WO2005036268A1

WO2005036268A1 - Photoresist composition

Info

Publication number: WO2005036268A1
Application number: PCT/JP2004/014832
Authority: WO
Inventors: Masaki Hosaka; Masatoshi Homma
Original assignee: Asahi Denka Co., Ltd.
Priority date: 2003-10-14
Filing date: 2004-10-07
Publication date: 2005-04-21
Also published as: CN1853138B; CN1853138A; TW200517779A; KR20070017962A; JPWO2005036268A1; TWI346836B; JP4673222B2; KR101073417B1

Abstract

A photoresist composition characterized by comprising: a polyetherester represented by the general formula {RCOO(AO)a}mX{O(AO')bH}n (1) (wherein RCO represents the residue formed by removing the hydroxy group from a C6-22 fatty acid; X represents the residue formed by removing the hydroxy groups from a polyol having at least three hydroxy groups; AO and AO' each represents C2-4 oxyalkylene; a is 0 or a number of 1 or larger; b is a number of 1 or larger; and m and n each is a number of 1 or larger, provided that the sum of m and n is the same as the number of hydroxy groups contained in the polyol) as an ingredient (A); and an alkali-soluble resin having anionic groups or a modification of the resin as an ingredient (B).

Description

Specification

Photoresist composition

Technical field

The present invention relates to a photoresist composition in which scum is reduced in an alkaline developing step of a photoresist.

Background art

[0002] Conventionally, photoresists have been widely used when forming wiring patterns such as printed circuit boards, integrated circuits, and color filters. In the process of forming a wiring pattern, usually, a film-like or liquid photoresist is laminated or coated on a substrate, and then irradiated with actinic radiation such as ultraviolet rays, X-rays, and electron beams, exposed, and cured. Thereafter, development is performed by removing the uncured photoresist with a developer to form a patterned resist film. As the developing solution, an alkaline aqueous solution is usually used, and as the alkaline agent of the developing solution, an inorganic alkaline compound such as an alkali metal carbonate or an alkali metal hydroxide, or an organic alkaline compound such as tetramethylammonium hydroxide is used. Are used.

[0003] In such an alkaline developing solution, uncured resin components, dyes, pigments, polymerization initiators, cross-linking agents, and the like aggregate and float on the surface of the developing solution or precipitate in the developing solution to form a so-called scum. Is generated. The scum adheres to the inside of the developing device and not only hinders the development. If the scum adheres to the object to be developed during the development, there is a problem that the resolution is reduced and a good resist pattern is not formed. For this reason, a developing solution that is excellent in dispersibility of a photoresist scum that does not easily generate scum is being studied.

On the other hand, bubbles are generated when air is entrained in the developing solution, but since the developing solution is usually used in circulation, if the generated foam has insufficient defoaming properties, the bubbles may accumulate. Become. In particular, due to the circulating use, as the resist component in the developer increases, the bubbles hardly disappear. Bubbles not only hinder the circulation of the developer but also hinder the contact between the developer and the photoresist, thus causing a problem that the uncured resist is not sufficiently removed and a good resist pattern is not formed.

[0004] A photoresist which is unlikely to generate scum includes a photopolymer having a polyoxyalkylene group. Photoresists containing compatible compounds (see, for example, Patent Documents 1 and 2), compounds that generate an acid upon irradiation with actinic rays or radiation, and are decomposed by the action of an acid to increase solubility in an alkaline developer. A photoresist containing a group-containing resin (see, for example, Patent Document 3) and a phenolic compound are blended to improve the resolution, thereby reducing the amount of additive and the scum due to the photosensitive agent. Photoresist (for example, refer to Patent Document 4) is known. However, in a photoresist containing a photopolymerizable compound having a polyoxyalkylene group, a relatively large amount of such a photopolymerizable compound needs to be blended in order to obtain sufficient scum dispersibility. Therefore, there is a disadvantage that the resolution of the photoresist is reduced and the bubbling of the developer is increased. Further, the scum-preventing effect of the photoresist containing the acid-generating compound and the resin having the acid-decomposable group and the photoresist having a reduced number of photosensitizers was not sufficient.

[0005] On the other hand, in a photosensitive lithographic printing plate, a polyoxyalkylene sorbitol fatty acid ester is used in order to improve resolution (for example, see Patent Documents 5 and 6). However, it is not known that blending of a polyoxyalkylene sorbite fatty acid ester is effective in dispersing scum and preventing foaming.

[0006] Further, in a photoresist developer, an alkali developer containing a nonionic surfactant IJ having an HLB of 0 to 4 and a nonionic surfactant having an HLB of 620 and an anionic polymer surfactant (for example, Alkaline developer containing an amphoteric surfactant and a nonionic surfactant (see, for example, Patent Literature 8), etc. are known to have excellent scum dispersibility. There was a problem that the liquid foamed a lot.

Patent Document 1: JP-A-5-232699

Patent Document 2: Japanese Patent Application Laid-Open No. 2003-149809

Patent Document 3: JP-A-10_133376

Patent Document 4: JP-A-5-204144

Patent Document 5: JP-A-1-302349

Patent Document 6: JP-A-2002-72461

Patent Document 7: JP-A-8-160632

Patent Document 8: JP-A-11-352700 Problems the invention is trying to solve

[0008] Accordingly, an object of the present invention is to provide a photoresist having excellent scum dispersibility and less bubbling of a developer.

Means for solving the problem

[0009] The present inventors have intensively studied the above problem, and by blending a polyetherester having a specific structure into the photoresist, a photoresist having excellent scum dispersibility and less foaming of the developing solution can be obtained. The inventors have found that the present invention can be obtained, and completed the present invention.

That is, the present invention provides, as the component (A), the following general formula (1)

{RCOO (AO)} Χ {θ (ΑΟ ') Η} (1)

a m b n

(Where RCO represents a residue obtained by removing a hydroxyl group from a fatty acid having 6 to 22 carbon atoms, X represents a residue obtained by removing a hydroxyl group from a polyol having at least three hydroxyl groups, and AO and A ′ ′ A represents an oxyalkylene group having 2 to 4 carbon atoms, a represents 0 or a number of 1 or more, b represents a number of 1 or more, m and n represent a number of 1 or more, provided that m and n The total is the same as the number of hydroxyl groups of the polyol.)

A polyetherester represented by the formula:

A photoresist composition comprising, as the component (B), an alkali-soluble resin having an anionic group or a modified product thereof.

The invention's effect

[0010] In the photoresist composition of the present invention, even when the resist component in the developing solution increases, bubbles with less scum generation are easily eliminated. Therefore, it is possible to reduce the resolution of the resist pattern and the trouble of the developing device due to the generation of scum and bubbles.

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] The component (A) of the present invention is a polyetherester represented by the general formula (1). General formula

In (1), RCO represents a residue obtained by removing a hydroxyl group from a fatty acid having 6 to 22 carbon atoms. Examples of the fatty acids having 6 to 22 carbon atoms include hexanoic acid (cabroic acid), heptanoic acid, octanoic acid (force prillic acid), nonanoic acid (pelargonic acid), decanoic acid (force pric acid), pendecane Acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic 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 (araquinic acid), docosanoic acid (behenic acid); isohexanoic acid, isoheptanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, 2 _ Propylheptanoic acid, isodecanoic acid, isopendecanoic acid, 2_butyloctanoic acid, isododecanoic acid, isotridecanoic acid, 2_pentylnonanoic acid, isotetradecanoic acid, 2_hexyldecanoic acid, 2-heptyldodecanoic acid, isostearic acid, etc. Branched fatty acids; 10-pandecenoic acid, palmitoleic acid, oleic acid, isoleate Phosphate, elaidic acid, linoleic acid, linolenic acid, ricinoleic acid, Gadore phosphate, El force acids, unsaturated fatty acids such as selacholeic acid. In the case of fatty acids having 5 or less carbon atoms, foaming of the developer increases, and in the case of fatty acids having 23 or more carbon atoms, the dispersibility of scum may be insufficient. Among these fatty acids, fatty acids having 10 to 14 carbon atoms are most preferable, and fatty acids having 8 to 18 carbon atoms are more preferable. Further, a saturated fatty acid is preferable since it has less foaming than an unsaturated fatty acid.

X represents a residue obtained by removing a hydroxyl group from a polyol having at least three hydroxyl groups. Examples of such polyolefins include glycerin, 1,2,3-butanetriol, 1,2,4_butanetriol, 2-hydroxymethinole-1,3_propanediol, and 2- 1,2,3-Pentontriol, 1,3,5_Pentantriol, 2,3,5_Pentantriol, 2—Methino-1,2,4_propanetriol, 2-hydroxymethyi 1,3-butanediol, trimethylolethane, 1,3,5-hexanetriol, 1,2,6-hexanetriol, 3-hydroxymethinol_1,5_pentanediol, 3-methylol Trivalent alcohols such as 1,3,5_pentanetriol, trimethylolpropane, trimethylolbutane, 2,5-dimethyl_1,2,5-hexanetriol and triethanolamine; pentaerythritol, 1,2 , 3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5_pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin , Ditrimethylolpropane, sorbitan, alkyldarcoside, N, N, N ', N-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, Ν' ,, tetrakis (2-hydroxyethynole) ethylenediamine, etc. The tetravalent alcohol Pentahydric alcohols such as aditol, arabitolone, xylitol, and triglycerin; hexavalent alcohols such as diantaerythritol, sonorebitone, mannitore, iditonore, inositotone, danoresitone, talose, arose, etc .; Trihydric alcohols; trivalent such as tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1,3-tris (3-t-butinole-1-hydroxy-6-methylphenylbutane) And the like.

[0013] Of these, glycerin and sorbitan are most preferred, with tri- and hexahydric alcohols being more preferred, and tri- and tetrahydric alcohols being more preferred.

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 (methinole) ethylene, oxybutylene, oxy (ethyl) ethylene and the like. A group represented by (AO) and a group represented by (ΑΟ ')

a b

The group can be obtained by addition-polymerizing an alkylene oxide having 2 to 4 carbon atoms to the polyol having at least three hydroxyl groups.

Examples of such alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran (1,4-butylene oxide) and the like. When alkylene oxide is polymerized, homopolymerization of one kind of alkylene oxide or the like, random polymerization of two or more kinds of alkylene oxides, block polymerization, random / block polymerization, or the like may be used. Of the alkylene oxides, ethylene oxide is preferred.

In the case of an addition polymer of two or more alkylene oxides, one of them is preferably ethylene oxide. However, if the ethylene oxide content is too low, the dispersion of the scum may be insufficient, whereas if the ethylene oxide content is high, the foaming of the developer may increase. The ethylene oxide content of the group represented by (AO) and the group represented by (Α〇 ') depends on the total

b

Against Renokishido, it is most preferable and it is Dearuko preferably fixture 60- 90 mass ^_0/0 is a 50- 95 mass ^_0/0 is more preferred instrument 70 to 85 wt%.

The total number of a and b is preferably 1 to 50, more preferably 2 to 20 force, and most preferably 4 to 15.

m and n are the total number of forces of m and n the same as the number of hydroxyl groups of the polyol 1 Represents the above numbers. The ratio of n to m is preferably 0.5-4 force S, more preferably 0.8-3, and most preferably 1-2.

The method for producing the polyetherester represented by the general formula (1) is not particularly limited, and can be produced by a known method. Examples of such a method include (A) a method in which an alkylene oxide is addition-polymerized to a partial ester of a fatty acid and a polyol, and (B) a method in which an alkylene oxide is addition-polymerized to a polyol, and then a fatty acid ester. No. Catalysts for addition polymerization of alkylenoxide include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide; alkali metal alkoxides such as sodium methylate and potassium butoxide; and trimethyl oxide. Tertiary amine conjugates such as min and triethylamine; and Lewis acids such as stannous salt, stannic chloride and boron trifluoride. When performing esterification, esterification may be performed directly with a fatty acid, or esterification may be performed by transesterification using a fatty acid lower alcohol such as fatty acid methyl or fatty acid butyl.

According to the method (B), in the polyetherester represented by the general formula (1), a polyetherester having a number of 0 is not obtained, and a polyetherester having the same number of a and b is obtained. Also, in the method (A), when an alkali metal hydroxide or an alkali metal alkoxide is used as a catalyst, a transesterification reaction occurs. May be

[0016] The content of the polyetherester represented by the general formula (1) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the solid content of the photoresist composition of the present invention. More preferably 15 parts by mass, most preferably 5-10 parts by mass. If the content of the polyetherester represented by the general formula (1) is less than 1 part by mass, the dispersibility of the scum may be insufficient. If the content exceeds 20 parts by mass, the adhesion of the resist to the base material may be reduced. This is because the resolution of the resist pattern after alkali development may be reduced.

[0017] The component (B) of the present invention is an alkali-soluble resin having an anionic group or a modified product thereof. Examples of the anionic group include a carboxyl group, a sulfonic acid group, an ester sulfate group, a phosphoric ester group, a phenolic hydroxyl group, and the like. Carboxy with preferred hydroxyl groups Sil groups are more preferred.

The alkali-soluble resin containing a carboxy group includes a radically polymerizable unsaturated acid such as acrylic acid, methacryloline acid, crotonic acid, fumaric acid, maleic anhydride (anhydride), and itaconic anhydride as an essential component. And a radical polymerizable monomer such as (meth) acrylic acid esters, styrene, acrylonitrile, and (meth) acrylamide.

The acid value of the alkali-soluble resin containing a carboxyl group is preferably 20-300 mgKOH / g, more preferably 40-200 mgKOH / g, and more preferably 60-170 mgK〇H / g. Is most preferred. If the acid value is less than 20 mgK〇H / g, the solubility in the alkaline developer may be insufficient and the developability may decrease.If the acid value exceeds 300 mgK〇H / g, the resolution of the resist pattern after alkali development May decrease.

[0019] Examples of the alkali-soluble resin having a phenolic hydroxyl group include, for example, a novolak resin obtained by polycondensation of a phenol compound and an aldehyde with an acid catalyst, and copolymerization of hydroxystyrene and another radical polymerizable monomer. Polybutylphenol resin and the like. Aldehydes used in the novolak resin include, for example, phenol, m-cresol, o-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, resorcinol, pyrogallol, bisphenol, bisphenol A , Ethyl phenol, propyl phenol, butyl phenol and the like. In addition, examples of the aldehydes used in the novolak resin include honolemuanolaldehyde, acetoaldehyde, propionaldehyde, and the like.

[0020] The molecular weight of the alkali-soluble resin is preferably 1,000 to 1,000,000, more preferably 2,000 to 100,000, and most preferably 3,000 to 50,000 in terms of weight average molecular weight. When the weight average molecular weight is less than 1000, the viscosity may be too low to form a film having a thickness usable for photoresist, and when the weight average molecular weight exceeds 1,000,000, the viscosity may be too high to apply easily. . Further, when the glass transition temperature (Tg) is 0 ° C. or higher, particularly in the range of 510 ° C. to 70 ° C., it is preferable because the coating film does not show tackiness.

[0021] The photoresist composition of the present invention may be a negative resist or a positive resist. Examples of the negative resist include a photo-radical polymerization type resist, a chemically amplified type resist, and a photo-ionization type resist. As a negative resist, for example, Non-diazide resists, chemically amplified resists, and the like can be used. Among these, a photo-radical polymerization type resist is preferred because of good scum dispersibility of the developer and little bubbling.

The photo-radical polymerization type negative resist is an alkali-soluble resin in which the component (B) has an anionic group, and further contains a poly (meth) acrylate of a polyhydric alcohol and a photopolymerization initiator. Or a modified product in which a component (B) is an alkali-soluble resin having an anionic group, in which a part of the anionic group is substituted with a radical polymerizable group. Contained photoresist.

Examples of the polyhydric alcohol of poly (meth) acrylate of polyhydric alcohol include neopentyl glycol, hexylene glycol, glycerin, trimethylolpropane, (poly) ethylene glycol, (poly) propylene glycol, Oxyethylene polyoxypropylene glycol, alkylene oxide adducts of bisphenol A, and the like can be mentioned.

[0024] Examples of the photopolymerization initiator include, for example, aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzylxanthone, thioxanthone, and anthraquinone; acetophenone, propiophenone, disease-hydroxyisobutyl phenone,痫， float quote—Dicronoleate 4-phenoxyacetophenone, 1-hydroxy-1-cyclohexynoleacetophenone, diacetinoleacetophenone, acetofenone, etc .; Organic peroxides such as _ethylhexanoate, t_butylhydroxide peroxide, di-t-butyldiperoxyisophthalate, 3,3 ', 4,4 and tetra (t_butylperoxycarbonyl) benzophenone Jifuji Diphenyl enohalonium salts such as leodobromide and diphenyl olenodium chloride; organic halides such as carbon tetrabromide, chloroform and eodoform; 3-phenyl 5-isoxazolone, 2 2,4,6-tris (trichloromethyl) -1,3,5-triazine benzoanthrone and other heterocyclic and polycyclic compounds; 2,2 thiazo (2,4-dimethylvaleronitrile), 2, Azo compounds such as 2-azobisisobutyronitrile, 1,1 azobis (cyclohexane_1-carbonitrile), 2,2 azobis (2-methylbutyronitrile); iron-allene complex, Titanocene compounds Bisimidazole compounds, N-arylglycidyl compounds, Ataridine System compounds, aromatic ketones Z, combinations of aromatic amines, and peroxy ketals.

[0025] The 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 is obtained by adding glycidyl acrylate or glycidyl methacrylate to the alkali-soluble resin having an anionic group. And glycidyl group-containing unsaturated compounds such as aryl glycidyl ether. The content of the radical polymerizable group is preferably from 200 to 3000, more preferably from 230 to 1500, most preferably from 250 to 750, in terms of unsaturated resin equivalent weight of the resin. If the radical polymerizable group content is less than 200 in terms of unsaturated equivalent, the peelability of the resist pattern after alkali development may be insufficient.If it exceeds 3,000, the resist pattern after alkali development may be insufficient. This is because developability may be insufficient.

The chemically amplified negative resist is a photoresist in which the component (B) is an alkali-soluble resin having a phenolic hydroxyl group, and further contains a photoacid generator and a crosslinking agent. Examples of the photoacid generator include bis (sulfonyl) diazomethanes such as bis (p-toluenesulfonyl) diazomethane; p-tonoleenesulfonic acid; nitrobenzyl derivatives such as 2-nitrobenzyl; methanesulfonic acid of pyrogallol Pyrogallol and aliphatic or aromatic sulfonic esters such as benzenesulfonate of esters and pyrogallol; onium salts such as diphenyl iodonium hexafluorophosphate and triphenylsulfonium trifluoromethane sulfate; henzointosylate and the like Benzoin tosylate; 2- (4-methoxyphenyl) -triazine compounds containing halogen such as 4,6-bis (trichloromethyl) -1,3,5-triazine; 2- (toluenesulfonyloximino ) —Fenilasetonitrile, 痫 _ (1_naphthylsul) Niruokishiimino) such Okishimusuru Honeto compounds such _4 over methoxybenzyl cyanide and the like. Examples of the crosslinking agent include N-alkoxy compounds such as alkoxymethylmelamine resins.

[0027] The negative resist of the photovoltaic thione polymerization type is a photoresist in which the component (B) is an alkali-soluble resin having a phenolic hydroxyl group, and further contains a cationic polymerizable compound and a photoacid generator. . Examples of the cationic polymerizable compound include p-diisopropylbenzene, m-diisopropylbenzene, diphenylethylene, indenone, and acena. Phthene, 2-norbornene, 2,5-norbornadiene, 2,3-benzofuran, indole, 5-methoxyindole, 5-methoxy_2_methylindole, N-butyl_2_pyrrolidone, N-bulcarbazole, bisphenolone A diepoxide, 4 1-Butylcyclohexenedioxide, limonenedioxide, dicyclopentagendioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, bis (2-methyl-4,5_epoxy) Cyclohexylmethyl) and the like.

[0028] The quinonediazide-based positive resist is a photoresist in which the component (B) is an alkali-soluble resin having a phenolic hydroxyl group and further contains a quinonediazide compound, and is insoluble in an alkaline developer before exposure. However, after exposure, the quinonediazide compound becomes alkali-soluble by becoming an indene carboxylic acid compound. Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid ester and 1,2-benzoquinonediazidesulfonic acid ester of a phenolic hydroxyl group-containing compound. Examples of the phenolic hydroxyl group-containing compound include, in addition to the above-mentioned phenols, 11-naphthol, 2-naphthol, dihydroxynaphthalene, gallic acid, gallic acid ester and the like.

[0029] The chemically amplified positive resist is a photoresist in which the component (B) is an alkali-soluble resin having an anionic group, and further contains a dissolution inhibitor having an acid-decomposable group and a photoacid generator; Alternatively, the photoresist is a modified product in which the component (B) is a modified product of an alkali-soluble resin having an anionic group in which the anionic group is protected with an acid-decomposable group, and further contains a photoacid generator.

[0030] 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 developer. Specifically, a phenol compound is a Compounds modified with butoxycarbonyl ether, tetrahydroviranyl ether, 3-bromotetrahydrovilaninoleatenoate, 1-methoxycyclohexinoleatenoate, t-butynoleatel, trimethylsilyl ether, triethylsilyl ether, etc. . Among them, t-butoxycarbonyl ether of polybutylphenol is preferred. Examples of the photoacid generator include those mentioned for the chemically amplified negative resist.

[0031] An anionic group of an alkali-soluble resin having an anionic group is protected by an acid-decomposable group. Examples of the modified products include a resin in which a carboxyl group of an alkali-soluble resin having a carboxy group is protected with an acid-decomposable group, and a phenolic hydroxyl group of an alkali-soluble resin having a phenolic hydroxyl group in which an phenolic hydroxyl group is an acid-decomposable group. And the like. Examples of such an acid-decomposable group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, a benzyloxymethyl group, a phenoxymethinole group, a 1-methoxyethyl group, a t-butyl group, and a benzyl group. Is an i_-substituted alkyl group; a silyl group such as a trimethylsilyl group; an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; an asinole group such as an acetyl group and a propionyl group; And the like.

The photoresist composition of the present invention may contain various additives such as a solvent, a photosensitizer (dye), a radical polymerization inhibitor, a thermal crosslinking compound, a coating improver, It may contain a property improver and the like.

[0032] Examples of the solvent include glycol solvents such as methoxyethanol, ethoxyethanol, butoxyethanol, methoxy-2-propanol, ethoxymethoxy-2-propanol; and methoxyethanol acetate, ethoxyethanol acetate, methoxy-2-propanol acetate, and the like. Ether acetate solvents; ester solvents such as ethyl acetate, butyl acetate, and ethyl 2-hydroxypropionate (ethyl ethyl lactate); alcohol solvents such as hexanol, cyclohexanol, diacetone alcohol; cyclohexanone; Ketone-based solvents such as methylethanol ketone and methyl isobutyl ketone; and hydrocarbon solvents such as cyclohexane, toluene and xylene.

Examples of the photosensitizer include thioxanthenes, xanthenes, ketones, thiopyridinium salts, basestyryls, merocyanines, 3_substituted coumarins, 3.4_substituted coumarins, and cyanines. And athalidine, thiazine, phenothiazine, anthracene, corone, benzanthracene, perylene, merocyanine, ketocoumarin, fumaline, and borate dyes.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, catechol, resorcinol, naphthylamine, t-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4- Methyl-6_t_butylphenol), 2,2 methylene Bis (4-ethyl-6_t_butylphenol) and the like.

Further, the photosensitive resin composition of the present invention contains additives such as a colorant (dye or pigment), a color former (a dye that develops a color when irradiated with light), a plasticizer, a flame retardant, an adhesion promoter, and an organic solvent. If necessary, it may be added.

When a photoresist pattern of the present invention is used to form a resist pattern on a copper-clad laminate, silicon resin, a glass plate, or the like, the photoresist composition is roll-coated, After coating by a knife coating method, a spray coating method, or the like, drying is performed as necessary, drawing is performed with an irradiation force through a desired mask pattern, an electron beam, and development processing is performed using an alkali developing solution.

Further, the photoresist composition of the present invention can be suitably used as a dry film resist after being coated on a polymer film and dried. Desirably, such a polymer film is capable of transmitting active light 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, polyvinyl chloride copolymer, and polymethacryl. Polyethylene terephthalate is preferred among the powers including a film composed of methyl acid copolymer, polystyrene, polystyrene copolymer, polyacrylonitrile, polyamide and the like. The thickness of the polymer film is preferably 5-100 m, more preferably 10-30 m. The thickness of the resist composition applied and dried on the polymer film varies depending on the application. If the thickness is too small, the film strength will be low. If the thickness is too large, the resolution will be low. One lOOm is preferred 5-60'm is more preferred.

[0036] In addition to the support and the photopolymerized layer, a protective film may be laminated on the surface of the photopolymerized layer. As the protective film, films such as polyethylene and polypropylene are preferable.

Examples of the method of applying the photosensitive resin composition include a roll coating method, a knife coating method, a spray coating method and the like, and the drying temperature and time are usually from 110 to 130 ° C for 110 minutes. The film thickness of the photopolymerized layer in the photosensitive element of the present invention varies depending on the application. Too thin a film reduces the film strength, while too thick reduces the resolution. Then 1 lOO 'm is preferred 5-60' m is more preferred Good.

[0037] After the photoresist composition of the present invention is applied and exposed, the alkali developing solution used in the developing step is not particularly limited, and a conventionally known alkali developing solution can be used. Examples of the alkali agent of such an alkali developer include alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; alkali metal bicarbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; Alkali metal borates such as lithium borate, sodium borate and potassium borate; alkali metal silicates such as lithium silicate, sodium silicate and potassium silicate; lithium hydroxide, sodium hydroxide, and hydroxide Inorganic alkaline compounds such as alkali metal hydroxides such as potassium; ethylenediamine, propylenediamine, piperidine, morpholine, piperazine, tetramethylammonium hydroxide, tetraethynoleammonium hydroxide, trimethyl (2- Organic alcohols such as hydroxyethyl) ammonium hydroxide Potassium compounds, and the like. Among these alkaline agents, sodium carbonate and tetramethylammonium hydroxide, which are preferred by alkali metal carbonates and organic alkaline compounds, are more preferred.

[0038] The concentration of the alkaline agent in the developer varies depending on the type of the alkaline agent used and the photoresist, but in the case of an alkali metal carbonate, 0.1 to 5 parts by mass of water is used. It is more preferably 0.3 to 3 parts by mass, most preferably 0.5 to 2 parts by mass. In the case of an organic alkaline compound, the concentration of the alkali agent in the developer is preferably 0.5 to 25 parts by mass with respect to 100 parts by mass of water, and is 1 to 15 parts by mass. More preferably, it is most preferably 1.5 to 10 parts by mass. The temperature of the developer is preferably from 15 to 50 ° C, more preferably from 20 to 40 ° C, and most preferably from 25 to 35 ° C. If the temperature of the developer is lower than 15 ° C, the dissolution of the uncured resist may be insufficient, and if it exceeds 50 ° C, the cured resist may peel off. .

Example

Hereinafter, the present invention will be described more specifically with reference to examples. In the following examples, parts and% are based on mass unless otherwise specified. Also, EO indicates CH〇, and PO indicates

twenty four

Indicates CH-1. <Production Example 1: A_1>

In a stainless steel autoclave equipped with a stirrer, thermometer, and nitrogen gas inlet tube, 92 g (1 mol) of glycerin and 4 g of sodium hydroxide as a catalyst were charged, and the system was replaced with nitrogen. Stir for 1 hour to dissolve the sodium hydroxide. 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 the catalyst was removed by a conventional method to obtain a polyether compound. Got. A glass flask equipped with a stirrer, thermometer and nitrogen gas inlet tube was charged with 207 g (0.5 mol) of a polyether compound, 219 g (0.5 mol) of coconut oil fatty acid, and 0.5 g of methanesulfonic acid as a catalyst. And reacted at 180 ° C. for 5 hours to obtain polyetherester A-11 of the present invention:

In the general formula (1),

R: residue obtained by removing a carboxy group from coconut oil fatty acid (a mixture of C12, C14, C16 and having a main component of C12);

(AO): (EO) (PO) block polymers (EO 82, 1 wt ^_0/0);

m: 丄；

X: residue obtained by removing a hydroxyl group from glycerin;

(ΑΟ '): (EO) (PO) block polymers (EO 82, 1 wt ^_0/0);

n: 2.

The same autoclave as in Production Example 1 was charged with 346 g (1 monole) of sorbitan monolaurate (manufactured by Kao Corporation, trade name: SP-L10) and a 28% methanol solution of sodium methylate as a catalyst at 100 ° C. The pressure was reduced to lkPa or less to remove methanol as a solvent. Next, a mixture of 264 g (6 mol) of ethylene oxide and 116 g (2 mol) of propylene oxide was fed at 140 ° C., aged at 140 ° C. for 2 hours, and the catalyst was removed by a conventional method. The polyether noreestenole A_2 of the invention was obtained:

In the general formula (1),

R: a residue obtained by removing a carboxyl group from lauric acid;

a: 0; m: 1;

X: residue obtained by removing a hydroxyl group from sorbitan;

(ΑΟ '): [(ΕΟ ) (ΡΟ)] block copolymer (Ipushiron_〇 69.4 mass ^{_0/0); η:} 3

b 2 0.67.

The same autoclave as in Production Example 1 was charged with 351 g (l mol) of glycerin monoolate and an ether complex lg of boron trifluoride as a catalyst. After feeding 176 g (4 mol) of ethylene oxide at C and aging at 60 ° C. for 2 hours, the catalyst was removed by a conventional method to obtain a polyester ester A-3 of the present invention:

In the general formula (1),

R: a residue obtained by removing a carboxy group from oleic acid;

a: 0;

m: 丄；

X: residue obtained by removing a hydroxyl group from glycerin;

(ΑΟ '): Ipushiron_〇 (Ipushiron'omikuron 100 mass ^_0/0);

b

b: 2;

n: 2.

The same glass flask as in Production Example 1 was charged with 134 g (l mol) of trimethylolpropane and 328 g (l.2 mol) of tallow fatty acid, and reacted at 220 ° C for 10 hours while removing generated water. A propane partially tallow fatty acid ester was obtained. Next, the same autoclave as in Production Example 1 was charged with 23 lg (0.5 mol) of trimethylolpropane partially tallow fatty acid ester and 4 g of potassium hydroxide as a catalyst, and 220 g (5 mol) of ethylene oxide was fed at 140 ° C. After aging at 140 ° C. for 2 hours, the catalyst was removed by a conventional method to obtain a polyester ester compound A-4 of the present invention:

In the general formula (1),

R: residue obtained by removing the carboxy group from tallow fatty acid (a mixture of C16, C18, C20 having a main component of C18);

a: 0; m: l.2;

X: residue obtained by removing a hydroxyl group from trimethylolpropane;

(ΑΟ '): (Ipushiron_〇) (Ipushiron'omikuron 100 mass ^_0/0);

b: 5.6

n: l.8.

The same glass flask as in Production Example 1 was charged with 92 g (l mol) of glycerin and 257 g (l.2 mol) of isotridecanoic acid, and reacted at 220 ° C for 10 hours while removing generated water. Isotridecanoate was obtained. Next, 164 g (0.5 mol) of glycerin partially isotridecanoate and 4 g of lithium hydroxide as a catalyst were charged into the same autoclave as in Production Example 1, and at 140 ° C., 220 g (5 mol) of ethylene oxide and propylene oxide were added. A mixture of 93 g (1.3 mol) of oxide was fed and aged at 140 ° C. for 2 hours, and then the catalyst was removed by a conventional method to obtain a polyetheresteride conjugate A-5 of the present invention: General formula: In (1), R: a residue obtained by removing a carboxy group from isotridecanoic acid;

a: 0;

m: l.2;

X: residue obtained by removing a hydroxyl group from glycerin;

(ΑΟ '): [(ΕΟ) (ΡΟ)] random polymer (Ε〇 is 85.5% by mass);

n: 2.

The following compounds were used for comparison.

B_l: Polyether compound which is an intermediate of A-1 (glycerin ethylene oxide

Adduct of 6 mol of side and 1 mol of propylene oxide)

B-2: Sorbitan monolaurate

B_3: Glycerin monolate

B— 4: Intermediate of A—4 Glycerin partial tallow fatty acid ester

B-5: 15 moles of ethylene oxide of noyurphenol and propylene oxide

2 mole block adduct

<Evaluation of Radical Polymerization Type Negative Resist> Component (A) used in the composition of the present invention: 7 parts by mass of A—11—A—5 or comparative product B_l—B_5, mass ratio of methyl methacrylate / methyl methacrylate / ethyl acrylate / ethyl methacrylate 22Z45Z27Z6 copolymer (Alkali-soluble resin: weight average molecular weight 100,000) 23 parts by weight, polyethylene glycol (number average molecular weight 400) dimethallate 20 parts by weight, tripropylene glycol dimethatalylate 20 parts by weight, benzophenone 7 parts by weight, and 4 Then, 0.7 parts by mass of bis (dimethylamino) benzophenone was dissolved in 40 parts by mass of a mixed solvent of 60 parts by mass of 2-methoxyethanol and 40 parts by mass of Z tonolene to prepare a photoresist composition.

This photoresist composition is uniformly applied to a 25-m-thick polyethylene terephthalate film and dried for 10 minutes with a hot air convection dryer at 100 ° C to form a 50-m-thick photopolymerizable layer. Then, a 35'm polyethylene film is laminated on the surface of the photopolymerizable layer.

The surface of the copper-clad laminate on which 35'm rolled copper foil is laminated is polished by wet puff-roll (Scotchbright SF, manufactured by 3LEM Co., Ltd., twice), and the photosensitive layer is peeled off by a hot roll laminator while peeling off the polyethylene film of the laminated film. Laminated with C.

<< Adhesion Test >>

The photopolymerizable layer of the copper-clad laminate laminated with the dry film resist was exposed at 60 mj / cm ² with a 3 kW high-pressure mercury lamp (HMW-201B manufactured by Oak Manufacturing Co., Ltd.). After peeling off the polyethylene terephthalate film, a 1% aqueous solution of sodium carbonate (developer) at 30 ° C. was sprayed for 60 seconds to dissolve and remove unexposed portions, washed with water, dried and developed. Using the substrate after the development, the adhesion was evaluated by the following cross cut test. Table 1 shows the results.

[0047] [Evaluation method]

Cut the cured film on the board with 10 cuts each in the vertical and horizontal directions at lmm intervals, make 100 grids, attach cellophane tape, apply sufficient pressure, peel off the tape, and count the number of peeled measurement points. The resist was evaluated for adhesion based on the following criteria.

〇: No peeling was observed at all measurement points, indicating good adhesion.

Δ: Peeling was observed at 1 to 20 points out of 100 measurement points, and the adhesion was slightly poor.

•: Peeling was observed at 21 or more points out of 100 measurement points, indicating poor adhesion.

[0048] << Bubbling test >> The polyethylene terephthalate film is peeled off from the copper-clad laminate on which the dry film resist is laminated, and without exposure, a 1% aqueous solution of sodium carbonate (developer) at 30 ° C is sprayed for 60 seconds to remove the uncured resist. A developer solution containing 1% by mass was prepared. Using this developer, foaming was evaluated by the following method. Table 1 shows the results.

[Evaluation method]

Place 50 mL of the test solution in a 100 mL stoppered graduated cylinder, shake vigorously 50 times a minute, read the amount of foam immediately after the end of shaking (mL), and foam according to the following criteria according to the amount of foam. The strength was evaluated.

〇: The amount of foam is less than 20 mL and the foaming property is low.

Δ: The amount of foam is 20 mL or more and less than 40 mL, and the foaming property is somewhat large.

': Foam volume ¾ OmL or more, and foaming is high.

[0050] << Scum dispersibility test >>

The same test solution lOOmL as used in the foaming test was placed in a lOOmL cylindrical glass bottle with a lid, and stored for 1 week in a 30 ° C constant temperature bath. The scum settling at the bottom of the glass bottle was visually observed, and the scum dispersibility was evaluated according to the following criteria. The results are shown in Table 1.

〇: No scum settling was observed, and scum dispersibility was good.

Δ: Scum settling was somewhat observed, and scum dispersibility was somewhat poor.

•: Lots of scum settled Poor scum dispersibility.

[Table 1]

Adhesive property Foaming property Scum dispersing property

1 A-1 〇〇〇 Real 2 A-2 〇〇〇

33 A-3 〇〇〇

Example 4 A-4 〇〇〇

5 A-5 〇〇〇

1 B- 1 X 〇 X ratio 2 B-2 △ mm △

Comparison 3 B-3 Δ △ X

Example 4 B-4 △ X Δ

5 B-5 〇 X △

<< Evaluation with Chemically Amplified Positive Resist >>

Component (A) used in the composition of the present invention: 7 parts by mass of A1-A5 or comparative product B-1-5, and 20 mol of hydroxyl groups of poly (hydroxystyrene). /. (Methyltarezol Z paracresol = 6Z4 mass ratio, weight average molecular weight 4500) 90 parts by mass of triphenylsulfonium 3 parts by mass of trifluoromethanesulfonate (photoacid generator) was dissolved in 400 parts by mass of ethyl 2-hydroxypropionate to prepare a photoresist composition. This photo resist composition was applied on a clean silicon wafer using a spinner, and dried on a hot plate at 90 ° C. for 60 seconds to obtain a resist film having a thickness of 1.5 ′ m. This was exposed to a laser beam having a wavelength of 248 nm, and immediately heated on a hot plate at 110 ° C for 120 seconds. C 2.4 mass ⁰ /. An aqueous solution of tetramethylammonium hydroxide (developer) was sprayed for 60 seconds to dissolve and remove the exposed portion of the resist, thereby preparing a developer containing 2% by mass of uncured resist. Using this developer, the foaming property and the scum dispersibility were evaluated in the same manner as in the evaluation with the radical polymerization type negative resist. Table 2 shows the results.

[0053] [Table 2] Foaming property Scum dispersing property

6 A-1 〇〇 Actual 7 A-2 〇〇 Application 8 A-3 〇〇 Example 9 A-4 〇〇

10 A-5 〇〇

6 B-1 〇 X ratio 7 B-2 △ X comparison 8 B-3 ΔX Example 9 B- ΔX

10 B-5 X Δ

Claims

The scope of the claims

[1] As the component (A), the following general formula (1)

{RCOO (AO)} Χ {θ (ΑΟ ') Η} (1)

a m b n

(Where RCO represents a residue obtained by removing a hydroxyl group from a fatty acid having 6 to 22 carbon atoms, X represents a residue obtained by removing a hydroxyl group from a polyol having at least three hydroxyl groups, and AO and A A ′ Represents an oxyalkylene group having 2 to 4 carbon atoms, a represents 0 or 1 or more, b represents 1 or more, m and n represent 1 or more, provided that m and n The total is the same as the number of the hydroxyl groups of the polyol described above.) A polyetherester represented by the following formula (B); Photoresist composition.

[2] The photoresist composition according to claim 1, wherein the content of the polyester ester represented by the general formula (1) is 120 parts by mass with respect to 100 parts by mass of the solid content of the photoresist composition.

[3] The photoresist composition according to claim 1 or 2 is coated on a polymer film and dried.