JPH0580501A - Photosensitive coating solution composition - Google Patents

Abstract

PURPOSE:To obtain a coating solution less in malodor and toxicity in production or after production and excellent in coating property by containing ethyleneglycohol monopropylether. CONSTITUTION:At least ethyleneglycohol monopropylether is contained. Ethyleneglycohol monopropylether is also used together with a well-known coating solvent. And the coating solution obtained by dissolving in the solvent containing ethykeneglycohol monopropylether can contain either a positive photosensitive composition or a negative photosensitive composition. A high polymer compound containing orthoquinone diazide group is mainly used as the positive photosensitive composition and in this case, the high polymer compound containing orthoquinone diazide group is an reaction product or the like of a compound containing orthoquinone diazide group with an alkali soluble resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive coating liquid composition, and more particularly to a photosensitive coating liquid composition which uses a coating liquid solvent having little odor and toxicity.

[0002]

BACKGROUND OF THE INVENTION The photosensitive layer of a photosensitive lithographic printing plate is usually obtained from a coating solution prepared by dissolving a composition containing a photosensitive substance and a binder resin in a coating solvent such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether. ..

However, since such a coating solvent has strong odor and toxicity, it has become a serious problem in the working environment during and after manufacture. Further, the use of such a coating solvent causes a serious problem of coating failure such as vertical stripes, which significantly deteriorates the coating property, which is also a serious problem.

Accordingly, it is an object of the present invention to provide a photosensitive coating liquid composition which has very little odor and toxicity during or after production and has excellent coating properties.

[0005]

SUMMARY OF THE INVENTION As a result of intensive studies by the present inventors in view of the above problems, the above object of the present invention can be achieved by providing a photosensitive coating liquid composition containing at least ethylene glycol monopropyl ether. I found that.

The present invention will be described in more detail below.

The ethylene glycol monopropyl ether used as a coating solvent in the present invention is preferably 30 to 100% by weight, more preferably 50% by weight in the coating liquid composition.
~ 100% by weight.

The above ethylene glycol monopropyl ether can also be used in combination with other conventionally known coating solvents.

In the present invention, the coating solution obtained by dissolving in a solvent containing ethylene glycol monopropyl ether may contain either a positive photosensitive composition or a negative photosensitive composition. As the positive photosensitive composition, a polymer compound containing an orthoquinonediazide group is mainly used. Here, the polymer compound containing an orthoquinonediazide group is a reaction product of a compound containing an orthoquinonediazide group and an alkali-soluble resin. In the case of a product or a mixture of a compound containing an orthoquinonediazide group and an alkali-soluble resin, it is used to mean either or both.

The typical ones will be described below.

Examples of the polymer compound containing an orthoquinonediazide group include ester compounds of o-naphthoquinonediazide sulfonic acid and a polycondensation resin of phenols and aldehydes or ketones.

Examples of the above-mentioned phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, catechol, resorcin, hydroquinone and the like. Examples thereof include trihydric phenols such as dihydric phenol, pyrogallol, and phloroglucin.

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

Preferred of these aldehydes are formaldehyde and benzaldehyde.

Further, examples of the above-mentioned ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m- and p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin and the like. Be done.

The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the o-naphthoquinonediazide compound (reaction rate for one OH group) is
It is preferably from 15 to 80%, more preferably from 20 to 45%.

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

Of the above o-quinonediazide compounds,
Most preferred is an o-quinonediazide ester compound obtained by reacting 1,2-benzoquinonediazidesulfonyl chloride or 1,2-naphthoquinonediazidesulfonyl chloride with pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone.

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

The polymer compound containing o-quinonediazide used in the present invention has a molecular weight of 15 when considering coatability.
Those having a molecular weight of 00 or more are preferable, and those having a molecular weight of 2000 or more are more preferable.

The above-mentioned o-quinonediazide compound is preferably used as a mixture with an alkali-soluble resin. Examples of the alkali-soluble resin include novolac resins, vinyl polymers having a phenolic hydroxyl group, and condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. As a novolac resin,
For example, phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde copolycondensation resin as described in JP-A-55-57841, as described in JP-A-55-127553 Examples thereof include co-polycondensation resins of p-substituted phenol and phenol, or cresol and formaldehyde.

Further, the vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and at least one of the following general formulas [I] to [V] Polymers containing one structural unit are preferred.

[0024]

[Chemical 1] [In the formula, R ₁ and R ₂ 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, preferably a hydrogen atom or an alkyl group, and preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A connects a nitrogen atom or an oxygen atom and an aromatic carbon atom,
Represents an alkylene group which may have a substituent, m represents an integer of 0 to 10, and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. .. ]

The polymer used in the photosensitive composition of the present invention preferably has a copolymer type structure, and is used in combination with the structural units represented by the above general formulas [I] to [V]. Examples of monomer units that can be used include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, and styrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene. , Acrylic acids such as acrylic acid and methacrylic acid, for example unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, such as methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate , Dodecyl acrylate, 2-chloroethyl acrylate, acrylate And α-methylene aliphatic monocarboxylic acid esters such as α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate, nitriles such as acrylonitrile and methacrylonitrile, and amides such as acrylamide. , Anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc., vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, eg methyl vinyl ether. , Vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene. , 1,1
-Dimethoxyethylene, 1,2-dimethoxyethylene,
1,1-dimethoxycarbonylethylene, 1-methyl-
Ethylene derivatives such as 1-nitroethylene, for example N-
There are N-vinyl monomers such as vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene, and N-vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

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

These alkali-soluble resins preferably have a molecular weight of 1500 or more in consideration of coating properties,
More preferably, it has a molecular weight of 2000 or more.

The negative type photosensitive material used in the present invention is
There are various ones, but representative ones will be described as described below. (1) Photosensitive Composition Containing Diazo Resin The diazo resin represented by the condensation product of p-diazodiphenylamine and formaldehyde may be water-soluble or water-insoluble, but is preferably JP-B-47-1167. Also, water-insoluble and ordinary organic solvent-soluble substances as described in JP-A-57-43890 and the like are used. Particularly preferred is a diazo resin represented by the following general formula [VI].

[0029]

[Chemical 2] [In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group. X represents PF ₆ or BF ₄ , and Y
Represents -NH-, -S- or -O-. ]

The diazo resin is preferably used as a mixture with a film-forming resin, particularly a lipophilic polymer compound having a hydroxyl group. As such a lipophilic polymer compound, in addition to those listed above, a monomer having an aliphatic hydroxyl group in its side chain, for example, 2-hydroxyethyl acrylate or 2-
Examples thereof include copolymers of hydroxyethyl methacrylate and other copolymerizable monomers. In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, if necessary,
Natural resins and the like may be added.

As the binder used in combination with the diazonium salt, various polymer compounds can be used, but preferably, a monomer having an aromatic hydroxyl group as described in JP-A-54-98613. , N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-hydroxystyrene, o-, m-, or p-hydroxyphenylmethacrylate, etc. Copolymer with a monomer, a polymer containing a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit as a main repeating unit as described in U.S. Pat.No. 4,123,276, shellac, a natural resin such as rosin, Polyvinyl alcohol, polyamide resins described in U.S. Pat. Linear polyurethane resins described in Specification No. 3,660,097, phthalated resins of polyvinyl alcohol, condensed epoxy resin from bisphenol A and epichlorohydrin, cellulose acetate, cellulose such as cellulose acetate phthalate is contained.

Examples of alkali-soluble resins include novolac resins, vinyl polymers having phenolic hydroxyl groups, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. .. Examples of the novolac resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-formaldehyde resin such as those described in JP-A-55-57841.
Cresol / formaldehyde copolycondensation resin, JP-A-55
Examples of the co-polycondensation resin of p-substituted phenol and phenol or cresol and formaldehyde as described in JP-A-127553.

In addition to the above-mentioned materials, these photosensitive compositions may further contain dyes, pigments and other dyes, oil sensitizers, if necessary.
A plasticizer, a surfactant, an organic acid, an acid anhydride, a compound capable of generating an acid upon exposure, and the like can be added.

These binders are contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 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 and other pigments, oil sensitizers, plasticizers, surfactants and the like can be added to these photosensitive compositions.

[0036] Photosensitive composition As such a high molecular compound, the main chain or side chain of the polymer is a photosensitive group. Those containing a photosensitive polymer as a main component (for example, US Pat. Nos. 3,030,208, 3,707,373 and 3,453,237).
Compounds as described in U.S. Pat. No. 6,058,058); and (2) -properidene) malonic acid compounds such as cinnamylidene malonic acid and photosensitive polyesters derived from bifunctional glycols as a main component (for example, US Pat. Photopolymers as described in US Pat. Nos. 2,956,878 and 3,173,787); cinnamic acid esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose and the like (eg, US Pat. No. 2,690,966, No. 2,752,372
Nos. 2,732,301 and the like, and photosensitive polymers) and the like.

These photosensitive compositions contain other sensitizers,
Stabilizers, plasticizers, pigments, dyes and the like can be included.

(3) Photopolymerizable Composition Comprising Addition-Polymerizable Unsaturated Compound This composition preferably comprises (a) a vinyl monomer having at least two terminal vinyl groups, and (b) initiation of photopolymerization. It is composed of a polymer compound as an agent and (c) a binder.

As the vinyl monomer of this component (a),
It is described in Japanese Patent Publication Nos. 35-5093, 35-14719, and 44-28727. Acrylic acid or methacrylic acid ester of polyol, that is, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc., bis (meth) acrylamides such as methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, or urethane group-containing Saturated monomers, for example diol mono (meth) acrylates and diisocyanates such as di- (2'-methacryloxyethyl) -2,4-tolylenediurethane, di- (2-acryloxyethyl) trimethylenediurethane and the like. And the reaction product thereof.

As the photopolymerization initiator of the above component (b),
Although the compound represented by the above general formula [VI] can be used,
Other types can also be used. For example, J. Kosa mentioned above.
Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes, etc. as described in Chapter 5 of "Light Sensitive Systems" by R. More specifically, it is disclosed in British Patent No. 1,459,563.

Further, as the binder of the component (c),
Various known polymers can be used. Details of specific binders are described in US Pat. No. 4,072,527.

The photopolymerizable composition may contain a thermal polymerization inhibitor, a plasticizer, a dye or a pigment.

(4) Photosensitive Composition Containing Azide Group As the photosensitive azide compound, an aromatic azide compound having an azido group bonded to an aromatic ring directly or through a carbonyl group or a sulfonyl group is preferably used. ..

For example, polyazidostyrene as described in US Pat. No. 3,096,311, polyvinyl-p-azidobenzoate, polyvinyl-p-azidobenzal, and azide described in JP-B-45-9613. Reaction product of aryl sulfonyl chloride and unsaturated hydrocarbon polymer, and Japanese Patent Publications No. 43-21017, No. 44-229, No. 44
The polymers having a sulfonyl azide or a carbonyl azide as described in JP-A-22954 and JP-A-45-24915 are mentioned.

An oil sensitizer added to the photosensitive composition,
The amount of the surfactant, sensitizer, stabilizer, thermal polymerization inhibitor, and plasticizer to be added varies depending on the type, but generally 0.01 to 0.01 to the photosensitive composition contained in the photosensitive coating liquid. 20% by weight, preferably 0.05-10% by weight is suitable.

In the present invention, various compounds are used as an oil sensitizer, but a resin obtained by condensing a substituted phenol and an aldehyde represented by the following general formula [VII] and an orthonaphtho of the resin are used. A quinonediazide sulfonic acid ester compound is preferably used.

[0047]

[Chemical 3] [In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or a halogen atom, and R ₃ represents an alkyl group having 2 or more carbon atoms or a cycloalkyl group. ]

The alkyl group of R ₁ and R ₂ represented by the general formula [VII] is an alkyl group having 1 to 3 carbon atoms, especially 1
Or an alkyl group of 2 is preferable. Moreover, as R ₃ ,
An alkyl group or a cycloalkyl group having 15 or less carbon atoms is preferable, and an alkyl group or a cycloalkyl group having 3 to 8 carbon atoms is particularly preferable.

Examples of the substituted phenols represented by the general formula [VII] include isopropylphenol, t-butylphenol, t-amylphenol, hexylphenol, octylphenol, cyclohexylphenol, 3-methyl-4-chloro-5-t. -Butylphenol, isopropylcresol, t-butylcresol,
Examples thereof include t-amyl resole, hexyl resole, octyl cresol, cyclooctyl cresol and the like, of which octyl phenol and t-butyl phenol are particularly preferable.

Examples of the aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, benzaldehyde, acetaldehyde, acrolein, crotonaldehyde and furfural, which have 1 to 7 carbon atoms.
Aldehydes are preferred. Particularly preferred are formaldehyde and benzaldehyde.

The resin obtained by condensing the above-mentioned substituted phenols and aldehydes used in the present invention can be obtained by polycondensing these under an acidic catalyst. Further, the orthonaphthoquinonediazide sulfonic acid ester of the resin is esterified by dissolving the condensed resin in a suitable solvent, adding orthonaphthoquinone diazide sulfonic acid chloride to this, and adding an alkali to the equivalent point while heating and stirring. can get.

The 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 (above, Hodogaya Chemical Co., Ltd.), Patent Pure Blue VX, Rhodamine B, Methylene. Blue (above, manufactured by Sumitomo Chemical Co., Ltd.), basic dyes such as ethyl violet and quinalidine red, as well as Sudan Blue II, Victoria Blue F4R (above BA.
S. F), oil blue # 603, oil blue BOS, oil blue IIN (above, manufactured by Orient Chemical Industry) and the like.

As the support suitable for producing the photosensitive printing plate by applying the photosensitive coating solution of the present invention, various supports can be used. For example, metal plates such as aluminum, zinc, copper and steel are used. , And metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, etc., hydrophilized paper and plastics, and papers and plastic films vapor-deposited with metal, glass plates, resin-coated paper, aluminum, etc. The paper etc. on which the metal foil of the above is stretched are mentioned.

Among these, an aluminum plate is preferable.

Particularly in the case of an aluminum plate support,
Surface treatment such as graining treatment, anodizing treatment and, if necessary, sealing treatment is preferably performed.

As a method for the graining treatment, a technique of degreasing the surface of an aluminum plate or the like and then applying a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method or the like is adopted.

The anodizing treatment is carried out by using an inorganic salt such as phosphoric acid, chromic acid, boric acid or sulfuric acid, or an organic acid such as oxalic acid or sulfamic acid alone or in an aqueous solution or a mixture of two or more kinds of these acids. It is performed by passing an electric current in an aqueous solution using an aluminum plate or the like as an anode.

Further, the sealing treatment is carried out with an aqueous solution of sodium silicate,
It is carried out by dipping in hot water and a hot aqueous solution of some inorganic or organic salt, or by a steam bath.

In the present invention, the coating amount of the photosensitive coating liquid on the support varies depending on the use, but generally a solid content of 0.5 to 3.5 g / m ² is suitable.

The coating solution of the present invention can be applied by 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. A coating method or the like is used, and the coating film thickness is 0.1 to
5 g / m ² is preferred. The drying temperature is in the range of 20 to 150 ° C, preferably 30 to 100 ° C.

[0061]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 A sensitizing solution having the following composition was prepared, and this was applied to a grained aluminum plate using a roll coater to obtain a solid content of 2.2 g /
After coating so as to have a coating amount of m ² , it was dried to obtain a photosensitive lithographic printing plate sample 1.

[Photosensitive Solution] Ester compound of m-cresol novolak resin and naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride (Mw = 2000) 2.3 parts by weight Phenol and m-, p-mixed cresol ( Copolycondensation resin (Mw = 7000) of each molar ratio 48:32:20) and formaldehyde 6.7 parts by weight Novolak resin (Mw = 1800) synthesized from paraoctylphenol and formalin 0.9 parts by weight 2-trichloromethyl-5 -(Β-benzofurylvinyl) -1,3,4-oxadiazole 0.05 part by weight Victoria Pure Blue BOH 0.07 part by weight Ethylene glycol monopropyl ether 45 parts by weight The organic solvent composition of the above photosensitive solution is shown in Table 1 as a compound. Samples 2 to 9 of the photosensitive lithographic printing plate were prepared in the same manner as in Sample 1 except that

With respect to each of the samples 1 to 9 thus obtained, the coating property of the photosensitive solution was observed for Marangoni and vertical streaks.

Here, the term Marangoni refers to a hazy, vortex-like coating unevenness that occurs on the coated surface after coating and drying.

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

The vertical streaks are non-uniform states of the film thickness of the photosensitive layer appearing in the running direction of the support because the smoothing of the coating solution does not proceed.

The results are shown in Table 1.

As is clear from Table 1, the observation results of Marangoni and vertical streaks were inferior in Samples 8 and 9 which were outside the present invention.

On the other hand, Samples 1 to 7 using the organic solvent used in the present invention as the coating solvent were all favorable because the evaluation of A was obtained.

Example 2 A sensitizing solution having the following composition was prepared, and this was applied to a grained aluminum plate using a roll coater to give a solid content of 1.6 g /
After coating so as to have a coating amount of m ² , it was dried to obtain a photosensitive lithographic printing plate sample 10.

[Photosensitive solution] Charged monomer molar ratio: N- (4-hydroxyphenyl) methacrylamide: acrylonitrile: ethyl acrylate: methacrylic acid: n-butyl acrylate = 8: 32: 40: 10: 10 No. 62-7045 DISCLOSURE OF THE INVENTION Copolymer (Mw = 55000) obtained by the method shown in Synthesis Example 1 6.0 parts by weight Hexafluoroline, a condensation resin of p-diazophenylamine and paraformaldehyde (molar ratio 1: 0.9) Acid salt (Mw = 2400) 0.48 part by weight Jurimer AC-10L [manufactured by Nippon Pure Chemical Co., Ltd.] 0.36 part by weight Victoria Pure Blue BOH 0.09 part by weight Ethylene glycol monopropyl ether 45 parts by weight In the above photosensitive solution composition, an organic solvent is used. Photosensitive lithographic printing plate samples 11 to 14 were prepared in the same manner as in sample 10 except that the compounds shown in Table 2 were used.

For each of the samples 10 to 14 thus obtained, the coating property of the photosensitive solution was observed for Marangoni and vertical streaks.

The results are shown in Table 2.

As is apparent from Table 2, the observation results of Marangoni and vertical streak were inferior in Samples 13 and 14 which were outside the present invention.

On the other hand, Samples 10 to 12 in which the organic solvent used in the present invention was used as the coating solvent were preferable because the evaluation of A was obtained.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

As described above in detail, the photosensitive coating liquid composition of the present invention has extremely little odor and toxicity during or after the production of a photosensitive lithographic printing plate and has improved coating properties. To be done.

Claims (1)

[Claims] 1. A photosensitive coating liquid composition containing at least ethylene glycol monopropyl ether.