KR20070017962A - Photoresist composition - Google Patents

Abstract

In the present invention, as the component (A), the following general formula (1) {RCOO (AO) _a } _m X {O (AO ') _b H} _n (1) (wherein, RCO is 6-22 Represents a residue from which a hydroxyl group is removed from a fatty acid, X represents a residue from which a hydroxyl group is removed from a polyol having at least three hydroxyl groups, AO and AO 'represent an oxyalkylene group having 2 to 4 carbon atoms, and a represents O or one or more B represents a number of 1 or more, m and n represent a number of 1 or more, provided that the sum of m and n is the same as the number of hydroxyl groups of the polyol. (B) As a component, Alkali-soluble resin which has an anionic group or its modified substance is contained, The photoresist composition characterized by the above-mentioned.

Description

Photoresist composition {PHOTORESIST COMPOSITION}

This invention relates to the photoresist composition in which generation | occurrence | production of scum was reduced in the alkali image development process of a photoresist.

Conventionally, photoresist is widely used at the time of formation of wiring patterns, such as a printed circuit board circuit, an integrated circuit, and a color filter. In the formation process of a wiring pattern, after laminating or apply | coating a film form or liquid photoresist on a base material normally, next, irradiating active radiation, such as an ultraviolet-ray, an X-ray, an electron beam, and exposing and hardening, The developer is developed by removing the uncured photoresist, thereby forming a patterned resist film. As a developing solution, alkaline aqueous solution is used normally, As an alkali agent of a developing solution, inorganic alkaline compounds, such as alkali metal carbonate and alkali metal hydroxide, organic alkaline compounds, such as tetramethylammonium hydroxide, etc. are used.

 As such an alkaline developer, an uncured resin component, a dye, a pigment, a polymerization initiator, a crosslinking agent, etc. aggregate, and float on the surface of a developer or precipitate in a developer, and what is called a scum is produced. If the scum is attached in the developing apparatus and not only the development is hindered, but also the scum is attached to the object to be developed at the time of development, there is a problem that the resolution is lowered and a good resist pattern is not formed. For this reason, the photoresist which is hard to generate | occur | produce scum, and the developing solution excellent in the dispersibility of scum are examined.

 In addition, bubbles are generated when air is drawn into the developer, but since the developer is usually used for circulation, bubbles are accumulated when the generated bubble removability is insufficient. In particular, due to circulation use, as the resist component in the developer increases, bubbles are hardly disappeared. The bubbles not only interfere with the circulation of the developer, but also inhibit the contact between the developer and the photoresist, thereby causing a problem that the uncured resist is not sufficiently removed and a good resist pattern is not formed.

 As a photoresist which is hard to generate | occur | produce scum, the photoresist containing the photopolymerizable compound which has a polyoxyalkylene group (for example, refer patent document 1, 2), the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation And a photoresist containing a resin having a group which decomposes by the action of an acid to increase solubility in an alkaline developer (see Patent Document 3, for example), and a phenolic compound to improve the resolution so that the amount of the photosensitive agent is increased. Photo resist (refer patent document 4) etc. which reduced and reduced scum by a photosensitive agent are known. However, in a photoresist containing a photopolymerizable compound having a polyoxyalkylene group, in order to obtain sufficient scum dispersibility, it is necessary to blend such a photopolymerizable compound in a relatively large amount, resulting in a decrease in resolution of the photoresist. There is a drawback that bubbles are generated in the developer. Moreover, the scum prevention effect of the photoresist containing the acid generating compound and resin which has an acid-decomposable group, or the photoresist which reduced the photosensitive agent was not enough.

 In addition, as a photosensitive flat plate printing plate, polyoxyalkylene sorbitol fatty acid ester is used in order to improve the resolution (for example, refer patent document 5, 6). However, by mixing polyoxyalkylene sorbitol fatty acid ester, it is not known that it is effective in dispersibility of scum and prevention of bubble generation.

 Moreover, in the developing solution of a photoresist, alkaline developing solution containing 0-4 nonionic surfactant of HLB, 6-20 nonionic surfactant, and anionic polymeric surfactant (For example, refer patent document 7). ), An alkaline developer containing an amphoteric surfactant and a nonionic surfactant (see, for example, Patent Document 8) and the like are known to be excellent in scum dispersibility, but there has been a problem that a large amount of bubbles are generated in the developer.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-232699

Patent Document 2: Japanese Unexamined Patent Publication No. 2003-149809

Patent document 3: Unexamined-Japanese-Patent No. 10-133376

Patent document 4: Unexamined-Japanese-Patent No. 5-204144

Patent document 5: Unexamined-Japanese-Patent No. 1-302349

Patent Document 6: Japanese Unexamined Patent Publication No. 2002-72461

Patent Document 7: Japanese Patent Application Laid-Open No. 8-160632

Patent Document 8: Japanese Patent Application Laid-Open No. 11-352700

Disclosure of the Invention

Problems to be Solved by the Invention

 Therefore, the objective of this invention is providing the photoresist which is excellent in the dispersibility of scum and few bubbles of a developing solution.

Means to solve the problem

 Therefore, the present inventors earnestly examine the above-mentioned problems, and find that a photoresist having excellent scum dispersibility and less foaming of the developer is obtained by blending a polyether ester having a specific structure in the photoresist. Completed.

 That is, this invention is a following general formula (1) as (A) component.

{RCOO (AO) _a } _m X {O (AO ') _b H} _n (1)

(Wherein RCO represents a moiety having a hydroxyl group removed from a fatty acid having 6 to 22 carbon atoms, X represents a moiety having a hydroxyl group removed from a polyol having at least three hydroxyl groups, and AO and AO ′ represent an oxyalkylene having 2 to 4 carbon atoms). Group, a represents 0 or 1 or more, b represents 1 or more, and m and n represent 1 or more, provided that the sum of m and n is the same as the number of hydroxyl groups of the polyol. Polyether esters represented by.);

 (B) As a component, Alkali-soluble resin which has an anionic group or its modified substance is contained, The photoresist composition characterized by the above-mentioned.

Effects of the Invention

 Even if the resist component in a developing solution increases, the photoresist composition of this invention produces little scum and air bubbles tend to disappear. For this reason, the fall of the resolution of a resist pattern by the generation of scum and a bubble, and the trouble of a developing apparatus can be reduced.

Best Mode for Carrying Out the Invention

(A) component of this invention is polyether ester represented by General formula (1). In General formula (1), RCO showed the residue remove | excluding the hydroxyl group from the C6-C22 fatty acid. Examples of the fatty acid having 6 to 22 carbon atoms include hexanoic acid (capronic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid (ferragonic acid), decanoic acid (capronic acid), undecanoic acid, and dodecanoic acid ( Lauric acid), tridecanoic acid, tetradecanoic acid (mylistic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), 12-hydroxyoctadecanoic acid (12 Linear saturated fatty acids such as hydroxystearic acid), eicosanoic acid (arachinic acid), and docoic acid (behenic acid); Isohexanoic acid, isoheptanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, 2-propylheptanoic acid, isodecanoic acid, isoundecanoic acid, 2-butyloctanoic acid, isododecanoic acid, isotridecanoic acid Branched fatty acids such as 2-pentylnonanoic acid, isotetradecanoic acid, 2-hexyldecanoic acid, 2-heptyldodecanoic acid and isostearic acid; Unsaturated fatty acids such as 10-undecenoic acid, palmitreic acid, oleic acid, isooleic acid, eraidinic acid, linoleic acid, linolenic acid, ricinolic acid, gadolenic acid, erucic acid, ceracoreic acid, and the like. In the case of a C5 or less fatty acid, the bubble generation of a developing solution increases, and in the case of a C23 or more fatty acid, scum dispersibility may become inadequate. Moreover, among these fatty acids, C6-C22 fatty acids are preferable, C8-C18 fatty acids are more preferable, C10-C14 fatty acids are the most preferable. In addition, saturated fatty acids have less bubbles and are preferable to unsaturated fatty acids.

 X represents the residue which removed the hydroxyl group from the polyol which has at least 3 hydroxyl group. As such a polyol, for example, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-hydroxymethyl-1,3-propanediol, 2-methyl-1,2 , 3-propanetriol, 1,2,5-pentanetriol, 1,3,5-pentanetriol, 2-methyl-1,2,4-propanetriol, 2-hydroxymethyl-1,3 -Butanediol, trimetholethane, 1,3,5-hexanetriol, 1,2,6-hexanetriol, 3-hydroxymethyl-1,5-pentanediol, 3-methyl-1,3,5 -Trihydric alcohols such as pentane triol, trimetholpropane, trimetholbutane, 2,5-dimethyl-1,2,5-hexanetriol, triethanolamine; pentaerythritol, 1,2,3, 4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethyrolpropane , Sorbitan, alkylglucoside, N, N, N ', N'- tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N', N'-tetrakis (2-hydroxyethyl) ethylene Tetrahydric alcohols such as diamine; adonitol, arabitol, xylitol, triglyceride 5, the alcohol and the like; Hexahydric alcohols such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dalcitol, taloose, and allose; Octahydric alcohols such as sucrose; Trivalent phenols such as tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1,3-tris (3-t-butyl-4-hydroxy-6-methylphenyl) butane Can be mentioned.

Among these, trihydric alcohol is preferable, trihydric and tetrahydric alcohol is more preferable, and glycerol and sorbitan are the most preferable.

AO and AO 'represent an oxyalkylene group having 2 to 4 carbon atoms, a represents 0 or 1 or more, and b represents 1 or more. Examples of the oxyalkylene group having 2 to 4 carbon atoms include oxyethylene, oxypropylene, oxy (methyl) ethylene, oxybutylene and oxy (ethyl) ethylene. The group represented by (AO) _a and the group represented by (AO ′) _b can be obtained by addition polymerization of an alkylene oxide having 2 to 4 carbon atoms to the polyol having at least three hydroxyl groups.

As such alkylene oxide, ethylene oxide, a propylene oxide, butylene oxide, tetrahydrofuran (1, 4- butylene oxide) etc. are mentioned, for example. When superposing | polymerizing an alkylene oxide, you may be homopolymerization, such as one type of alkylene oxide, random polymerization of two or more types of alkylene oxide, block polymerization, or random / block polymerization. Among the alkylene oxides, ethylene oxide is preferable.

In the case of addition polymerization of two or more alkylene oxides, one of them is preferably ethylene oxide. However, when the ethylene oxide content is too low, the dispersion of scum may be insufficient. On the contrary, when the ethylene oxide content is high, bubbles of the developing solution may increase, so that the group represented by (AO) _a And the content of ethylene oxide of the group represented by (AO ′) _b is preferably from 50 to 95 mass%, more preferably from 60 to 90 mass%, based on all alkylene oxide to be polymerized by addition. Most preferably, it is 85 mass%.

Moreover, it is preferable that the number of the sum total of a and b is 1-50, 2-20 are more preferable, and 4-15 are the most preferable.

m and n showed the number of 1 or more that the number of the sum total of m and n is the same as the number of hydroxyl groups of the said polyol. 0.5-4 are preferable, as for ratio of n with respect to m, 0.8-3 are more preferable, and 1-2 are the most preferable.

The manufacturing method of the polyether ester represented by General formula (1) is not specifically limited, It can manufacture by a well-known method. As such a method, for example, (A) a method of addition polymerization of an alkylene oxide to a partial ester of a fatty acid and a polyol, (B) a method of addition polymerization of an alkylene oxide to a polyol, and then a method of making an ester of a fatty acid, etc. Can be mentioned. As a catalyst in the case of addition-polymerizing an alkylene oxide, For example, alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, cesium hydroxide; Alkali metal alkoxides such as sodium methylate and potassium-t-butoxide; Tertiary amine compounds such as trimethylamine and triethylamine; Lewis acids, such as 1st tin chloride, 2nd tin chloride, and boron trifluoride, etc. are mentioned. In the case of esterification, it may be esterified directly with a fatty acid, and may be esterified by transesterification using fatty acid lower alcohols, such as fatty acid methyl and fatty acid butyl.

In addition, as the method (B), in the polyether ester represented by the general formula (1), it is not obtained that the number of a is 0, and that in which the number of a and the number of b are substantially the same is obtained. Moreover, also in the method (A), when an alkali metal hydroxide or an alkali metal alkoxide is used as a catalyst, since a transesterification reaction occurs, the thing of the same number of a and the number of b may be obtained similarly.

It is preferable that it is 1-20 mass parts with respect to 100 mass parts of solid content of the photoresist composition of this invention, and, as for content of the polyether ester represented by General formula (1), it is more preferable that it is 3-15 mass parts, Most preferably, it is 10 mass parts. When the content of the polyether ester represented by the general formula (1) is less than 1 part by mass, the dispersibility of scum may become insufficient. When the content of the polyether ester exceeds 20 parts by mass, the adhesion of the resist to the substrate is reduced or after alkali development. It is because the resolution of a resist pattern may fall.

(B) component of this invention is alkali-soluble resin which has an anionic group, or its modified substance. Examples of the anionic group include a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, a phenolic hydroxyl group, and the like, but from the viewpoint of good dispersibility of scum, a carboxyl group and a phenolic hydroxyl group are preferable. Carboxyl groups are more preferred.

Alkali-soluble resin containing a carboxyl group uses radically polymerizable unsaturated acids, such as acrylic acid, methacrylic acid, clotonic acid, fumaric acid, (maleic anhydride), and (anhydrous) itaconic acid, as an essential component, and the (meth) acrylic acid It is obtained by copolymerizing radically polymerizable monomers, such as ester, styrene, acrylonitrile, and (meth) acrylamide.

It is preferable that the acid value of alkali-soluble resin containing a carboxyl group is 20-300 mgKOH / g, It is more preferable that it is 40-200 mgKOH / g, It is most preferable that it is 60-170 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in an alkaline developer may be insufficient, and developability may decrease. When the acid value exceeds 300 mgKOH / g, the resolution of the resist pattern after alkali development may decrease.

Moreover, as alkali-soluble resin which has a phenolic hydroxyl group, the novolak resin which polycondensed a phenol compound and aldehydes with the acid catalyst, the polyvinyl phenol resin etc. which copolymerized hydroxy styrene and another radically polymerizable monomer, etc. are mentioned, for example. Can be. Examples of the phenols used in the novolak resins include phenol, m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcin, pyrogallol and bisphenol , Bisphenol A, ethylphenol, propylphenol, butylphenol and the like. Moreover, as aldehydes used for novolak resin, formaldehyde, acetaldehyde, propionaldehyde, etc. are mentioned, for example.

It is preferable that the molecular weight of alkali-soluble resin is 1000-1 million in a weight average molecular weight, It is more preferable that it is 2000-100000, It is most preferable that it is 3000-50000. When the weight average molecular weight is less than 1000, the viscosity may be too low and may not become a film having a thickness usable for photoresist. When the weight average molecular weight exceeds 1000000, the viscosity may be too high and may be difficult to apply. Moreover, since glass coating temperature does not show adhesiveness, when glass transition temperature (Tg) exists in the range of 0 degreeC or more, especially 5-70 degreeC, it is suitable.

The photoresist composition of the present invention may be a negative resist or a positive resist. As a negative resist, an optical radical polymerization resist, a chemical amplification resist, a photocationic polymerization resist, etc. are mentioned, for example. Moreover, as a positive resist, a quinonediazide type resist, a chemically amplified resist, etc. are mentioned, for example. Among these, since the scum dispersibility of a developing solution is good and there is little bubble generation, an optical radical polymerization type resist is preferable.

The photoradical polymerization type negative resist is a photoresist (B) which is alkali-soluble resin which has an anionic group, and also contains the poly (meth) acrylic acid ester of a polyhydric alcohol, and a photoinitiator; Alternatively, the component (B) is a modified product in which a part of the anionic group of the alkali-soluble resin having an anionic group is substituted with a radical polymerizable group, and is a photoresist containing a photopolymerization initiator.

As a polyhydric alcohol of the poly (meth) acrylic acid ester of polyhydric alcohol, for example, neopentyl glycol, hexylene glycol, glycerin, trimetholpropane, (poly) ethylene glycol, (poly) propylene glycol, polyoxyethylene polyoxy Propylene glycol, the alkylene oxide adduct of bisphenol A, etc. are mentioned.

Moreover, as a photoinitiator, For example, aromatic carbonyl compounds, such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl xanthone, thioxanthone, anthraquinone; Acetophenone, propiophenone, a-hydroxyisobutylphenone, ah, min quote-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone, diacetylacetophenone, acetophenone, etc. Acetophenones; Benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylhydroperoxide, di-t-butyldiperoxyisophthalate, 3,3 ', 4,4'-tetra (t-butylper Organic peroxides such as oxycarbonyl) benzophenone; Diphenylhalonium salts such as diphenyl iodide bromide and diphenyl iodonium chloride; Organic halides such as carbon tetrabromide, chloroform and iodine form; Heterocyclic and polycyclic compounds such as 3-phenyl-5-isoxazolone and 2,4,6-tris (trichloromethyl) -1,3,5-triazinebenzanthrone; 2,2'-azo (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'- Azo compounds such as azobis (2-methylbutyronitrile); Peroxy ketal which is a combination of an iron- allene complex, a titanocene compound, a bisimidazole type compound, an N-arylglycidyl type compound, an acridine type compound, an aromatic ketone / aromatic amine, etc. are mentioned.

The modified substance in which a part of the anionic group of the alkali-soluble resin having an anionic group is substituted with the radical polymerizable group is glycidyl acrylate, glycidyl methacrylate, allyl glycidyl in the alkali-soluble resin having the anionic group. It can obtain by making glycidyl-group containing unsaturated compounds, such as ether, react. The content of the radical polymerizable group is preferably 200 to 3000, more preferably 230 to 1500, and most preferably 250 to 750 in the unsaturated equivalent of the resin. When the content of the radical polymerizable group is less than 200 in unsaturated equivalents, the peelability of the resist pattern after alkali development may be insufficient, and when it exceeds 3000, the developability of the resist pattern after alkali development may be insufficient. Because there is.

The negative type resist of a chemical amplification type | mold is alkali-soluble resin in which (B) component has a phenolic hydroxyl group, and is a photoresist containing a photo-acid generator and a crosslinking agent. As a photo-acid generator, For example, Bissulfonyl diazomethanes, such as bis (p-toluenesulfonyl) diazomethane; nitrobenzyl derivatives such as p-toluenesulfonyl acid-2-nitrobenzyl; Pyrogalol and aliphatic or aromatic sulfonic acid esters such as methane sulfonic acid ester of pyrogallol and benzene sulfonic acid ester of pyrogallol; Onium salts such as diphenyl iodonium hexafluorophosphate and triphenylsulfonium trifluoromethane sulfate; Benzointosilates such as benzointosirate; Halogen-containing triazine compounds such as 2- (4-methoxyphenyl) -4 and 6-bis (trichloromethyl) -1,3,5-triazine; And oxime sulfonate compounds such as 2- (toluenesulfonyloxyimino) -phenylacetonitrile and a- (1-naphthylsulfonyloxyimino) -4-methoxybenzyl cyanide. As a crosslinking agent, N-alkoxy compounds, such as an alkoxy methyl melamine resin, are mentioned.

The photocationic polymerization type negative resist is alkali-soluble resin in which (B) component has a phenolic hydroxyl group, Furthermore, it is a photoresist containing a cationically polymerizable compound and a photo-acid generator. Examples of the cationically polymerizable compound include p-diisopropenylbenzene, m-diisopropenylbenzene, diphenylethylene, indenone, acenaphthene, 2-norbornene, 2,5-norbornadiene, 2, 3-benzofuran, indole, 5-methoxyindole, 5-methoxy-2-methylindole, N-vinyl-2-phyllolidon, N-vinylcarbazole, bisphenol A diepoxide, 4-vinyl Cyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, (3,4-epoxycyclohexyl) methyl-3, 4-epoxycyclohexylcarboxylate, bis (2-methyl-4, 5-epoxycyclohexylmethyl) Can be mentioned.

The quinonediazide-based positive resist is a photoresist in which (B) component is an alkali-soluble resin having a phenolic hydroxyl group, and also contains a quinonediazide compound, which is insoluble in an alkaline developer before exposure, but after exposure, quinonedia Alkali-soluble becomes because a jide compound turns into an indencarboxylic acid compound. As a quinonediazide compound, the 1, 2-naphthoquinone diazide sulfonic acid ester or 1,2-benzoquinone diazide sulfonic acid ester of a phenolic hydroxyl group containing compound is mentioned, for example. Examples of the phenolic hydroxyl group-containing compound include 1-naphthol, 2-naphthol, dihydroxynaphthalene, gallic acid, gallic acid ester and the like in addition to the phenols.

The positive type resist of chemically amplified type is a photoresist (B) which is alkali-soluble resin which has an anionic group, and also contains the dissolution inhibitor and the photo-acid generator which have an acid-decomposable group; Alternatively, the component (B) is a modified product in which an anionic group of an alkali-soluble resin having an anionic group is protected with an acid-decomposable group, and is a photoresist containing a photoacid generator.

The dissolution inhibitor having an acid-decomposable group is a compound having a property of reducing the dissolution of an alkali-soluble resin having an anionic group in a developing solution. Specifically, a phenolic compound is selected from t-butoxycarbonyl ether and tetrahydropyranyl. And compounds modified with ether, 3-bromotetrahydropyranyl ether, 1-methoxycyclohexyl ether, t-butyl ether, trimethylsilyl ether, triethylsilyl ether and the like. Especially, t-butoxycarbonyl ether of polyvinyl phenol is preferable. Examples of the photoacid generator include those obtained by chemically amplified negative resists.

Examples of the modified product in which the anionic group of the alkali-soluble resin having an anionic group is protected with an acid-decomposable group include, for example, a resin in which the carboxyl group of the alkali-soluble resin having a carboxyl group is protected with an acid-decomposable group, and a phenol of an alkali-soluble resin having a phenolic hydroxyl group. And resins in which the hydroxyl group is protected with an acid-decomposable group. Moreover, as such an acid-decomposable group, 1-substituted methoxymethyl group, methylthiomethyl group, ethoxymethyl group, benzyloxymethyl group, phenoxymethyl group, 1-methoxyethyl group, t-butyl group, benzyl group etc. are mentioned, for example. An alkyl group; Silyl groups such as trimethylsil group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; Acyl groups, such as an acetyl group and a propionyl group; Cyclic acid-decomposable groups, such as a cyclohexyl group, etc. are mentioned.

The photoresist composition of the present invention is a variety of additives, for example, solvents, photosensitizers (pigments), radical polymerization inhibitors, thermal crosslinkable compounds, coatability improving agents, adhesion improving agents, etc., in a range that does not impair the performance thereof. It may contain.

Examples of the solvent include glycol solvents such as methoxy ethanol, ethoxy ethanol, butoxy ethanol, methoxy-2-propanol and ethoxy methoxy-2-propanol; Ether acetate solvents such as methoxy ethanol acetate, ethoxy ethanol acetate and methoxy-2-propanol acetate; Ester solvents such as ethyl acetate, butyl acetate and ethyl 2-hydroxypropionate (ethyl lactate); Alcohol solvents such as hexanol, cyclohexanol and diacetone alcohol; Ketone solvents such as cyclohexanone, methyl ethanol ketone and methyl isobutyl ketone; Hydrocarbon solvents, such as cyclohexane, toluene, and xylene, etc. are mentioned.

As the photosensitizer, for example, thioxanthene, xanthene, ketone, thiopyryllium salt, base styryl, merocyanine, 3-substituted coumarin, 3,4-substituted coumarin, cyanine, And pigments such as acridine-based, thiazine-based, phenothiazine-based, anthracene-based, coronene-based, benzanthracene-based, perylene-based, merocyanine-based, ketocoumarin-based, fumarine-based, and borate-based.

As the radical polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, catechol, resorcin, naphthylamine, t-butylcatechol, 2, 6-di-t-butyl-p-cresol, 2, 2 '-Methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), and the like.

 Moreover, you may add additives, such as a coloring agent (dye or pigment), a coloring agent (dye which develops color by light irradiation), a plasticizer, a flame retardant, an adhesive imparting agent, an organic solvent, to the photosensitive resin composition of this invention as needed.

When forming a resist pattern on copper foil laminated sheets, silicon wafers, glass plates, etc. using the photoresist composition of this invention, a photoresist composition is apply | coated by methods, such as a roll coat method, the knife coat method, and a spray coat method. Then, it is made to dry as needed, it irradiates through a desired mask pattern, it is drawn by an electron beam, and it develops with alkaline developing solution.

Moreover, the photoresist composition of this invention can be apply | coated and dried on a polymer film, and can be used suitably as a dry film resist. As such a polymer film, it is preferable that actinic light is permeable and can be easily removed from the applied and dried resist composition later. Examples of such a polymer film include polyethylene, polypropylene, polyethylene terephthalate, polyvinyl alcohol, polyvinyl chloride, polyvinyl chloride copolymer, polyvinylidene chloride, polyvinylidene chloride copolymer, and polymethyl methacrylate. The film which consists of copolymer, polystyrene, a polystyrene copolymer, polyacrylonitrile, polyamide, etc. is mentioned, Especially, a polyethylene terephthalate is preferable. The thickness of the polymer film is preferably 5 to 100 m, and more preferably 10 to 30 m. In addition, although the film thickness of the resist composition apply | coated and dried on a polymer film changes with a use, when too thin, film strength will fall, and when too thick, the resolution will fall, and therefore, for printed circuit board manufacture, it is 1-100. m is preferable and 5-60 * m is more preferable.

In addition to the support and the photopolymerization layer, a protective film may be laminated on the surface of the photopolymerization layer. As a protective film, films, such as polyethylene and a polypropylene, are preferable.

As a coating method of the photosensitive resin composition, the roll coat method, the knife coat method, the spray coat method, etc. are mentioned, for example, A drying temperature and time are 1 to 30 minutes at 80-150 degreeC normally. The film thickness of the photopolymerization layer in the photosensitive element of the present invention varies depending on the application. However, if the film thickness is too thin, the film strength is lowered. If the film thickness is too thick, the resolution is lowered. 1-100 * m is preferable and 5-60 * m is more preferable.

After apply | coating and exposing the photoresist composition of this invention, the alkali developing solution used at the image development process is not specifically limited, A conventionally known alkaline developing solution can be used. As an alkali agent of such alkaline developing solution, For example, Alkali metal carbonate, such as lithium carbonate, sodium carbonate, potassium carbonate; Alkali metal hydrogencarbonates such as lithium bicarbonate, sodium bicarbonate and potassium bicarbonate; Alkali metal borate salts such as lithium borate, sodium borate and potassium borate; Alkali metal silicates such as lithium silicate, sodium silicate and potassium silicate; Inorganic alkaline compounds such as alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Organic alkaline compounds such as ethylenediamine, propylenediamine, pyrrolidine, morpholine, piperazine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, and the like. Can be. Among these alkaline agents, alkali metal carbonates and organic alkaline compounds are preferred, and sodium carbonate and tetramethylammonium hydroxide are more preferred.

The concentration of the alkali agent in the developer is different depending on the type of alkali agent used and the photoresist, but in the case of alkali metal carbonate, it is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of water. It is most preferable that it is 0.5-2 mass parts. In the case of the organic alkaline compound, the concentration of the alkali agent in the developer is preferably 0.5 to 25 parts by mass, more preferably 1 to 15 parts by mass, and most preferably 1.5 to 10 parts by mass with respect to 100 parts by mass of water. .

15-50 degreeC is preferable, as for the temperature of a developing solution, 20-40 degreeC is more preferable, and 25-35 degreeC is the most preferable. This is because when the temperature of the developing solution is lower than 15 ° C., dissolution of the uncured resist may be insufficient, and when the temperature exceeds 50 ° C., the cured resist may cause peeling.

Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, in a following example, a part and% are mass references | standards unless there is particular notice. In addition, EO represents -C ₂ H ₄ O-, and PO represents -C ₃ H ₆ O-.

<Production Example 1: A-1>

92 g (1 mol) of glycerin and 4 g of sodium hydroxide as a catalyst were put into a stainless autoclave equipped with a stirring device, a thermometer, and a nitrogen gas introduction tube, and after replacing the system with nitrogen, the mixture was stirred at 100 ° C. for 1 hour, Sodium hydroxide was dissolved. Next, 264 g (6 mol) of ethylene oxide and 58 g (1 mol) of propylene oxide were sequentially fed at 140 ° C., aged at 140 ° C. for 2 hours, and then the catalyst was removed by a conventional method to obtain a polyether compound. Got it.

To a glass flask equipped with a stirring device, a thermometer, and a nitrogen gas introduction tube, 207 g (0.5 mole) of polyether compound, 219 g (0.5 mole) of palm oil fatty acid, and 0.5 g of methanesulfonic acid were added as a catalyst, and reacted at 180 ° C for 5 hours. , Polyetherester A-1 of the present invention was obtained:

In general formula (1),

R: The residue which removed the carboxyl group from palm oil fatty acid (C12-valent main component by the mixture of C10, 12, 14, 16);

(AO) _a : (EO) ₂ (PO) _0.33 block polymer (EO is 82.1 mass%);

m: 1;

X: residue which removed hydroxyl group from glycerin;

(AO ′) _b : (EO) ₂ (PO) _0.33 block polymer (EO is 82.1 mass%);

n: 2.

<Production Example 2: A-2>

346 g (1 mol) of sorbitan monolaurate (Cao Co., Ltd. brand name SP-L10) and a catalyst of 28% methanol of sodium methylate were thrown into the same autoclave as Preparation Example 1, and 1 kPa at 100 ° C. The pressure was reduced below, and the methanol of the solvent was removed. Next, a mixture of 264 g (6 mol) of ethylene oxide and 116 g (2 mol) of propylene oxide was fed at 140 DEG C, aged at 140 DEG C for 2 hours, and then the catalyst was removed by a conventional method. Polyetherester A-2 was obtained:

In general formula (1),

R: residue which removed carboxyl group from lauric acid;

a: O;

m: 1;

X: residue which removed hydroxyl group from sorbitan;

(AO ′) _b : [(EO) ₂ (PO) _0.67 ] block polymer (EO is 69.4 mass%); n: 3.

<Production Example 3: A-3>

Into the same autoclave as in Production Example 1, 351 g (1 mol) of glycerin monooleate and 1 g of an ether complex of boron trifluoride were added as a catalyst, and 176 g (4 mol) of ethylene oxide was fed at 60 ° C, followed by 2 at 60 ° C. After ageing, the catalyst was removed by conventional methods to obtain the polyetherester A-3 of the present invention:

In general formula (1),

R: residue which removed carboxyl group from oleic acid;

a: O;

m: 1;

X: residue which removed hydroxyl group from glycerin;

(AO ′) _b : EO (EO is 100% by mass);

b: 2;

n: 2.

<Manufacture example 4: A-4>

134 g (1 mol) of trimethylolpropane and 328 g (1.2 mol) of Uji fatty acid were added to the same glass flask as Preparation Example 1, and the resultant was reacted at 220 ° C for 10 hours while removing the produced water, thereby producing trimethylolpropane partial Uji fatty acid ester. Got. Next, 231 g (0.5 mol) of trimethylolpropane partial Uji fatty acid ester and 4 g of potassium hydroxide were added to the same autoclave as Production Example 1, 220 g (5 mol) of ethylene oxide was fed at 140 ° C, and 140 ° C. After aging for 2 hours, the catalyst was removed by a conventional method to obtain the polyetherester compound A-4 of the present invention:

In general formula (1),

R: residue which removed the carboxyl group from the fatty acid of fatty acids (a C18 main component in a mixture of C16, 18, 20 carbon atoms);

a: O;

m: 1.2;

Residues obtained by removing a hydroxyl group from X: trimethyrolpropane;

(AO ') _b : (EO) (EO is 100% by mass)

b: 5.6

n: 1.8.

Production Example 5: A-5

Glycerine 92g (1 mol) and isotridecanoic acid 257g (1.2 mol) were put into the glass flask similar to the manufacture example 1, and it reacted at 220 degreeC for 10 hours, removing the produced water, and glycerin partial isotridecanoic acid ester Got. Next, 164 g (0.5 mol) of glycerin partial isotridecanoic acid ester and 4 g of potassium hydroxide were added as a catalyst to the same autoclave as Preparation Example 1, 220 g (5 mol) of ethylene oxide and 93 g (1.3 mol) of propylene oxide at 140 ° C. Mole), the mixture was aged at 140 ° C for 2 hours, and then the catalyst was removed by a conventional method to obtain a polyether ester compound A-5 of the present invention: In general formula (1),

R: residue which removed carboxyl group from isotridecanoic acid;

a: O;

m: 1.2;

X: residue which removed hydroxyl group from glycerin;

(AO ') _b : [(EO) _5.6 (PO) _0.72 ] Random polymer (EO is 85.5% by mass)

n: 2.

In addition, the following compounds were used for the comparison.

Polyether compound that is an intermediate of B-1: A-1 (6 mol of ethylene oxide and 1 mol of propylene oxide adduct)

B-2: sorbitan monolaurate

B-3: glycerin monooleate

Glycerine partial Uji fatty acid ester, an intermediate of B-4: A-4

B-5: 15 moles of ethylene oxide and 2 moles of propylene oxide of nonylphenol

<< evaluation in the negative type resist of radical polymerization type >>

(A) component used for the composition of this invention: 7 mass parts of A-1-A-5 or comparative products B-1-B-5, and methacrylic acid / methyl methacrylate / ethyl acrylate / ethyl methacrylate Copolymer (alkali-soluble resin: weight average molecular weight 100,000) 23 mass parts, polyethyleneglycol (number average molecular weight 400) dimethacrylate 20 mass parts, tripropylene glycol dimethacrylate of the mass ratio 22/45/27/6 20 mass parts, 7 mass parts of benzophenone, and 0.7 mass of 4, 4'-bis (dimethylamino) benzophenone are melt | dissolved in 40 mass parts of mixed solvents of 60 mass parts of 2-methoxyethanol / 40 mass parts of toluene, and the photoresist composition Was prepared.

This photoresist composition is uniformly applied to a 25-m-thick polyethylene butyrate film, dried for 10 minutes in a 100 ° C hot air convection dryer, and a 50-m thick photopolymerizable layer is formed, and then the surface of the photopolymerizable layer. A 35-m polyethylene film was unfolded on and the dry film resist was obtained.

The copper clad laminated board surface which laminated | stacked 35-m rolled copper foil was wet buff-roll-polishing (Three Scotch Bright SF, 2 pass), and peeling the polyethylene film of this laminated film, 120 degreeC by a hot roll laminator, peeling off the polyethylene film. Laminated at

`` Adhesion test ''

The photopolymerizable layer of the copper clad laminated board laminated the dry film resist was exposed at 60 mJ / cm <^2> by the 3 kW high pressure mercury lamp (HMW-201B by Oak Corporation). After peeling a polyethylene terephthalate film, 30 degreeC 1% sodium carbonate aqueous solution (developing solution) was sprayed for 60 second, the unexposed part was melt | dissolved, washed with water, and developed. The adhesiveness was evaluated by the following crosscut test using the board | substrate after this image development. The results are shown in Table 1.

[Assessment Methods]

100 checkerboard eyes with 10 sheaths formed vertically and horizontally at 1 mm intervals on the cured film on the substrate were made by attaching a cellophane tape and sufficiently compressed, then peeled off the tape, and the number of peeled measuring points was counted. The adhesion of the resist was evaluated.

(Circle): Peeling is not recognized at all the measuring points at all, and adhesiveness is favorable.

(Triangle | delta): Peeling is recognized by the point of 1-20 among 100 measuring points, and adhesiveness is slightly bad.

: Peeling is recognized at 21 or more points out of 100 measurement points, and adhesiveness is bad. ≪Bubble generation test≫

The polyethylene terephthalate film was peeled off from the copper clad laminate laminated the dry film resist, and in the state without exposure, 30 degreeC 1% sodium carbonate aqueous solution (developing solution) was sprayed for 60 second, and 2 mass% of uncured resist was contained. The developer was prepared. Using this developer, bubble generation was evaluated by the following method. The results are shown in Table 1.

[Assessment Methods]

50 mL of the test solution was put into a 100 mL volumetric cylinder, and the mixture was shaken vigorously 50 times for 1 minute, the amount of air bubbles immediately after completion of shaking was measured (mL), and the amount of air bubbles was evaluated according to the following criteria. .

(Circle): The quantity of bubbles is less than 20 mL, and there is little bubble generation.

(Triangle | delta): The quantity of foam | bubble is 20 mL or more and less than 40 mL, and foam generation is a little high.

: The amount of bubbles is 40 mL or more, and bubble generation is large.

≪Sum dispersibility test≫

100 mL of the same test solution used for the bubble generation test was placed in a 100 mL cylindrical glass bottle with a lid, and stored in a 30 ° C. thermostat for 1 week. The scum that settled to the bottom part of a glass bottle was visually evaluated, and scum dispersibility was evaluated by the following reference | standard. The results are shown in Table 1.

(Circle): Sedimentation of scum is not seen, and scum dispersibility is good.

(Triangle | delta): Slight sedimentation of scum is seen and scum dispersibility is slightly bad.

: Many scum sediments and poor scum dispersibility.

Adhesion Bubble generation Scum dispersibility  Example One A-1 ○ ○ ○ 2 A-2 ○ ○ ○ 3 A-3 ○ ○ ○ 4 A-4 ○ ○ ○ 5 A-5 ○ ○ ○ Comparative example One B-1 × ○ × 2 B-2 △ △ △ 3 B-3 △ △ × 4 B-4 △ × △ 5 B-5 ○ × △

`` Evaluation in Positive Amplification of Chemically Amplified Type ''

(A) component used for the composition of this invention: 7 mass parts of A1-A5 or comparative products B-1-5, and 20 mol% of the hydroxyl groups of poly (hydroxy styrene) are bromoacetic acid-t-butyl ether Alkali-soluble resin in which the phenoxy group is protected with an acid-decomposable group: metacresol / paracresol = 6/4 mass ratio, weight average molecular weight 4500) 90 parts by mass, triphenylsulfonium trifluoromethanesulfonite (mining generator ) 3 parts by mass was dissolved in 400 parts by mass of ethyl 2-hydroxypropionate to prepare a photoresist composition. This photoresist composition was apply | coated using the spinner on the clean silicon wafer, it dried for 60 second on the 90 degreeC hotplate, and the resist film of the film thickness 1.5m was obtained. This was exposed to a laser beam having a wavelength of 248 nm, immediately heated on a 110 ° C. hot plate for 120 seconds, and then sprayed at 30 ° C. in a 2.4 mass% tetramethylammonium hydroxide aqueous solution (developing solution) for 60 seconds to expose the resist of the exposed portion. It melt | dissolved and removed and prepared the developing solution containing 2 mass% of uncured resist. Using this developer, the bubble generation property and scum dispersibility were evaluated by the same method as the evaluation in the radical polymerization type negative resist. The results are shown in Table 2.

Bubble generation Scum dispersibility  Example 6 A-1 ○ ○ 7 A-2 ○ ○ 8 A-3 ○ ○ 9 A-4 ○ ○ 10 A-5 ○ ○  Comparative Example 6 B-1 ○ × 7 B-2 △ × 8 B-3 △ × 9 B-4 △ × 10 B-5 × △

Claims (3)

As (A) component, following General formula (1) {RCOO (AO) _a } _m X {O (AO ') _b H} _n (1) (Wherein RCO represents a moiety having a hydroxyl group removed from a fatty acid having 6 to 22 carbon atoms, X represents a moiety having a hydroxyl group removed from a polyol having at least three hydroxyl groups, and AO and AO ′ represent an oxyalkylene having 2 to 4 carbon atoms). Group, a represents 0 or 1 or more, b represents 1 or more, and m and n represent 1 or more, provided that the sum of m and n is the same as the number of hydroxyl groups of the polyol. Polyether ester represented by); As the component (B), an alkali-soluble resin having an anionic group or a modified product thereof, A photoresist composition comprising: The method of claim 1, The photoresist composition whose content of the polyether ester represented by General formula (1) with respect to 100 mass parts of solid content of a photoresist composition is 1-20 mass parts. The dry film resist obtained by apply | coating and drying the photoresist composition of Claim 1 or 2 on a polymer film.