JP2010039052A - Photosensitive composition and method of manufacturing pattern film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition, eliminating a baking process after exposure in forming a pattern film made of a hardened material of the photosensitive composition by exposure and development, and further restraining migration of metal when metal comes into contact with the pattern film, and a method of manufacturing the pattern film using the photosensitive composition. <P>SOLUTION: This photosensitive composition includes a siloxane polymer having a carboxyl group, a compound having an olefinic double bond and a photoradical generating agent. According to this method of manufacturing a pattern film 1A, after the photosensitive composition is coated on a substrate 2 to form a photosensitive composition layer 1 on the substrate 2, the photosensitive composition layer 1 is partially exposed to harden the photosensitive composition layer 1 of an exposed part 1a and insoluble to a developing liquid, and subsequently the photosensitive composition layer 1 is developed by the developing liquid to eliminate the photosensitive composition layer 1 of an unexposed part 1b. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive composition used for forming a pattern film used for an insulating film of an electronic device such as a semiconductor device, and more specifically, from a cured product of the photosensitive composition by exposure and development. The present invention relates to a photosensitive composition capable of suppressing metal migration when a metal is in contact with the pattern film, and a method for producing a pattern film using the photosensitive composition.

  In an electronic device such as a semiconductor device, it is necessary to form a thin film having excellent insulating properties in order to reduce the size and thickness. In addition, it is necessary to form an insulating film having a fine pattern shape for a passivation film or a gate insulating film of a semiconductor device. Then, the photosensitive composition using the alkoxysilane condensate is proposed as a photosensitive composition which can be patterned.

  For example, Patent Document 1 below discloses a photosensitive composition containing an alkali-soluble siloxane polymer, a compound that generates a reaction accelerator by light, and a solvent. The alkali-soluble siloxane polymer is an alkoxysilane condensate obtained by removing water and catalyst from a reaction solution obtained by hydrolyzing and condensing water and a catalyst with alkoxysilane. In addition, as the compound that generates the reaction accelerator by the light, a photoacid generator or a photobase generator is used.

When forming a thin film having a fine pattern shape using the photosensitive composition containing the alkoxysilane condensate as described above, first, the photosensitive composition is applied on a substrate. Next, the photosensitive composition layer on the substrate is dried and partially exposed through a mask. By exposure, an acid or a base is generated from the photoacid generator or photobase generator contained in the photosensitive composition. Crosslinking of the alkoxysilane condensate proceeds with the acid or base, and the photosensitive composition layer in the exposed area is cured. The cured photosensitive composition layer in the exposed area does not dissolve in the developer. Thereafter, the photosensitive composition layer is developed with an alkaline solution. After development, the remaining cured product of the photosensitive composition is heated to obtain a hard and dense thin film with a fine pattern.
Japanese Patent Laid-Open No. 6-148895

  However, when a thin film having a fine pattern shape is formed using the photosensitive composition described in Patent Document 1, the photosensitive composition layer coated on the substrate is exposed to an acid before being developed. Or in order to diffuse a base, it was necessary to perform a baking process. Therefore, the process becomes complicated, and a residue tends to be generated after development.

  Moreover, in the obtained thin film, the acid or base which arose from the photo-acid generator or the photobase generator by exposure remains. Therefore, for example, when a metal is in contact with the thin film, migration is likely to occur due to an acid or a base.

  An object of the present invention is to form a patterned film made of a cured product of a photosensitive composition by exposure and development, and it is not necessary to perform a baking process after exposure, and when the metal is in contact with the pattern film, It is in providing the photosensitive composition which can suppress migration of this, and the manufacturing method of the pattern film using this photosensitive composition.

  According to this invention, the photosensitive composition characterized by including the siloxane polymer which has a carboxyl group, the compound which has an olefin double bond, and a photoradical generator is provided.

  In a specific aspect of the photosensitive composition according to the present invention, the siloxane polymer having a carboxyl group has an organic group in which a carbon atom is directly bonded to a silicon atom, and 1 to 25% of the organic group Has a carboxyl group. In this case, the developability of the photosensitive composition can be further enhanced.

  In another specific aspect of the photosensitive composition according to the present invention, the compound having an olefin double bond is a siloxane polymer having an olefin double bond.

  In still another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer having an olefin double bond has an organic group in which a carbon atom is directly bonded to a silicon atom, and 5 of the organic group. ~ 100% have olefinic double bonds. In this case, since the siloxane polymer having an olefin double bond is effectively crosslinked by radicals generated during exposure, a pattern can be formed without performing a baking step after exposure.

  In still another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer having a carboxyl group and the siloxane polymer having an olefin double bond are the same siloxane polymer, and A siloxane polymer having a heavy bond is included.

  The method for producing a patterned film according to the present invention comprises a step of coating a photosensitive composition constituted according to the present invention on a substrate, forming a photosensitive composition layer on the substrate, and the photosensitive composition layer. The photosensitive composition layer of the exposed portion is cured by partially exposing the photosensitive composition layer so as to have an exposed portion irradiated with light and an unexposed portion not irradiated with light. And making the photosensitive composition layer insoluble in a developing solution, and developing the photosensitive composition layer with a developing solution, thereby removing the photosensitive composition layer in the unexposed area and curing the photosensitive composition. And a step of forming a pattern film comprising:

  Since the photosensitive composition concerning this invention contains the siloxane polymer which has a carboxyl group, the developability at the time of forming a pattern film | membrane by exposure and image development can be improved. In development, a relatively low concentration alkaline solution can be used as a developer.

  Furthermore, since the photosensitive composition which concerns on this invention contains the compound which has an olefin double bond, the said siloxane polymer can be bridge | crosslinked effectively with the radical produced from the photoradical generator by exposure. Therefore, it is not necessary to use a photoacid generator or a photobase generator. Since it is not necessary to use a photoacid generator or a photobase generator, no acid or base remains in the formed pattern film. Therefore, when a metal is in contact with the pattern film, metal migration can be suppressed.

  In the method for producing a patterned film according to the present invention, the photosensitive composition layer made of the photosensitive composition constituted according to the present invention is partially exposed and developed, so that developability can be improved. Moreover, when a metal is in contact with the obtained pattern film, metal migration can be suppressed.

  Details of the present invention will be described below.

  The photosensitive composition according to the present invention includes a siloxane polymer having a carboxyl group, a compound having an olefin double bond, and a photoradical generator.

(Siloxane polymer having carboxyl group)
The siloxane polymer having a carboxyl group contained in the photosensitive composition of the present invention is not particularly limited as long as it has a carboxyl group. Only one type of siloxane polymer may be used, or two or more types may be used in combination. The siloxane polymer having a carboxyl group is excellent in solubility in a developing solution such as an alkaline solution. Therefore, developability can be improved in the photosensitive composition according to the present invention.

  The carboxyl group-containing siloxane polymer is a carboxyl group-containing alkoxysilane condensate obtained by condensing a carboxyl group-containing alkoxysilane or an alkoxysilane condensate obtained by condensing an alkoxysilane having no carboxyl group. A carboxyl group-containing alkoxysilane condensate into which a carboxyl group has been introduced is preferred. When these preferable carboxyl group-containing alkoxysilane condensates are used, the developability of the photosensitive composition can be further enhanced.

  The method for introducing a carboxyl group into an alkoxysilane condensate obtained by condensing an alkoxysilane having no carboxyl group is not particularly limited. Examples of this method include a method in which a carboxylic anhydride is reacted with a cyclic ether group-containing alkoxysilane condensate obtained by condensing an alkoxysilane having a cyclic ether group.

  When obtaining a carboxyl group-containing alkoxysilane condensate, one type of alkoxysilane may be used, or two or more types of alkoxysilane may be used.

Various alkoxysilanes can be used as the alkoxysilane. The alkoxysilane is preferably an alkoxysilane represented by the following formula (1).
Si (X1) _p (X2) _q (X3) _4-pq Formula (1)

  In the above formula (1), X1 represents hydrogen or a non-hydrolyzable organic group having 1 to 30 carbon atoms, X2 represents an alkoxy group, X3 represents a hydrolyzable group other than an alkoxy group, p represents an integer of 0 to 3, q represents an integer of 1 to 4, and p + q ≦ 4. When p is 2 or 3, the plurality of X1s may be the same or different. When q is 2-4, several X2 may be the same and may differ. When p + q ≦ 2, the plurality of X3 may be the same or different.

  The alkoxy group X2 and the hydrolyzable group X3 other than the alkoxy group are usually hydrolyzed and silanol when heated to room temperature (25 ° C.) to 100 ° C. in the presence of excess water and without catalyst. A group capable of generating a group or a group capable of further condensation to form a siloxane bond.

  The alkoxy group X2 is not particularly limited. Specifically as said alkoxy group X2, C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, or a propoxy group, etc. are mentioned.

  The hydrolyzable group X3 other than the alkoxy group is not particularly limited. Specific examples of the hydrolyzable group X3 other than the alkoxy group include halogen groups such as chlorine and bromine, acetyl groups, hydroxyl groups, and isocyanate groups.

  The non-hydrolyzable organic group X1 is not particularly limited. Examples of the non-hydrolyzable organic group X1 include organic groups having 1 to 30 carbon atoms, which are hardly hydrolyzed and are stable hydrophobic groups. The organic group having 1 to 30 carbon atoms which is a stable hydrophobic group includes an alkyl group having 1 to 30 carbon atoms, a halogenated alkyl group, an aromatic substituted alkyl group, an aryl group, a group containing a vinyl group, and an epoxy group. Examples thereof include an organic group, an organic group containing an amino group, or an organic group containing a thiol group.

  Examples of the alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, pentyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group. Or an eicosyl group etc. are mentioned.

  Examples of the halogenated alkyl group include a fluorinated group of an alkyl group, a chlorinated group of an alkyl group, or a brominated group of an alkyl group. Examples of the halogenated alkyl group include 3-chloropropyl group, 6-chloropropyl group, 6-chlorohexyl group, 6,6,6-trifluorohexyl group, and the like.

  Examples of the aromatic substituted alkyl group include a benzyl group and a halogen-substituted benzyl group. Examples of the halogen-substituted benzyl group include 4-chlorobenzyl group and 4-bromobenzyl group.

  Examples of the aryl group include a phenyl group, a tolyl group, a mesityl group, and a naphthyl group.

  Specific examples of the alkoxysilane represented by the above formula (1) include, for example, triphenylethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triethylmethoxysilane, ethyldimethylmethoxysilane, and methyldiethylmethoxysilane. , Ethyldimethylethoxysilane, methyldiethylethoxysilane, phenyldimethylmethoxysilane, phenyldiethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylethoxysilane, methyldiphenylmethoxysilane, ethyldiphenylmethoxysilane, methyldiphenylethoxysilane, ethyldiphenylethoxysilane , Tert-butoxytrimethylsilane, butoxytrimethylsilane, dimethylethoxysilane, methoxy Dimethylvinylsilane, ethoxydimethylvinylsilane, diphenyldiethoxysilane, phenyldiethoxysilane, dimethyldimethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane, diethoxydimethylsilane Diacetoxymethylvinylsilane, diethoxymethylvinylsilane, diethoxydiethylsilane, dimethyldipropoxysilane, dimethoxymethylphenylsilane, methyltrimethoxysilane, methyltriethoxysilane, methyl-tri-n-propoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyl-tri-n-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Propyl-tri-n-propoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, n-hexyltrimethoxysilane, n-hexyltri Ethoxysilane, n-hexyltripropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, Dodecyltripropoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, tetradecyltripro Poxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane, eicosyldecyltrimethoxysilane, eicosyltriethoxysilane, eicosyl Tripropoxysilane, 6-chlorohexyltrimethoxysilane, 6,6,6-trifluorohexyltrimethoxysilane, benzyltrimethoxysilane, 4-chlorobenzyltrimethoxysilane, 4-bromobenzyltri-n-propoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Toxisilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Pyrtriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, triethoxysilane, trimethoxysilane, triisopropoxysilane, tri-n-propoxysilane, triacetoxysilane , Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetraacetoxysilane and the like.

  The weight average molecular weight of the siloxane polymer having a carboxyl group is preferably in the range of 500 to 30000, and more preferably in the range of 1000 to 20000. If the weight average molecular weight of the siloxane polymer is too small, it may be difficult to control the solubility of the photosensitive composition in the developer. When the weight average molecular weight of the siloxane polymer is too large, a gel-like substance is easily generated in the photosensitive composition, and a residue is easily generated after development.

  The siloxane polymer having a carboxyl group has an organic group in which a carbon atom is directly bonded to a silicon atom, and 1 to 25% of the organic group preferably has a carboxyl group. When the ratio of the organic group having a carboxyl group in 100% of the organic group in which the carbon atom is directly bonded to the silicon atom is less than 1%, the developability of the photosensitive composition may not be sufficiently improved. If it exceeds 25%, the photosensitive composition tends to dissolve in water as well as the developer, and it may be difficult to form a pattern film.

  The photosensitive composition according to the present invention preferably further contains a siloxane polymer having at least one of a cyclic ether group and a thiol group. In this case, the adhesion of the pattern film to the substrate can be improved. In particular, when the substrate on which the pattern film is formed is made of metal or metal oxide, the adhesion of the pattern film to the substrate can be extremely enhanced.

(Compound having olefin double bond)
The compound having an olefin double bond group contained in the photosensitive composition of the present invention is not particularly limited as long as it has an olefin double bond group. As for the compound which has the said olefin double bond, only 1 type may be used and 2 or more types may be used together.

  The compound having an olefin double bond is preferably a siloxane polymer having an olefin double bond group. As for the said siloxane polymer which has an olefin double bond, only 1 type may be used and 2 or more types may be used together.

  The siloxane polymer having an olefin double bond is easily compatible with the siloxane polymer having a carboxyl group.

  The siloxane polymer having a carboxyl group and the siloxane polymer having an olefin double bond may be different siloxane polymers or the same siloxane polymer. The photosensitive composition according to the present invention may contain a siloxane polymer having a carboxyl group and an olefin double bond. The siloxane polymer having a carboxyl group and an olefin double bond may be used alone or in combination of two or more.

  Examples of the siloxane polymer having an olefin double bond include an alkoxysilane condensate obtained by condensing an alkoxysilane having an olefin double bond, and an alkoxysilane that forms an olefin double bond when condensed. The resulting alkoxysilane condensate or an alkoxysilane condensate into which an olefinic double bond has been introduced after the alkoxysilane is condensed is preferred. When these alkoxysilane condensates are used, the siloxane polymer can be more effectively cross-linked.

  The method for introducing the olefin double bond after the alkoxysilane is condensed is not particularly limited. Examples of this method include a method using a hydrosilylation reaction.

  In obtaining an alkoxysilane condensate, one type of alkoxysilane may be used, or two or more types of alkoxysilane may be used.

  Examples of the alkoxysilane having an olefin double bond include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxy. Examples include loxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

  In obtaining the alkoxysilane condensate having the olefin double bond, various alkoxysilanes can be used. As alkoxysilane, the alkoxysilane represented by the formula (1) described above can be used.

  The weight average molecular weight of the siloxane polymer having an olefin double bond is preferably in the range of 500 to 30000, and more preferably in the range of 1000 to 20000. If the weight average molecular weight is too small, the photosensitive composition may not be sufficiently cured by exposure. When the said weight average molecular weight is too large, a gel-like thing will arise easily in a photosensitive composition, and it will become easy to produce a residue after image development.

  The siloxane polymer having an olefin double bond has an organic group in which a carbon atom is directly bonded to a silicon atom, and 5 to 100% of the organic group preferably has an olefin double bond. When the ratio of the organic group having an olefin double bond in 100% of the organic group in which a carbon atom is directly bonded to the silicon atom is less than 5%, the siloxane polymer may not be sufficiently crosslinked by exposure.

  The compound having an olefin double bond is preferably contained within a range of 10 to 1000 parts by weight, and preferably within a range of 20 to 500 parts by weight with respect to 100 parts by weight of the siloxane polymer having a carboxyl group. It is particularly preferable that it is contained in the range of 50 to 200 parts by weight. If the amount of the compound having an olefin double bond is too small, it may be difficult to sufficiently crosslink the siloxane polymer. When there is too much quantity of the compound which has the said olefin double bond, the developability of the photosensitive composition may fall.

(Photo radical generator)
Specific examples of the photo radical generator contained in the photosensitive composition according to the present invention include halomethylated triazine derivatives, halomethylated oxadiazole derivatives, imidazole derivatives, benzoin, benzoin alkyl ethers, anthraquinone derivatives, benzanthrone. Derivatives, benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzoate derivatives, acridine derivatives, phenazine derivatives, titanocene derivatives, α-aminoalkylphenone compounds, oxime derivatives, and the like. A photoradical generator may be used independently and 2 or more types may be used together.

  Examples of the halomethylated triazine derivative include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, or 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s- Examples include triazine.

  Examples of the imidazole derivative include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2 -(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, or 2- (o-methoxyphenyl) -4,5 -Diphenylimidazole dimer etc. are mentioned.

  Examples of the benzoin alkyl ethers include benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.

  Examples of the anthraquinone derivative include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.

  Examples of the benzophenone derivative include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, and the like.

  Examples of the acetophenone derivative include 2,2, -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1- Methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, or 1, Examples include 1,1, -trichloromethyl- (p-butylphenyl) ketone.

  Examples of the thioxanthone derivative include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

  Examples of the benzoic acid ester derivative include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the acridine derivative include 9-phenylacridine or 9- (p-methoxyphenyl) acridine.

  Examples of the phenazine derivative include 9,10-dimethylbenzphenazine.

  Examples of the titanocene derivative include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3,4,5. , 6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2 , 4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di- Fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2 , - di - fluoro-1-yl, or di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - 1-yl, and the like.

  Examples of the α-aminoalkylphenone compounds include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4- Diethylaminobenzoyl) coumarin or 4- (diethylamino) chalcone It is below.

  Examples of the oxime derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), or ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  The photosensitive composition according to the present invention preferably contains the photo radical generator in the range of 0.1 to 30 parts by weight, based on 100 parts by weight of the siloxane polymer having a carboxyl group, and 1 to 15 parts by weight. It is more preferable to include within the range. If the amount of the photo radical generator is too small, a sufficient amount of radicals may not be generated by exposure. If the amount of the photo radical generator is too large, it may be difficult to uniformly apply the photosensitive composition or a residue may be generated after development.

(Other ingredients)
The photosensitive composition according to the present invention may contain a solvent. As the solvent, an appropriate solvent capable of dissolving the components blended in the photosensitive composition can be used.

  The solvent is not particularly limited. Examples of the solvent include aromatic hydrocarbon compounds, saturated or unsaturated hydrocarbon compounds, ethers, ketones, and esters.

  Examples of the aromatic hydrocarbon compound include benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene.

  Examples of the saturated or unsaturated hydrocarbon compound include cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, and n-decane. , Isodecane, tetrahydrofuran, tetrahydronaphthalene, squalane and the like.

  Examples of the ethers include diethyl ether, di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether. , Dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, Lopylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethylcyclohexane, methylcyclohexane, p-menthane, o-menthane, m-menthane, dipropyl ether or dibutyl ether Etc.

  Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

  Examples of the esters include ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl acetate cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. It is done.

  For example, when the photosensitive composition is applied onto a substrate to form a photosensitive composition layer, the amount of the solvent is appropriately set so that the solvent is uniformly applied. The solvent is preferably contained so that the solid content concentration is in the range of 0.5 to 70% by weight, and more preferably contained so that the solid content concentration is in the range of 2 to 50% by weight. preferable.

  If necessary, other additives may be further added to the photosensitive composition according to the present invention. Examples of the additives include fillers such as fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, Examples thereof include a plastic accelerator and a sagging inhibitor.

(Pattern film manufacturing method)
Hereinafter, a pattern film manufacturing method according to an embodiment of the present invention will be described with reference to FIGS.

  As shown in FIG. 1 (a), first, the photosensitive composition of the present invention is coated on a substrate 2, and a photosensitive composition layer 1 having a predetermined thickness made of the photosensitive composition is formed on the substrate 2. To do.

  As a coating method, a general coating method can be used. For example, the photosensitive composition is applied by dip coating, roll coating, bar coating, brush coating, spray coating, spin coating, extrusion coating, gravure coating, or the like. The thickness of the photosensitive composition layer 1 is about 10 nm to 10 μm.

  When the photosensitive composition layer 1 contains a solvent, it is desirable to heat-treat the photosensitive composition layer 1 before exposure in order to remove the solvent. The pre-exposure heat treatment temperature is generally in the range of 40 to 200 ° C. The pre-exposure heat treatment temperature is appropriately selected according to the boiling point and vapor pressure of the solvent.

  Next, as shown in FIG. 1B, the photosensitive composition layer 1 has an exposed portion 1a irradiated with light and an unexposed portion 1b not irradiated with light. 1 is partially exposed.

  In order to partially expose the photosensitive composition layer 1, for example, a mask 3 having an opening 3 a and a mask portion 3 b may be used. As the mask 3, a commercially available general mask is used.

  In the photosensitive composition layer 1 of the exposed portion 1a irradiated with light, radicals are generated from the photoradical generator. In the photosensitive composition layer 1 of the unexposed portion 1b not irradiated with light, radicals are not generated from the photoradical generator.

  Since the photosensitive composition contains the compound having the olefin double bond, in the photosensitive composition layer 1 of the exposed portion 1a, the crosslinking of the siloxane polymer is caused by the action of radicals generated from the photoradical generator. Proceed effectively. When the siloxane polymer is crosslinked, the photosensitive composition layer 1 in the exposed portion 1a is cured. As a result, the photosensitive composition layer 1 in the exposed area 1a becomes insoluble in the developer. The photosensitive composition layer 1 in the unexposed area 1b is not exposed to light. Therefore, the photosensitive composition layer 1 in the unexposed portion 1b is not cured and is soluble in the developer.

The light source for irradiating active energy rays such as ultraviolet rays or visible rays during exposure is not particularly limited. As the light source, an ultrahigh pressure mercury lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser, or the like can be used. These light sources are appropriately selected according to the photosensitive wavelength of the constituent components of the photosensitive composition. The irradiation energy of light is appropriately selected depending on the desired film thickness and the constituent components of the photosensitive composition. The irradiation energy of light is generally in the range of 10 to 3000 mJ / cm ² . When the irradiation energy of light is less than 10 mJ / cm ² , the photosensitive composition layer 1 of the exposed portion 1a may not be sufficiently cured. When the irradiation energy of light exceeds 3000 mJ / cm ² , the exposure time may be too long, and the production efficiency of the pattern film may be reduced.

  Next, the photosensitive composition layer 1 is developed with a developer. By development, the photosensitive composition layer 1 in the unexposed area 1b is dissolved in the developer and removed. As a result, as shown in FIG.1 (c), the pattern film 1A of the pattern shape which consists of a hardened | cured material film of a photosensitive composition is obtained. This pattern is referred to as a negative pattern because the photosensitive composition layer 1 in the unexposed area 1b is removed.

  The development operation includes various operations for treating the photosensitive composition layer 1 with a developer such as an alkaline aqueous solution. As the development operation, an operation of immersing the photosensitive composition layer 1 in a developer, an operation of washing the surface of the photosensitive composition layer 1 with the developer, or a jet of the developer onto the surface of the photosensitive composition layer 1. Operation etc. are mentioned.

  The developer is a solution that dissolves the photosensitive composition layer 1 in the unexposed portion 1b after the photosensitive composition layer 1 is partially exposed. Since the photosensitive composition layer 1 of the exposed portion 1a is cured, it does not dissolve in the developer. The developer is not limited to an alkaline aqueous solution. A solvent may be used as the developer. Examples of the solvent include the solvents described above.

  An alkaline aqueous solution is preferably used as the developer. Since the photosensitive composition which concerns on this invention contains the siloxane polymer which has a carboxyl group, the developability with respect to alkaline aqueous solution of a photosensitive composition can be improved by presence of this carboxyl group. A photosensitive composition containing a siloxane polymer having a carboxyl group has high solubility in a developer, particularly an alkaline solution. For this reason, the photosensitive composition layer 1 in the unexposed portion 1b can be easily removed by development. Therefore, it is difficult for residues to occur after development. In development, a relatively low concentration alkaline solution can be used as a developer. Therefore, it is possible to prevent the working environment from deteriorating and reduce the environmental load due to the waste liquid. Furthermore, when an alkaline aqueous solution is used, explosion-proof equipment is unnecessary, and equipment burden due to corrosion or the like can be reduced.

  Examples of the alkaline aqueous solution include tetramethylammonium hydroxide aqueous solution, sodium silicate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, and sodium carbonate aqueous solution. The development time is appropriately set depending on the thickness of the photosensitive composition layer 1 and the type of solvent. The development time is preferably in the range of 1 second to 10 minutes because the development can be efficiently performed and the production efficiency can be increased. After the development, the pattern film 1A is preferably washed with distilled water to remove the developer such as an alkaline aqueous solution remaining on the pattern film 1A.

  When a photosensitive composition containing a siloxane polymer having at least one of a cyclic ether group and a thiol group is used, the adhesion of the pattern film 1A to the substrate 2 can be enhanced.

  After development, the pattern film 1A made of a cured product of the photosensitive composition remaining on the substrate 2 may be heated. When the pattern film 1A is heated, the pattern film 1A is further baked. For this reason, a more dense and hard pattern film can be obtained.

  The heating temperature is about 100 to 500 ° C. The heating time is about 30 minutes to 2 hours.

  In the formation of the pattern film 1A, since the crosslinking of the siloxane polymer effectively proceeds due to radicals generated from the photoradical generator by exposure, a photoacid generator and a photobase generator are used to crosslink the siloxane polymer. It may not be used. When a photoacid generator and a photobase generator are not used, no acid and base remain in the formed pattern film. Therefore, in the obtained pattern film 1A, since an acid and a base do not remain, metal migration can be suppressed when, for example, a metal is in contact with the pattern film 1A. Since the photosensitive composition which concerns on this invention can suppress metal migration, it is preferable that neither a photo-acid generator nor a photobase generator is included.

(Application of pattern film)
The pattern film formed with the photosensitive composition according to the present invention is suitably used for forming pattern films for various apparatuses. For example, a protective film such as an insulating protective film of an electronic device, an alignment film of a display element such as a liquid crystal display element, a protective film, a protective film of an EL element, or a gap spacer of a field emission display is formed by the photosensitive composition of the present invention. It is formed.

  Examples of the protective film include a black matrix, a spacer, a passivation film, and an overcoat film.

  Also, diffusion plate, prism lens sheet, light guide plate, phase difference plate, lenticular sheet, microlens array, refractive index gradient sheet, birefringent film, elliptical lens, waveguide, optical switch, non-reflective film, hologram, optical disk HVD , Photosensitive coverlays, resin core bumps, chip stacking gap retention agents, CCD dam materials, coil materials for internal organ boards, LSI testing prober cores, three-dimensional wiring materials, biofilms, letterpress original plates, intaglio original plates, resins The photosensitive composition of the present invention can be used for a mold or a polishing tape.

  Next, the present invention will be further clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

  In preparing the photosensitive composition, the following materials were prepared.

  In order to synthesize siloxane polymers A to M, methyltrimethoxysilane, 3- (trimethoxysilyl) propyl succinic anhydride trimethoxysilane (Shin-Etsu Chemical Co., X12-967), 3-acryloxypropyl as alkoxysilanes At least one of trimethoxysilane and 3-methacryloxypropyltrimethoxysilane was used.

(Siloxane polymer A)
To a 100 ml flask equipped with a condenser, 40.8 g of methyltrimethoxysilane, 0.3 g of oxalic acid, 15 ml of water and 20 ml of propylene glycol monomethyl ether acetate were added to obtain a solution.

  Using a semicircular mechanical stirrer, the resulting solution was reacted at 80 ° C. for 3 hours with a mantle heater while stirring. Next, using an evaporator, ethanol produced by a condensation reaction with water and residual water were removed at 500 Pa at 40 ° C. over 1 hour. Then, the flask was left to reach room temperature to obtain a solution containing the siloxane polymer A. The solid content concentration of the resulting solution containing the siloxane polymer A was 50% by weight.

  The obtained siloxane polymer A had a polystyrene-reduced weight average molecular weight Mw of 5,500 as measured using gel permeation chromatography.

(Siloxane polymers B to M)
A solution containing siloxane polymers B to M was obtained in the same manner as siloxane polymer A, except that the type and blending amount of alkoxysilane were changed as shown in Tables 1 and 2 below. The solid content concentration of the solution containing the obtained siloxane polymers B to M was 50% by weight.

  Further, the weight average molecular weight Mw of the obtained siloxane polymers B to M, the ratio of the organic group having a carboxyl group in 100% of the organic groups in which carbon atoms are directly bonded to the silicon atoms of the siloxane polymers B to M, and Tables 1 and 2 below show the proportions of organic groups having olefinic double bonds in 100% of organic groups in which carbon atoms are directly bonded to silicon atoms of siloxane polymers B to M.

(Photoinitiator)
Type A: Irgacure 907 (manufactured by Ciba Specialty Chemicals, photo radical generator)
Type B: Irgacure 819 (manufactured by Ciba Specialty Chemicals, photo radical generator)
Type C: PAI-101 (manufactured by Midori Chemical Co., photoacid generator)

(Examples 1-20 and Comparative Examples 1-3)
Each component was mixed in the proportions shown in Tables 3 to 5 below, and then dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a photosensitive composition.

(Evaluation)
(1) Developability A glass substrate having aluminum deposited on the surface layer was prepared. Each photosensitive composition was spin-coated at a rotation number of 1500 rpm on a glass substrate. After coating, it was dried in a 120 ° C. hot air oven for 5 minutes to form a coating film.

Next, through a photomask having a predetermined pattern, the coating film is partially irradiated with an ultraviolet irradiation device (Spot Cure SP-5, manufactured by Ushio Electric Co., Ltd.) so that the coating film has an exposed portion and an unexposed portion. ) Was irradiated for 5 seconds at an ultraviolet intensity of 100 mW / cm ² so that the irradiation energy was 500 mJ / cm ² . The photosensitive compositions of Comparative Example 2 and Comparative Example 3 were baked at 100 ° C. for 2 minutes after irradiation with ultraviolet rays.

  Thereafter, the coating film was immersed in a 1% by weight aqueous solution of sodium carbonate and developed to remove the photosensitive composition layer in the unexposed area. After removing the photosensitive composition layer in the unexposed area, it was washed with distilled water, and the remaining alkaline aqueous solution was removed to obtain a pattern film made of a cured product of the photosensitive composition in the exposed area on the substrate. .

  When the pattern film was obtained, whether or not a pattern was formed after development was evaluated by the following evaluation criteria by observing with an electron microscope.

[Development evaluation criteria]
○: A pattern of L / S 20 μm was formed. Δ: Although a pattern of L / S 20 μm was formed, there was a variation of 10% or more in the length direction dimension of the pattern. ×: L / S 20 μm The pattern was not formed

(2) Corrosiveness An evaluation sample was obtained by leaving the pattern film obtained by the evaluation of the above (1) developability for 1000 hours at 85 ° C. and a relative humidity of 85%. In the obtained evaluation samples, whether or not metal corrosion occurred was observed with a microscope and evaluated according to the following evaluation criteria.

[Corrosion Evaluation Criteria]
○: No change in the aluminum pattern ×: Change in the aluminum pattern The results are shown in Tables 3 to 5 below.

(A)-(c) is front sectional drawing which shows typically each process for demonstrating the method to manufacture the pattern film which concerns on one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive composition layer 1a ... Exposed part 1b ... Unexposed part 1A ... Pattern film 2 ... Substrate 3 ... Mask 3a ... Opening part 3b ... Mask part

Claims (6)

  A photosensitive composition comprising a siloxane polymer having a carboxyl group, a compound having an olefin double bond, and a photoradical generator.   The photosensitive composition according to claim 1, wherein the siloxane polymer having a carboxyl group has an organic group in which a carbon atom is directly bonded to a silicon atom, and 1 to 25% of the organic group has a carboxyl group. .   The photosensitive composition of Claim 1 or 2 whose compound which has the said olefin double bond is a siloxane polymer which has an olefin double bond.   The siloxane polymer having an olefin double bond has an organic group in which a carbon atom is directly bonded to a silicon atom, and 5 to 100% of the organic group has an olefin double bond. Photosensitive composition.   The siloxane polymer having a carboxyl group and the siloxane polymer having an olefin double bond are the same siloxane polymer, and the siloxane polymer having a carboxyl group and an olefin double bond is included. Photosensitive composition. Applying the photosensitive composition according to any one of claims 1 to 5 on a substrate, and forming a photosensitive composition layer on the substrate;
By partially exposing the photosensitive composition layer so that the photosensitive composition layer has an exposed portion irradiated with light and an unexposed portion not irradiated with light, the photosensitive portion of the exposed portion is exposed. Curing the composition layer to make it insoluble in a developer,
Developing the photosensitive composition layer with a developer to remove the photosensitive composition layer in the unexposed areas and forming a pattern film made of a cured product of the photosensitive composition. A method for producing a patterned film, characterized in that:

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