JP2008116854A - Photosensitive composition and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition including an unsaturated double bond and containing modified polyvinyl alcohol and its use. <P>SOLUTION: The photosensitive composition includes the modified polyvinyl alcohol containing a bond unit including the unsaturated double bond represented by general formula (1) in a molecular backbone. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a photosensitive composition and use thereof.

In order to manufacture a printed circuit board having a plurality of anisotropic layers, it is necessary to soft-bake a resist layer formed on the substrate and then apply a resist material to form a multilayer structure. In this case, the resist material applied later may be mixed with the resist material in the lower layer, and the performance of the original resist material may be impaired.

As a means to prevent the resist materials from mixing with each other, a resin thin film that is soluble in an alkali developer and insoluble in a solvent that dissolves the resist material in the unexposed area is interposed as an interlayer separation film between these resist materials. In addition, a technique for dissolving and removing an interlayer separation film after forming a circuit in a resist layer is known (see, for example, Patent Document 1).
In addition, a water-soluble resist material that can be developed with a dilute alkaline aqueous solution does not require this interlayer separation film and does not require the use of a solvent during development. In particular, it is actively used in the fields of printed wiring board manufacturing ink, gravure roll etching ink, color filter pixel manufacturing ink, screen printing plate manufacturing photosensitive composition, color filter protective film manufacturing ink, etc. For example, refer to Patent Documents 2 to 3).

A water-soluble resist material using polyvinyl alcohol as a base material is also known (see, for example, Patent Documents 4 to 6).

JP-A-63-202026 JP 05-224413 A JP 05-241340 A JP 2006-064851 A JP 2004-348141 A JP-A-11-172179

This invention makes it a subject to provide the photosensitive composition using the modified polyvinyl alcohol which has unsaturated double derived from a specific monomer in the principal chain in a molecule | numerator, and its use.

Said subject can be solved by the photosensitive composition containing the modified polyvinyl alcohol obtained by copolymerizing and saponifying a specific monomer, and a photoinitiator.

（式中、Ｘ１とＸ２は、炭素数１〜１２の低級アルキル基、水素原子、金属塩のいずれか一種を表す。ｇは、０〜３の整数を表す。ｈは、０〜１２の整数を表す。Ｙ１は、カルボン酸、カルボン酸エステル、カルボン酸金属塩、水素原子のいずれか一種を表す。） That is, the present invention is a photosensitive composition containing a modified polyvinyl alcohol containing a bond unit represented by the general formula (Formula 9) and a photopolymerization initiator in the molecular main chain. The modified polyvinyl alcohol is preferably 0.2% by weight, having an absorbance at 270 nm of 0.05 or more according to the ultraviolet absorption spectrum of an aqueous solution, methanol solution or aqueous methanol mixed solution, and the amount of unmodified polyvinyl alcohol is 25%. The following is preferable.
The photosensitive composition can be used as a resist material by containing a photopolymerizable monomer. The obtained resist material can be applied to a support and dried to form a photosensitive film, or directly applied to a substrate and dried to form a resist layer.
The resist layer is modified by using an edging solution containing an acid catalyst and an aldehyde as an edging solution for dissolving and removing the unexposed part when the unexposed part is dissolved and removed after image exposure to obtain a printed circuit board. Polyvinyl alcohol can also be acetalized.

(In the formula, X1 and X2 represent any one of a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom, and a metal salt. G represents an integer of 0 to 3. h represents an integer of 0 to 12. Y1 represents any one of carboxylic acid, carboxylic acid ester, carboxylic acid metal salt, and hydrogen atom.)

A photosensitive composition containing a modified polyvinyl alcohol having an unsaturated double derived from a specific monomer in the main chain in the molecule is obtained.

The modified polyvinyl alcohol is obtained by copolymerizing a monomer having an ethylenically unsaturated double bond and a monomer having a vinyl ester unit, followed by saponification to obtain a carbonyl group-containing polyvinyl alcohol, washing and drying. In this case, an unsaturated double bond starting from a carboxyl group is randomly introduced into the main chain.

（式中、Ｘ３とＸ４は、炭素数１〜１２の低級アルキル基、水素原子のいずれか一種を表す。ｉは、０〜１２の整数を表す。Ｙ２は、カルボン酸、カルボン酸エステル、カルボン酸金属塩、水素原子のいずれか一種を表す。）
これらモノマーとしては、例えば、マレイン酸ジメチル、マレイン酸ジエチル等がある。 As the monomer having an ethylenically unsaturated double bond, those represented by the general formula (Formula 10) can be suitably used.

(Wherein X3 and X4 represent any one of a lower alkyl group having 1 to 12 carbon atoms and a hydrogen atom. I represents an integer of 0 to 12. Y2 represents a carboxylic acid, a carboxylic acid ester, a carboxylic acid. (Represents either an acid metal salt or a hydrogen atom.)
Examples of these monomers include dimethyl maleate and diethyl maleate.

（式中、Ｘ５とＸ６は、炭素数１〜１２の低級アルキル基、水素原子のいずれか一種を表す。ｊは、０〜１２の整数を表す。Ｙ３は、カルボン酸、カルボン酸エステル、カルボン酸金属塩、水素原子のいずれか一種を表す。）
これらモノマーとしては、例えば、フマル酸ジメチル、フマル酸モノエチル、フマル酸ジエチル、シトラスコン酸ジメチル等がある。 Moreover, the monomer represented by the general formula (Chemical Formula 11) can also be suitably used.

(In the formula, X5 and X6 represent any one of a lower alkyl group having 1 to 12 carbon atoms and a hydrogen atom. J represents an integer of 0 to 12. Y3 represents a carboxylic acid, a carboxylic acid ester, a carboxylic acid. (Represents either an acid metal salt or a hydrogen atom.)
Examples of these monomers include dimethyl fumarate, monoethyl fumarate, diethyl fumarate, and dimethyl citrus acid.

（式中、ｋは、０〜１２の整数を表す。Ｙ４は、カルボン酸、カルボン酸エステル、カルボン酸金属塩、水素原子のいずれか一種を表す。）
これらモノマーとしては、例えば、無水マレイン酸、無水シトラスコン酸等がある。 Moreover, the monomer represented by the general formula (Chemical Formula 12) can also be suitably used.

(In the formula, k represents an integer of 0 to 12. Y4 represents any one of a carboxylic acid, a carboxylic acid ester, a carboxylic acid metal salt, and a hydrogen atom.)
These monomers include, for example, maleic anhydride, citraconic anhydride and the like.

The content (copolymerization amount) of these monomers is not particularly limited, but is preferably 0.1 to 50 mol% from the viewpoint of securing the amount of unsaturated double bonds in the molecule and water solubility, 1-10 mol% is more preferable.

The monomer having a vinyl ester unit is not particularly limited, but vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate In addition, vinyl acetate is preferable from the viewpoint of stable polymerization.

Moreover, you may copolymerize the monomer which can be copolymerized with these monomers as needed. The copolymerizable monomer is not particularly limited, but examples thereof include olefins such as ethylene, propylene, 1-butene and isobutene, acrylic acid, methacrylic acid, crotonic acid, phthalic acid, maleic acid, itaconic acid and the like. Unsaturated acids, or salts thereof, monoalkyl esters or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkyl acrylamides having 1 to 18 carbon atoms, N, N-dialkyl acrylamides, diacetone acrylamides, 2 Acrylamides such as acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its salts or quaternary salts thereof, methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N-dialkylmethacrylamide, di Methacrylamides such as seton methacrylamide, 2-methacrylamide propanesulfonic acid and salts thereof, methacrylamide propyldimethylamine and salts thereof or quaternary salts thereof, alkyl vinyl ethers having an alkyl chain length of 1 to 18 carbon atoms, hydroxyalkyl Vinyl ethers such as vinyl ether and alkoxyalkyl vinyl ether, N-vinyl amides such as N-vinyl pyrrolidone, N-vinyl formamide and N-vinyl acetamide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl chloride, vinylidene chloride, fluorine Vinyl halides such as vinyl chloride, vinylidene fluoride, vinyl bromide, vinylidene bromide, vinyl silanes such as trimethoxyvinyl silane, allyl acetate, allyl chloride, allyl alcohol Allyl compounds such as dimethyl allyl alcohol, vinyl silyl compounds such as vinyltrimethoxysilane, there is isopropenyl acetate and the like. Although the usage-amount of these copolymerizable monomers is not specifically limited, 0.001-20 mol% is preferable with respect to all the monomers to be used.

The number average molecular weight (hereinafter abbreviated as Mn) of the modified polyvinyl alcohol is not particularly limited, but is generally in the range of 1900 to 66500 which is generally used, and the viewpoint of improving the balance between water solubility and protective colloid properties. To 3800-28500 is more preferable.

The method for polymerizing the monomer is not particularly limited, and a known polymerization method is used, and solution polymerization is usually performed using an alcohol such as methanol, ethanol or isopropyl alcohol as a solvent. Bulk polymerization, emulsion polymerization, and suspension polymerization can also be performed. Such solution polymerization may be continuous polymerization or batch polymerization, and the monomer may be charged in a divided manner, may be charged all at once, or any means such as adding continuously or intermittently may be used.

The polymerization initiator used in the solution polymerization is not particularly limited, but azobisisobutyronitrile, azobis-2,4-dimethylpareronitrile, azobis (4-methoxy-2,4-dimethylpareronitrile). ) And other azo compounds, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, acetylcyclohexylsulfonyl peroxide, peroxides such as 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, and diisopropylpropyl Percarbonate compounds such as dicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate, t-butylperoxyneodecanate, α-cumylperoxyneodecanate, t-butylperoxyneo Decanate The perester compound, azobisdimethylvaleronitrile can be used a known radical polymerization initiator such as azo-bis-methoxy valeronitrile. The polymerization reaction temperature is usually selected from the range of about 30 ° C to 90 ° C.

In saponification, a copolymer obtained by copolymerizing monomers is dissolved in alcohol, and an ester in the molecule is hydrolyzed in the presence of an alkali catalyst or an acid catalyst. Examples of the alcohol include methanol, ethanol, butanol and the like. The concentration of the copolymer in the alcohol is not particularly limited, but is selected from a range of 10 to 80% by weight. As the alkali catalyst, for example, alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate can be used. For example, an inorganic acid aqueous solution such as hydrochloric acid or sulfuric acid, or an organic acid such as p-toluenesulfonic acid can be used. These catalysts are preferably used in an amount of 1 to 100 mmol equivalents relative to the copolymer. The saponification temperature is not particularly limited, but is in the range of 10 to 70 ° C, preferably 30 to 40 ° C. Although reaction time is not specifically limited, It is performed over 30 minutes-3 hours.

The absorbance of the modified polyvinyl alcohol is not particularly limited, but it is preferable that the absorbance at 270 nm by an ultraviolet absorption spectrum of 0.2% by mass of an aqueous solution, a methanol solution, or a water-methanol mixed solution is 0.05 or more. This absorbance can be adjusted to any value by changing the amount of catalyst used in the saponification step, the saponification time, and the saponification temperature.

Here, regarding the attribution of the ultraviolet absorption spectrum, JP-A-2004-250695 and the like, the absorption at 215 nm is attributed to the structure of —CO—CH═CH— in the polyvinyl alcohol resin, and the absorption at 280 nm is the polyvinyl alcohol type. There is a description that it is attributed to the structure of —CO— (CH═CH) ₂ — in the resin, and the absorption at 320 nm relates to the structure of —CO— (CH═CH) ₃ — in the polyvinyl alcohol resin.

The UV absorption spectrum derived from the double-chain structure (—CO— (CH═CH) ₂ —) of an unsaturated double bond of polyvinyl alcohol using a general aldehyde as a chain transfer agent has a peak top in the vicinity of 280 nm. Is derived from the structure of the general formula (Chemical Formula 13) in the modified polyvinyl alcohol of the present invention and has a peak included in the range of 265 to 275 nm at the center of 270 nm. A comparison chart is shown in FIG.

The saponification degree of the modified polyvinyl alcohol is not particularly limited, but is preferably 30 mol% to 99.9 mol% from the viewpoint of generating sufficient unsaturated double bonds.

The photopolymerization initiator is a compound that is blended to generate radicals by light irradiation to crosslink the modified polyvinyl alcohol, and has a molecular extinction coefficient of at least about 50 in the range of about 300 to 800 nm, more preferably 330 to 500 nm. It is preferable to contain one or more components having Examples of the photopolymerization initiator include aromatic ketones, lophine dimers, benzoin and benzoin ethers, polyhalogens, and combinations of two or more thereof.

Specific examples of these photopolymerization initiators are not particularly limited, but include benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4 ′. -Dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, Examples include 2,4-diethylthioxanthone, fluorenone, and acridone.

The content of the photopolymerization initiator is preferably 0.1 to 20 wt%, more preferably 0.2 to 10 wt%, based on the solid content of the photopolymerizable composition. By limiting to this range, a sufficient effect for crosslinking the modified polyvinyl alcohol can be obtained, and the film forming property of the photosensitive composition can be maintained.

The photosensitive composition can be used as a resist material by adding a photopolymerizable monomer.
Examples of the photopolymerizable monomer include known (meth) acrylic acid esters as described in JP-A-60-258539 and JP-A-2-269721.

Specific examples of these compounds include, but are not limited to, compounds obtained by adding an α or β unsaturated carboxylic acid to a polyhydric alcohol, such as trimethylolpropane di (meth) acrylate, trimethylolpropane trimethyl. (Meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc .; α , A compound obtained by adding a β-unsaturated carboxylic acid, such as trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether di (meth) acrylate, etc .; a polyvalent carboxylic acid such as phthalic anhydride water Substances having a group and an ethylenically unsaturated group, for example, esterified products with β-hydroxyethyl (meth) acrylate, etc .; alkyl esters of acrylic acid or methacrylic acid, such as methyl ethyl (meth) acrylate, (meth) acrylic acid Ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, etc. are used, and trimethylhexamethylene diisocyanate, dihydric alcohol and dihydric alcohol (meth) acrylic acid monoester are reacted. The resulting urethane diacrylate compound, bisphenol A, alkylene glycol and an adduct of acrylic acid or methacrylic acid, β-phenoxyethoxyethyl acrylate, and the like are also used. These compounds are used alone or in combination of two or more.

If necessary, the resist material may contain known additives such as a thermal polymerization inhibitor, a plasticizer, a dye, a color changing agent, an adhesion promoter, talc, etc. A combination of a halogen compound such as carbon fluoride and a leuco dye may be added. In addition, the intended resist material, resin relief plate, planographic printing plate, photomask and the like can be prepared in a wide range.

The resist material may contain colorants such as dyes and pigments. As the colorant, for example, fuchsin, auramine base, crystal violet, victoria pier blue, malachite green, methyl orange, acid violet RRH and the like are used.

The thermal polymerization inhibitor is added to prevent thermal polymerization and temporal polymerization of resist materials, which can be used for preparation of photopolymerizable compositions and storage until they are stacked on a metal plate. The chemical stability of time can be increased. Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, benzoquinone, o-toluquinone, p-toluquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, first chloride Copper, phenothiazine, phenidone, floranyl, chloranil, naphthylamine, pyridine, p-toluidine, β-naphthol, 2,6-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, N-nitrosophenylhydroxylamine Aluminum salt or ammonium salt, methylene blue organic copper, methyl salicylate, aryl phosphite and the like. A preferable addition amount of the thermal polymerization inhibitor is 0.001 to 10 wt%, more preferably 0.01 to 3 wt% with respect to the solid content of the resist material. By limiting to this range, thermal stability can be improved and sensitivity to light during exposure can be maintained.
I will give you.

The plasticizer is added to adjust the film quality of the resist material before and after photocuring, other physical properties, photosensitivity, and the like. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and diallyl phthalate, glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate, p-toluenesulfone Amides, benzenesulfonamides, acid amides such as Nn-butylbenzenesulfonamide, aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl azelate, dibutyl maleate, tributyl citrate, glycerol triacetate, lauric acid And butyl 4,5-diepoxycyclohexane-1,2-dicarboxylate dioctyl. A preferable addition amount of the plasticizer is 0.001 to 50 wt% of the solid content of the resist material, and more preferably 0.01 to 20 wt%. By limiting to this range, the above effects can be obtained without degrading the developability and image quality.

A dye is added for coloring the resist material. Examples of pigments include malachite green, methyl green, bririato green, methyl violet, crystal violet, ethyl violet, Victoria pure blue BOH, oil blue # 603 (manufactured by Orient Chemical Co., Ltd.), eosin, erythrosin B, rose bengal , Rhodamine B, rhodamine 6G, 2,7-dichlorofluorescein, phenolphthalein, alizarin red S, thymolphthalein, quinaldine red, methanyl yellow, thymolsulfophthalein, diphenyltriazene, xylenol blue, methylcongo red, Diphenylthiocarbazone, paramethyl red, congo red, benzobulbulin 4B, α-naphthyl red, Nile blue A, phenacetalin, parafuchsin, basi And the like can be given Kufukushin. A preferable addition amount of the dye is 0.001 to 10 wt%, more preferably 0.1 to 5 wt% of the solid content of the resist material. By limiting to this range, the above effects can be obtained while maintaining the sensitivity to light during exposure.

The color changing agent is added so that a visible image can be obtained when light is irradiated onto the resist material through a photomask. Examples of the color changing agent include diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4,4′-biphenyldiamine, o-chloroaniline, in addition to the above-mentioned dyes. Examples thereof include p, p ′, p ″ -hexamethyltriaminotriphenylmethane, p, p′-tetramethyldiaminotriphenylmethane, p, p ′, p ″ -triaminotriphenylcarbinol and the like. A preferable amount of the color changing agent is 0.001 to 10 wt%, more preferably 0.01 to 5 wt% of the solid content of the resist material. By limiting to this range, image fogging can be suppressed while maintaining sensitivity to light during exposure.

The resist material can be applied to a substrate by a known method and dried to form a resist layer. After exposing the image using a light source, the unexposed portion is dissolved and removed (developed) with a developer. A resist image can be formed on the substrate. The substrate having the resist image thus obtained is then exposed to an exposed metal plate or metal foil on the exposed substrate using an etching solution such as ferric chloride, cupric chloride, hydrogen peroxide-sulfuric acid, alkaline ammonia. After removing the portion, the resist image itself can be removed with an alkaline aqueous solution such as caustic soda or caustic potash or methylene chloride to obtain a printed circuit board.

The light source for exposing the resist material is preferably an apparatus capable of generating a large amount of ultraviolet rays, for example, ultra-high pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, ultraviolet light. Various laser lamps, fluorescent lamps, tungsten lamps and the like.

Examples of the developer for dissolving and removing the unexposed portion of the resist layer include 0.1 to 10 wt% of water, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, ammonia and the like. Alkaline aqueous solutions can be used, and amines such as primary amines such as butylamine, hexylamine, benzylamine and allylamine, secondary amines such as diethylamine and benzylethylamine, tertiary amines such as triethylamine, ethanolamine and diethanolamine , Hydroxylamines such as triethanolamine and 2-amino-1,3-propanediol, cyclic amines such as morpholine, pyridine, piperazine and piperidine, sulfates, carbonates, bicarbonates and alkali metal phosphates of the amines , Bases such as pyrophosphate Salts, tetramethylammonium hydroxide, may also be used hydroxy salts choline and the like.

The resist material can be applied to a support and dried, and then peeled off from the support and used as a photosensitive film. As the support, a polymer film such as a film made of polyethylene terephthalate, polypropylene, polyethylene or the like is used, and a polyethylene terephthalate film is preferable. Since these polymer films must be removable from the photosensitive layer later, they must not be made of a material that cannot be removed or have been subjected to a surface treatment. The thickness of these polymer films is usually 5 to 100 μm, preferably 10 to 30 μm. One of these polymer films may be laminated on both sides of the photosensitive layer as a support film for the photosensitive layer and the other as a protective film for the photosensitive layer.

In producing a photosensitive film, first, a resist material is dissolved or dispersed in a solvent. The solvent may be any solvent that dissolves or disperses the resist material. For example, ketone solvents such as water, acetone, methyl ethyl ketone, and methyl isobutyl ketone, ether solvents such as methyl cellosolve and ethyl cellosolve, dichloromethane, chloroform, and the like. And chlorinated hydrocarbon solvents such as methyl alcohol and ethyl alcohol. These solvents may be used alone or in combination of two or more.

Next, the resist material in the form of a solution or emulsion is uniformly applied on the polymer film, the solvent is removed by heating and / or hot air blowing, and the resist material is dried and then peeled off from the support to form a photosensitive film. . There is no restriction | limiting in particular in the thickness of a photosensitive film, Usually, 10-100 micrometers, Preferably it is 20-60 micrometers.

A photosensitive film can be made into a resist layer by laminating on a substrate. This resist layer can form a resist image on the substrate by the same method as the resist layer obtained by directly applying the resist material to the substrate and drying, and further obtain a printed circuit board by the same method. Can do.

The photosensitive film can be used as a resist film for tenting or etching by laminating on a substrate, exposing an image, and dissolving and removing (developing) an unexposed portion with a developer. At this time, by adding an acid catalyst and an aldehyde to the developer, the modified polyvinyl alcohol may be acetalized to improve water resistance. Note that the developer described above may be used.

Examples of aldehydes include, but are not limited to, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, t-butyraldehyde, amylaldehyde, hexylaldehyde, and 2-ethylhexylaldehyde, cyclohexyl Examples include alicyclic aldehydes such as aldehyde and furfural, aromatic aldehydes such as benzaldehyde, alkyl-substituted benzaldehyde, halogen-substituted benzaldehyde, and phenyl-substituted alkyl aldehyde. Among these, acetaldehyde and butyraldehyde are preferably used because they are easy to handle. These aldehydes may be used alone or in combination of two or more.

  The acid catalyst is not particularly limited, and examples thereof include organic acids such as formic acid, acetic acid, propionic acid, lactic acid, succinic acid, succinic acid, citric acid, and paratoluenesulfonic acid; hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, and the like. There are inorganic acids and the like, and these acid catalysts may be used alone or in combination of two or more. In general, it is preferable to add these acid catalysts after adjusting the pH of the reaction solution to be 0.3 to 2.0.

Hereinafter, the present invention will be described in more detail with reference to examples.
Unless otherwise specified, “parts” and “%” mean “parts by mass” and “mass%”.

Example 1
<Production of modified polyvinyl alcohol>
17 parts of vinyl acetate, 14 parts of methanol, 0.023 part of dimethyl maleate and 0.10% azobisisobutyronitrile with respect to vinyl acetate are charged into the polymerization vessel, heated after nitrogen substitution and heated to the boiling point. Furthermore, a mixed solution of 6 parts of vinyl acetate, 5 parts of methanol and 0.207 parts of dimethyl maleate was continuously added until a polymerization rate of 75% was reached, and the polymerization was carried out when the polymerization rate reached 90%. Stopped. Subsequently, unpolymerized vinyl acetate was removed by a conventional method, and the resulting polymer was saponified with sodium hydroxide by a conventional method. Thereafter, it was dried with hot air at 90 ° C. for 90 minutes, molecular weight (Mn) 11000, saponification degree 88.0 mol%, dimethyl maleate 0.6 mol%, 0.2% abs. A modified polyvinyl alcohol having a modified polyvinyl alcohol content of 13% was obtained.

<Analysis method>
The degree of saponification of the modified polyvinyl alcohol is measured according to JIS K 6276 “3.5 degree of saponification”. The molecular weight of the modified polyvinyl alcohol is GPC and the sample concentration is 0.25 w / v% aqueous solution. Is measured at 40 ° C., and Mn is calculated in terms of standard polyethylene glycol. The content of the unmodified polyvinyl alcohol was determined by completely saponifying the modified polyvinyl alcohol with an alkali catalyst in methanol, adjusting the Soxhlet-extracted sample to an aqueous solution of 0.01 w / v%, using ion exclusion HPLC, IR It is calculated by the area ratio of the detector. The absorbance at 270 nm is obtained by adjusting the absorbance of ultraviolet rays at 270 nm by adjusting the modified polyvinyl alcohol to a 0.2% by mass aqueous solution.

10 parts by weight of the obtained polyvinyl alcohol, 70 parts by weight of water, 10 parts by weight of methyl methacrylate, 5 parts by weight of methacrylic acid, 5 parts by weight of trimethylolpropane triacrylate (TMPTA), 2-hydroxyethoxy-2-methyl-1 A photosensitive composition was obtained by mixing 0.4 parts by mass of -phenyl-propan-1-one (photocatalyst).
The obtained photosensitive composition was coated on a polyethylene terephthalate support having a thickness of 20 μm and dried at 100 ° C. for 2 minutes to obtain a photosensitive film having a thickness of about 40 μm.
This photosensitive film was laminated at 105 ° C. on a cleaned copper clad laminate (copper thickness 35 μm). After 15 minutes, exposure was performed at an exposure amount of 1500 mJ / cm ² using a 100 w mercury lamp (SBL-100B manufactured by SZAX Co., Ltd.) through a negative document having the characteristics described below.

As the negative document, line width / space width (L / S) = 1/3 and line width = 100 μm to 600 μm (100 μstep, each line has 5 lines) were used.

<Performance evaluation immediately after exposure>
After 20 minutes of exposure, spray development was performed with 30 ° C. water for 40 seconds, followed by washing with 20 ° C. water for 40 seconds. The resist pattern of the original thus obtained was observed visually and with an optical microscope. Evaluation was performed as follows.

<Photocurability>
The resist pattern was observed, and the line width of the thinnest line in which all five lines remained without being twisted or peeled was recorded as photocurability. In this method, it can be seen that the smaller the line width, the higher the photocurability.

<Etching property>
The sample was etched under the following conditions. It is preferable that no copper remains in the non-image portion of the obtained sample.
Liquid composition: ferric chloride dihydrate 400 g / l, 35% hydrochloric acid 100 g / l, butyraldehyde 10 g / l
・ Liquid temperature 50 ℃
・ Etching time 20 minutes ・ Washing time 2.0 minutes

Examples 2-6
A modified polyvinyl alcohol was prepared in the same manner as in Example 1 except that the degree of saponification, molecular weight (Mn), the type of monomer having an ethylenically unsaturated double bond, and the amount of modification were changed as shown in Table 1. Then, the evaluation was performed in the same manner as in Example 1.

Comparative Examples 1-3
Polyvinyl alcohol was prepared in the same manner as in Example 1 except that the saponification degree and the molecular weight (Mn) were changed as described in Table 1, and evaluation was performed in the same manner as in Example 1.

Comparative Example 4
A modified polyvinyl alcohol was prepared in the same manner as in Example 1 except that the degree of saponification, molecular weight (Mn), chain transfer agent other than methanol, and the amount of chain transfer agent were changed as shown in Table 1, respectively. Evaluation was performed in the same manner as in 1.

The photosensitive composition of the present invention is a water-soluble photosensitive composition capable of forming a pattern when using a lithography technique in the production of semiconductor devices, magnetic bubble elements, optical disks, liquid crystals, etc. It is useful as a photoresist ink. Moreover, it can be easily cured by energy rays such as ultraviolet rays and electron beams, and can also be used for paints, inks, adhesives, printing plates, etching resists, and solder resists.

The figure which compared the ultraviolet absorption spectrum of Example 2 and Example 4, and the ultraviolet absorption spectrum of the conventional aldehyde modified polyvinyl alcohol.

Explanation of symbols

1 UV absorption spectrum of Example 2 UV absorption spectrum of Example 4 UV absorption spectrum of conventional aldehyde-modified polyvinyl alcohol (L-8, Kuraray Co., Ltd.) 4 Conventional aldehyde-modified polyvinyl alcohol (Alcotex manufactured by Sintomer Limited) 72.5) UV absorption spectrum

Claims (11)

A photosensitive composition containing a modified polyvinyl alcohol containing a bond unit represented by the general formula (Chemical Formula 1) in the molecular main chain and a photopolymerization initiator.

(In the formula, X1 and X2 represent any one of a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom, and a metal salt. G represents an integer of 0 to 3. h represents an integer of 0 to 12. Y1 represents any one of carboxylic acid, carboxylic acid ester, carboxylic acid metal salt, and hydrogen atom.) 2. The photosensitive material according to claim 1, wherein the modified polyvinyl alcohol has an absorbance at 270 nm of 0.2% by mass or more in an ultraviolet absorption spectrum of an aqueous solution, a methanol solution or a water-methanol mixed solution of 0.05 or more. Sex composition. The modified polyvinyl alcohol has a peak top of an ultraviolet absorption spectrum derived from an unsaturated double bond represented by the general formula (Chemical Formula 2) between 265 and 275 nm. 2. The photosensitive composition described in 2.

Content of unmodified polyvinyl alcohol is 25% or less, The photosensitive composition as described in any one of Claims 1-3 characterized by the above-mentioned. A modified polyvinyl alcohol obtained by copolymerizing at least one monomer represented by the general formula (Chemical Formula 3) to the general formula (Chemical Formula 5) and a monomer having a vinyl ester unit and then saponifying the copolymer. It is a photosensitive composition as described in any one of Claims 1-4 characterized by the above-mentioned.

(Wherein X3 and X4 represent any one of a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom and a metal salt. I represents an integer of 0 to 12. Y2 represents a carboxylic acid or a carboxylic acid. It represents any one of ester, metal carboxylate and hydrogen atom.)

(In the formula, X5 and X6 represent any one of a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom, and a metal salt. J represents an integer of 0 to 12. Y3 represents a carboxylic acid or a carboxylic acid. It represents any one of ester, metal carboxylate and hydrogen atom.)

(In the formula, k represents an integer of 0 to 12. Y4 represents any one of a carboxylic acid, a carboxylic acid ester, a carboxylic acid metal salt, and a hydrogen atom.) The modified polyvinyl alcohol is obtained by copolymerizing at least one monomer represented by the general formula (Chemical Formula 6) to the general formula (Chemical Formula 8), a monomer having a vinyl ester unit, and a monomer copolymerizable with these monomers. The photosensitive composition according to any one of claims 1 to 4, which is obtained by saponification afterwards.

(Wherein X3 and X4 represent any one of a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom and a metal salt. I represents an integer of 0 to 12. Y2 represents a carboxylic acid or a carboxylic acid. It represents any one of ester, metal carboxylate and hydrogen atom.)

(In the formula, X5 and X6 represent any one of a lower alkyl group having 1 to 12 carbon atoms, a hydrogen atom, and a metal salt. J represents an integer of 0 to 12. Y3 represents a carboxylic acid or a carboxylic acid. It represents any one of ester, metal carboxylate and hydrogen atom.)

(In the formula, k represents an integer of 0 to 12. Y4 represents any one of a carboxylic acid, a carboxylic acid ester, a carboxylic acid metal salt, and a hydrogen atom.) Resist material containing the photosensitive composition as described in any one of Claims 1-6, and a photopolymerizable monomer. A photosensitive film obtained by applying the resist material according to claim 7 on a support, drying the resist material, and then peeling the resist material from the support. An edging solution for dissolving and removing unexposed portions when a resist layer obtained by laminating the photosensitive film according to claim 8 on a substrate is subjected to image exposure and then unexposed portions are dissolved and removed to obtain a printed circuit board. A method for producing a printed circuit board comprising acetalizing a modified polyvinyl alcohol using an edging solution containing an acid catalyst and aldehydes. A resist layer obtained by applying and drying the resist material according to claim 7 on a substrate. An edging solution containing an acid catalyst and an aldehyde as an edging solution for dissolving and removing the unexposed portion when the resist layer according to claim 10 is image-exposed and then the unexposed portion is dissolved and removed to obtain a printed circuit board. A method for producing a printed circuit board comprising acetalizing a modified polyvinyl alcohol using

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