current density of 3 A/d1, and a treatment time of 1 minute. Further, hot book sealing treatment was performed for 20 seconds with hot water at 30° C. to produce an aluminum plate as a support for lithographic printing plate material.

A photosensitive composition coating solution having the following composition was applied to the aluminum plate prepared as above using a roll coater, and dried at 90° C. for 45 minutes to obtain positive-working photosensitive lithographic printing plate sample No. 091. .

Note that the amount of photosensitive composition was 24 B/di2.

[Coating liquid composition of photosensitive liquid] Binder (BD-1) 7.0g
Quinonediazide compound (QD-1) 1.682
-Trichloromethyl-5-(β-benzofuryl vinyl)
-1,3,4-oxadiazole 0.06g Ester compound of novolac resin synthesized from roseoctylphenol and formalin and 1,2-quinonediazide-5-sulfonic acid chloride (average molecular weight 2000
) 0.06g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.05g
4-Hydroxy-2-butanone 30g Diethylene glycol dimethyl ether 70g Photosensitive coating was carried out in the same manner as Sample No. 001 except that the binder, quinonediazide compound and solvent were changed as shown in Table 1 in the coating solution composition of the above photosensitive composition. Liquid sample No.
, 2-12 were obtained.

Samples Nos. 011 to 12 thus obtained were divided into two parts, one of which was coated with a photosensitive liquid immediately after the photosensitive liquid was prepared, and the coatability and developability of this sample were evaluated. The other samples Nos. 011 to 12 were placed in a sealed container and stored at 30° C. for 7 days, and then the presence or absence of precipitation of the photosensitive solution and the developability of the samples coated with the photosensitive solution were evaluated.

[/! 5 Compounds used in light liquid] QD-1 QD-2 x/y-1/2, Mw of resin before reacting Q2
-9002 QD-3 14 x/y-1/2, Mw of resin before reacting with Q+
=900Q+)U2 ■ Mw of the resin before reacting with Ql-1500D-4 H Mw of the resin before reacting with Q2-1500QD-5 BD-1 Phenol and m-, p-mixed cresol (each molar ratio 4
Copolymer resin BD-2 of 8:32:20) and formaldehyde [Development conditions] Developer: 4% sodium metasilicate aqueous solution to which 0.1% sodium benzenesulfonate was added (contains no organic solvent) Automatic Developing machine: Conical S plate automatic developing machine RPS to 910J (manufactured by Konica) Developing temperature = 27°C Developing time: 20 seconds The developer under the standard conditions was diluted as follows and each sample was developed and exposed. The status of remaining layers was evaluated.

(k:u:m:n-25:20:50:2, M+1
l-60000) [Exposure conditions] A positive transparent original image was brought into close contact with a sample of a photosensitive lithographic printing plate,
Exposure was carried out from a distance of 90 cm using a lKw metal halide lamp (Idol Fin 2000 manufactured by Iwasaki Electric Co., Ltd.) as a light source.

The evaluations in Table 1 are as follows.

Precipitation: A: None, B: A small amount, C: Developability: A: No photosensitive layer remains B: A small amount of photosensitive layer remains, but it can withstand practical use C: Photosensitive layer remains, and it is not suitable for practical use Slightly affected degree D = Significant photosensitive layer remains [Coatability] Marangoni 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.

Each item of coating property: : Excellent B: Good C: Slightly poor D: Poor The results of the obtained samples are shown in Table 1.

As is clear from Table 1 below, the non-preserved products according to the present invention are rated as A, but the non-preserved products are not constant. Regarding the evaluation after storage, in the present invention, the evaluation is substantially A-B in terms of precipitation, coating properties, and developability, whereas in the case of the products other than the present invention, the evaluation is mostly C, although there are A%B. -D.

Margin below Example 2 A photosensitive solution having the following composition was prepared, the aluminum plate prepared in Example 1 was grained, and then applied to the aluminum plate using a roll coater, and then dried at 90°C for 4 minutes. Sample No. 13 of a negative planographic printing plate was obtained. In addition,
The photosensitive coating weight was 16 mg/da+2.

[Coating liquid composition of photosensitive liquid] The molar ratio of charged monomers is N-(4-hydroxyphenyl) methacrylamide: acrylonitrile ethyl acrylate: methacrylic acid: n-butyl acrylate = 8:
32:40:10:10 raw material
Copolymer obtained by the method shown in Synthesis Example 1 of Publication No. 45 (average molecular weight 55,000)
12.0 g Hexafluorophosphate (average molecular weight 2400) of condensation resin of p-diazodiphenylamine and paraformaldehyde (molar ratio 1:0.9)
0.48g Jurimer AC-10L [manufactured by Hiki Junyaku Co., Ltd. 0.31ig Victoria Pure Blue B OH0,0934-hydroxy-2-butanone 30g diethylene glycol dimethyl ether 70g The composition of the organic solvent in the above photosensitive solution is shown in Table 2 Sample 13 except for replacing with compound
Photosensitive liquid samples 14 to 22 were prepared in the same manner as described above.

Samples 14 to 22 thus obtained were evaluated in exactly the same manner as in Example 1, and the results are shown in Table 2.

[Development conditions] Development Fl: Phenyl cellosolve 480g Jetanolamine (SO%) 159g Bionin A44
13 (manufactured by Takemoto Yushi Co., Ltd.) 180g water
12
11 Automatic developing machine: Konica PS version automatic developing machine rpsx-9t OJ (manufactured by Konica) Development temperature = 2
7°C Development time: 20 seconds The dilution rate of the developer is as follows.

[Diazo Remains] "Diazo Remains" refers to organic dyes in the photosensitive resin or photosensitive composition that remain in the non-image areas of the printing plate after development in negative photosensitive lithographic printing plates using diazo resin. This is a phenomenon that remains and is not completely removed. This may cause staining of the printing plate in non-image areas, but it is also a problem because it deteriorates the plate inspection properties and becomes smudged after erasing the printing plate, causing trouble during printing.

[Method for evaluating diazo residue] An unexposed sample is developed using a developer under standard conditions under the development conditions shown in Examples. After that, part of the sample is covered with light-shielding paper and exposed to light. At this time, the reflection density of the exposed area and the unexposed area was measured using a densitometer (Konica Densitometer PDA-65, manufactured by Konica Corporation), and the difference between the two values is shown in the table. The smaller the value, the less the photosensitive composition remained before exposure, which is preferable.

As is clear from Table 2 in the margin below, in the evaluation after storage, the present invention was evaluated as substantially A in terms of precipitation, coatability, and developability, whereas those other than the present invention were evaluated as A. Most of the evaluations are C to D, although there are some Bs. Regarding the diazo residue, the value of the present invention is as small as 0.03 to 0.07, whereas the value of the value is relatively large for the products other than the present invention.

[Effects of the Invention] The present invention uses a compound having a ketone group and an alcoholic hydroxyl group as a solvent for a photosensitive coating solution, which improves odor, has low toxicity, and improves the coating properties and storage stability of the photosensitive coating solution. An excellent photosensitive coating solution can be obtained.

Furthermore, a photosensitive coating liquid with improved diazo residue and material solubility can be obtained.

Claims (1)

[Claims] A photosensitive coating liquid characterized by containing at least one compound having a ketone group and an alcoholic hydroxyl group as a coating solvent.