JP2010039056A - Photosensitive composition and method of manufacturing pattern film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition, enhancing flexibility of an obtained pattern film in forming the pattern film made of a hardened material of a photosensitive composition on a substrate by exposure and development, so that durability of the pattern film can be improved. <P>SOLUTION: This photosensitive composition includes: a siloxane polymer, which is obtained by polymerizing at least one kind of silane compound expressed by the formula (1): Si(X)<SB>p</SB>(R)<SB>4-p</SB>, (in the formula (1), X indicates a hydrolytic group, R indicates a 1-30C non-hydrolytic organic group and p indicates integers of 1-4); and a photopolymerization initiator, wherein at least one kind of silane compound expressed by the formula (1) includes a silane compound expressed by the formula (1) in which p in the formula (1) is 2, the weight average molecular weight of the siloxane polymer ranges from 500 to 60,000, and a solid content acid number of the siloxane polymer ranges from 5 to 800 KOHmg/g. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive composition capable of forming a pattern film used for an insulating film of an electronic device such as a semiconductor device. More specifically, the present invention relates to a pattern film made of a cured product of a photosensitive composition by exposure and development. The present invention relates to a photosensitive composition that can be used to form the pattern film and can increase the durability of 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 an insulating 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. In order to form such an insulating film, a patternable photosensitive composition containing an alkoxysilane condensate has been proposed.

  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. As a compound that generates a 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. The photosensitive composition layer in the exposed area is cured and does not dissolve in the developer. Thereafter, the photosensitive composition is developed with an alkaline solution, and the photosensitive composition layer in the unexposed area is removed. By heating the remaining cured product of the photosensitive composition layer after development, a hard and dense thin film with a fine pattern can be obtained.
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 flexibility of the thin film is insufficient, and the durability of the thin film, such as heat resistance or moisture heat resistance, is low. . For this reason, it has been difficult to use a thin film for applications requiring high reliability.

  It is an object of the present invention to have excellent developability when a patterned film made of a cured product of a photosensitive composition is formed on a substrate by exposure and development, and the flexibility of the obtained pattern film can be increased. Accordingly, it is an object of the present invention to provide a photosensitive composition capable of enhancing the durability of a pattern film, and a method for producing a pattern film using the photosensitive composition.

  According to the present invention, it contains a siloxane polymer obtained by polymerizing at least one silane compound represented by the following formula (1), and a photopolymerization initiator, and is represented by the formula (1). The at least one silane compound includes a silane compound represented by the following formula (1) and p in the following formula (1) being 2, and the weight average molecular weight of the siloxane polymer is 500 to 60000. The photosensitive composition is characterized in that the solid content acid value of the siloxane polymer is in the range of 5 to 800 KOHmg / g.

Si (X) _p (R) _4-p (1)
In said formula (1), X represents a hydrolysable group, R represents a C1-C30 non-hydrolyzable organic group, and p represents the integer of 1-4. When p is 2 to 4, a plurality of X may be the same or different. When p is 1 or 2, the plurality of R may be the same or different.

  In a specific aspect of the photosensitive composition according to the present invention, 100 mol% of the silane compound represented by the formula (1) is represented by the formula (1), and p in the formula (1) is 2 is included in the range of 5 to 60 mol%.

  In another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer has at least one of a carboxyl group and a mercapto group.

  In still another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer has an organic group in which a carbon atom is directly bonded to a silicon atom, and 1 to 25% of the organic group is a carboxyl group. Have

  In still another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer has an organic group in which a carbon atom is directly bonded to a silicon atom, and 1 to 50% of the organic group is a mercapto group. Have

  In still another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer has a ratio of the number of SiOH groups to the number of Si—O—Si bonds (number of SiOH groups / Si—O—Si bonds). Number) is a siloxane polymer in the range of 0.02 to 0.2.

  In another specific aspect of the photosensitive composition according to the present invention, the photopolymerization initiator includes a photoradical generator.

  In still another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer has an organic group in which a carbon atom is directly bonded to a silicon atom, and 5 to 99% of the organic group is unsaturated. Has a double bond.

  In another specific aspect of the photosensitive composition according to the present invention, a compound having an unsaturated double bond is further contained within a range of 10 to 50 parts by weight with respect to 100 parts by weight of the siloxane polymer.

  In still another specific aspect of the photosensitive composition according to the present invention, the compound having an unsaturated double bond is a (meth) acrylic compound, and the (meth) acrylic compound has an unsaturated double bond of 1 to 1. 10 and the (meth) acrylic compound has a weight average molecular weight in the range of 100 to 5,000.

  In another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer has at least one of a carboxyl group and a mercapto group, and the photopolymerization initiator includes a photoacid generator.

  In another specific aspect of the photosensitive composition according to the present invention, the siloxane polymer has a carboxyl group and a cyclic ether group, and the ratio of the number of cyclic ether groups of the siloxane polymer to the number of carboxyl groups (cyclic ether) The number of groups / number of carboxyl groups)) is in the range of 0.1-2.

  The method for producing a patterned film according to the present invention includes 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 comprising: The photosensitive composition layer of the exposed portion is cured by partially exposing the photosensitive composition layer to have an exposed portion irradiated with light and an unexposed portion not irradiated with light. And developing the photosensitive composition layer with a developer to remove the photosensitive composition layer in the unexposed area, and from the cured product of the photosensitive composition. And a step of forming a pattern film.

  In the pattern film manufacturing method according to the present invention, it is preferable that a heating process of the pattern film is further provided after the development process.

  In the photosensitive composition concerning this invention, the weight average molecular weight of the siloxane polymer obtained by polymerizing the said specific silane compound exists in the range of 500-60000, and the solid content acid value of a siloxane polymer is 5-5. Since it exists in the range of 800 KOHmg / g, when the pattern film which consists of hardened | cured material of a photosensitive composition by exposure and image development is formed on a board | substrate, the flexibility of a pattern film can be improved. For this reason, durability, such as crack resistance of a pattern film, can be improved.

  In 100 mol% of the silane compound represented by the above formula (1), the silane compound represented by the above formula (1) and having p of 2 in the above formula (1) is contained within a range of 5 to 60 mol%. When it is, the developability of the photosensitive composition can be improved. Furthermore, the flexibility of the obtained pattern film can be further enhanced.

  In the method for producing a patterned film according to the present invention, the photosensitive composition layer composed of the photosensitive composition constituted according to the present invention is partially exposed and developed, so that the flexibility of the patterned film can be increased, Therefore, a highly durable pattern film can be obtained.

  Details of the present invention will be described below.

  The photosensitive composition according to the present invention contains a siloxane polymer and a photopolymerization initiator.

(Siloxane polymer)
The siloxane polymer contained in the photosensitive composition according to the present invention is a siloxane polymer obtained by polymerizing a silane compound represented by the following formula (1).

Si (X) _p (R) _4-p (1)
In said formula (1), X represents a hydrolysable group, R represents a C1-C30 non-hydrolyzable organic group, and p represents the integer of 1-4. When p is 2 to 4, a plurality of X may be the same or different. When p is 1 or 2, the plurality of R may be the same or different.

  The at least one silane compound represented by the above formula (1) includes a silane compound represented by the above formula (1) and p in the above formula (1) being 2.

  X in the above formula (1) is a group that can be hydrolyzed to produce a silanol group when heated to room temperature (25 ° C.) to 100 ° C., usually in the presence of excess water and without catalyst, Or, it is a group that can be further condensed to form a siloxane bond.

  Examples of the hydrolyzable group include an alkoxy group. Specific examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

  The hydrolyzable group may be a hydrolyzable group other than an alkoxy group. Specific examples of the hydrolyzable group other than the alkoxy group include a halogen group such as chlorine or bromine, an acetyl group, a hydroxyl group, or an isocyanate group.

  Examples of the non-hydrolyzable organic group include organic groups having 1 to 30 carbon atoms that are hardly hydrolyzed and are stable hydrophobic groups.

  Examples of the organic group having 1 to 30 carbon atoms include 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, an organic group containing an epoxy group, and 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. Specific examples of the halogenated alkyl group include, for example, 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 or 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 silane compound 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, methoxydi Tilvinylsilane, 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, pro Ru-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, tetradecyltripropoxy Sisilane, 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) ethyltrimeth Sisilane, 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 Triethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, triethoxysilane, trimethoxysilane, triisopropoxysilane, tri-n-propoxysilane, triacetoxysilane, Examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetraacetoxysilane.

  In 100 mol% of the silane compound represented by the above formula (1), the silane compound represented by the above formula (1) and having p of 2 in the above formula (1) is contained within a range of 5 to 60 mol%. It is preferable that When the amount of the silane compound represented by the above formula (1) and p in the above formula (1) is 2 is within the above range, the flexibility of the pattern film can be further enhanced. In addition, in 100 mol% of the silane compound represented by the above formula (1), the silane compound represented by the above formula (1) and p in the above formula (1) is within the range of 5 to 60 mol%. In this case, at least two silane compounds represented by the above formula (1) are used.

  In 100% by weight of the silane compound represented by the above formula (1), the silane compound represented by the above formula (1) and p in the above formula (1) is 2 is within the range of 10 to 50 mol%. It is more preferable that it is contained.

  Specific examples of the silane compound represented by the above formula (1) and p in the above formula (1) are 2, for example, diphenyldiethoxylane, dimethyldimethoxysilane, diethoxydimethylsilane, diethoxymethylvinylsilane , Diethoxydiethylsilane, dimethyldipropoxysilane, dimethoxymethylphenylsilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N-2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc. are mentioned.

  The weight average molecular weight of the siloxane polymer is in the range of 500 to 60000. If the weight average molecular weight is less than 500, the photosensitive composition may be difficult to cure. When the weight average molecular weight exceeds 60000, a gel-like material is likely to be generated in the photosensitive composition, and a residue is likely to be generated after development. The minimum with a preferable weight average molecular weight is 1000, and a preferable upper limit is 20000.

  The solid content acid value of the siloxane polymer is in the range of 5 to 800 KOHmg / g. When the solid content acid value is less than 5 KOH mg / g, the photosensitive composition may not be dissolved in the alkaline developer. If the solid content acid value exceeds 800 KOHmg / g, the photosensitive composition may be completely dissolved in the alkaline developer, and the pattern film may not be obtained. The preferable lower limit of the solid content acid value is 20 KOH mg / g, the preferable upper limit is 750 KOH mg / g, the more preferable upper limit is 700 KOH mg / g, and the further preferable upper limit is 400 KOH mg / g.

  Examples of the functional group capable of imparting an acid value to the siloxane polymer include a carboxyl group, a mercapto group, a silanol group, a phenolic OH group, and an alcoholic OH group.

  The siloxane polymer preferably has at least one of a carboxyl group and a mercapto group.

  A siloxane polymer having a carboxyl group is excellent in solubility in a developing solution such as an alkaline solution. Therefore, when a siloxane polymer having a carboxyl group is used, the developability of the photosensitive composition can be improved.

  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 preferable. When these carboxyl group-containing alkoxysilane condensates are used, the developability of the photosensitive composition can be further enhanced.

  As a method of introducing a carboxyl group into an alkoxysilane condensate obtained by condensing an alkoxysilane having no carboxyl group, a cyclic ether group-containing alkoxysilane condensation obtained by condensing an alkoxysilane having a cyclic ether group Examples thereof include a method of reacting a product with carboxylic anhydride.

  When obtaining the said carboxyl group-containing alkoxysilane condensate, 1 type of alkoxysilane may be used and 2 or more types of alkoxysilane may be used.

  The siloxane polymer 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 siloxane polymer preferably has an organic group in which a carbon atom is directly bonded to a silicon atom, and 1 to 50% of the organic group preferably has a mercapto group. When the proportion of the organic group having the mercapto group in 100% of the organic group in which the carbon atom is directly bonded to the silicon atom is less than 1%, the adhesion of the pattern film to the substrate cannot be sufficiently improved. If it exceeds 50%, the solubility of the siloxane polymer is increased by the mercapto group, and therefore a pattern in photolithography may not be formed.

  When a siloxane polymer having a mercapto group is used, 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 a metal oxide such as ITO, the adhesion of the pattern film to the substrate can be greatly enhanced. Only one type of siloxane polymer may be used, or two or more types may be used in combination.

  The above-mentioned siloxane polymer having a mercapto group is an alkoxysilane condensate obtained by condensing an alkoxysilane having a mercapto group, or an alkoxysilane condensation having an mercapto group introduced after condensing an alkoxysilane having no mercapto group. It is preferable that it is a thing.

  The method for introducing a mercapto group into an alkoxysilane condensate obtained by condensing alkoxysilane is not particularly limited. Examples of this method include a method using a hydrosilylation reaction. When the above alkoxysilane condensate is used, the adhesion of the pattern film to the substrate can be enhanced.

  When obtaining the alkoxysilane condensate having the mercapto group, it is preferable to use at least two types of alkoxysilanes.

  In the siloxane polymer, the ratio of the number of SiOH groups to the number of Si—O—Si bonds (number of SiOH groups / number of Si—O—Si bonds) is in the range of 0.02 to 0.2. preferable. When the ratio is less than 0.02, the siloxane polymer may not be sufficiently crosslinked by exposure, or the developability of the photosensitive composition may not be sufficiently improved. When the ratio exceeds 0.2, the photosensitive composition may not be sufficiently cured by exposure, and the exposed photosensitive composition may be dissolved in the developer.

  When the photopolymerization initiator includes a photoradical generator, the siloxane polymer preferably has an unsaturated double bond.

  In the siloxane polymer having an unsaturated double bond, an unsaturated double bond is introduced after an alkoxysilane condensate obtained by condensing an alkoxysilane having an unsaturated double bond or an alkoxysilane is condensed. An alkoxysilane condensate is preferred. When the alkoxysilane condensate is used as the siloxane polymer having an unsaturated double bond, developability can be further improved.

  Examples of a method for introducing an unsaturated double bond after the alkoxysilane is condensed include a method using a hydrosilylation reaction.

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

  It is preferable that the siloxane polymer has an organic group in which a carbon atom is directly bonded to a silicon atom, and 5 to 99% of the organic group has an unsaturated double bond. When the ratio of the organic group having an unsaturated double bond in 100% of the organic group in which the carbon atom is directly bonded to the silicon atom is less than 5%, the siloxane polymer may not be sufficiently crosslinked by exposure.

  The siloxane polymer preferably has a carboxyl group and a cyclic ether group. When a siloxane polymer having a carboxyl group and a cyclic ether group is used, the carboxyl group and the cyclic ether group can be reacted by heating the pattern film formed by exposure and development. Therefore, the amount of carboxyl groups in the pattern film can be reduced. Since the amount of carboxyl groups can be reduced, the electrical insulation of the pattern film can be enhanced.

  The siloxane polymer having a cyclic ether group is obtained by condensing an alkoxysilane condensate obtained by condensing an alkoxysilane having a cyclic ether group or an alkoxysilane not having a cyclic ether group, and An alkoxysilane condensate into which an ether group has been introduced is preferred.

  Examples of a method for introducing a cyclic ether group into an alkoxysilane condensate obtained by condensing an alkoxysilane include a method using a hydrosilylation reaction.

  The siloxane polymer having a carboxyl group and a cyclic ether group is obtained by condensing an alkoxysilane condensate obtained by condensing an alkoxysilane having a carboxyl group and a cyclic ether group, and an alkoxysilane having a cyclic ether group. After condensing an alkoxysilane condensate having a carboxyl group, an alkoxysilane having a carboxyl group, an alkoxysilane condensate having a cyclic ether group introduced, or after condensing an alkoxysilane, a carboxyl group and a cyclic ether group are introduced. It is preferable that it is the alkoxysilane condensate made.

  When the alkoxysilane condensate is used as the siloxane polymer having a carboxyl group and a cyclic ether group, the adhesion of the pattern film to the substrate can be further enhanced. When obtaining the said alkoxysilane condensate which has a carboxyl group and a cyclic ether group, 1 type of alkoxysilanes may be used and 2 or more types of alkoxysilanes may be used.

  Examples of the alkoxysilane having a cyclic ether group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycol. Sidoxypropyltriethoxysilane etc. are mentioned.

  When a siloxane polymer having a cyclic ether group is used, the adhesion of the pattern film to the substrate can be enhanced. In particular, when the substrate on which the pattern film is formed is made of metal or a metal oxide such as ITO, the adhesion of the pattern film to the substrate can be greatly enhanced. Only one type of siloxane polymer may be used, or two or more types may be used in combination.

  The ratio of the number of cyclic ether groups in the siloxane polymer to the number of carboxyl groups (number of cyclic ether groups / number of carboxyl groups) is preferably in the range of 0.1-2. When the ratio (number of cyclic ether groups / number of carboxyl groups) exceeds 2, the developability of the photosensitive composition may be low, and when it is less than 0.1, the number of cyclic ether groups is too small. The electrical insulation of the pattern film may not be sufficiently improved. The cyclic ether group is preferably an epoxy group.

(Compound having an unsaturated double bond)
When the photopolymerization initiator includes a photoradical generator, the photosensitive composition according to the present invention preferably contains a compound having an unsaturated double bond other than the siloxane polymer.

  The compound having an unsaturated double bond is not particularly limited as long as it has an unsaturated double bond. The compound having an unsaturated double bond is preferably a (meth) acrylic compound.

  The compound having an unsaturated double bond preferably has 1 to 10 unsaturated double bonds. When the number of unsaturated double bonds exceeds 10, the flexibility of the cured product may be lowered and durability may be lowered.

  The weight average molecular weight of the compound having an unsaturated double bond is preferably in the range of 100 to 5,000. If the weight average molecular weight is less than 100, the photosensitive composition may not be sufficiently cured, and the photosensitive composition may be completely dissolved during development and a pattern cannot be formed. The photosensitive composition is sufficiently cured by exposure. There are things that do not. When the said weight average molecular weight exceeds 5000, the developability of a photosensitive composition will become low and it will become easy to produce a residue after image development.

(Photopolymerization initiator)
The photopolymerization initiator contained in the photosensitive composition according to the present invention is not particularly limited as long as the siloxane polymer is cross-linked by stimulation with light or heat.

  The photopolymerization initiator is preferably contained within a range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the siloxane polymer. If the amount of the photopolymerization initiator is too small, the photosensitive composition may not be sufficiently cured by exposure. If the amount of the photopolymerization initiator is too large, it may be difficult to uniformly apply the photosensitive composition, or a residue may be generated after development.

  The photopolymerization initiator is preferably at least one of a photoacid generator and a photoradical generator. When either one of a photo acid generator and a photo radical generator is used, the photosensitive composition according to the present invention is a negative photosensitive composition.

  When the photoacid generator is used, the siloxane polymer can be cross-linked with the acid generated from the photoacid generator by exposure to cure the photosensitive composition.

  The photoacid generator is not particularly limited as long as it generates an acid when irradiated with light. Examples of the photoacid generator include onium salts.

Specific examples of the photoacid generator include trade names “TPS-105” (CAS No. 66003-78-9) and “TPS-109” (CAS No. 144317-44-2) manufactured by Midori Chemical Co., Ltd. "MDS-105" (CAS No. 116808-67-4), "MDS-205" (CAS No. 81416-37-7), "DTS-105" (CAS No. 111281-12-0), "NDS -105 "(CAS No. 195057-83-1)," NDS-165 "(CAS No. 316821-98-4) and other sulfonium salt compounds," DPI-105 "(CAS No. 66003-76-7) , “DPI-106” (CAS No. 214534-44-8), “DPI-109” (CAS No. 194999-82-1), “DPI -201 "(CAS No. 6293-66-9)," BI-105 "(CAS No. 154557-16-1)," MPI-105 "(CAS No. 115298-63-0)," MPI-106 " (CAS No. 260061-46-9), "MPI-109" (CAS No. 260061-47-0), "BBI-105" (CAS No. 84563-54-2), "BBI-106" ( CAS No. 185195-30-6), “BBI-109” (CAS No. 194999-85-4), “BBI-110” (CAS No. 213740-80-8), “BBI-201” (CAS No. , 142342-33-4), trade name “NAI-106” (Naphthalimide camphorsulfo, manufactured by Midori Chemical Co., Ltd.) Acid salt, CAS No. 83697-56-7), “NAI-100” (CAS No. 83697-53-4), “NAI-1002” (CAS No. 76656-48-9), “NAI-1004” (CAS No. 83697-60-3), “NAI-101” (CAS No. 5551-72-4), “NAI-105” (CAS No. 85342-62-7), “NAI-109” (CAS No. 171417-91-7), "NI-101" (CAS No. 131526-99-3), "NI-105" (CAS No. 85342-63-8), "NDI-101" (CAS No. 141714-82-1), "NDI-105" (CAS No. 133710-62-0), "NDI-106" (CAS No. 210218-57-8), "NDI-109" (CAS No. 307531-76-6), "PAI-01" (CAS No. 17512-88-8), "PAI-101" (CAS No. 82424) 53-1), “PAI-106” (CAS No. 202419-88-3), “PAI-1001” (CAS No. 193222-02-5), “SI-101” (CAS No. 55048-39-). 0), "SI-105" (CAS No. 34684-40-7), "SI-106" (CAS No. 179419-32-0), "SI-109" (CAS No. 25937-66-9) , “PI-105” (CAS No. 41580-58-9), “PI-106” (CAS No. 83697-51-2), Ciba Specialty Trade names “CGI 1397”, “CGI 1325”, “CGI 1380”, “CGI 1311”, “CGI 263”, “CGI 268” and the like manufactured by Micals, Inc., trade names “DTS200” (CAS No. .203573-06-2), Rhodia Japan Co., Ltd. under the trade name "RHODORSIL PHOTOINITIATOR-2074" (CAS No.178233-72-2) compound and ^{BF 4-counterions} such like. A photo-acid generator may be used independently and 2 or more types may be used together.

  The photoacid generator is preferably at least one selected from the group consisting of an onium salt, a diazonium salt, and a sulfonic acid ester because of its high reactivity.

  When the photosensitive composition according to the present invention contains a photoacid generator, the photoacid generator is preferably contained within a range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the siloxane polymer. More preferably, it is contained within the range of 0.3 to 5 parts by weight. If the amount of the photoacid generator is too small, a sufficient amount of acid may not be generated by exposure. If the amount of the photoacid generator is too large, it may be difficult to uniformly apply the photosensitive composition, or a residue may be generated after development.

  When the photo radical generator is used, the photosensitive composition can be cured by crosslinking the siloxane polymer with radicals generated from the photo radical generator by exposure.

  When the photo radical generator is contained, it is preferable that a siloxane polymer having an unsaturated double bond is contained or a compound having an unsaturated double bond is further contained. In this case, the photosensitive composition may be cured by crosslinking the siloxane polymer having an unsaturated double bond or the compound having an unsaturated double bond with radicals generated from a photoradical generator upon exposure. it can.

  When the said photoradical generator is contained, it is preferable that the photosensitive composition does not contain any of a photoacid generator and a photobase generator. In this case, no acid or base remains in the formed pattern film. For this reason, when a metal is in contact with the pattern film, metal migration can be suppressed.

  Specific examples of the photo radical generator include halomethylated triazine derivatives, halomethylated oxadiazole derivatives, imidazole derivatives, benzoin, benzoin alkyl ethers, anthraquinone derivatives, benzanthrone derivatives, benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzoic acid. Examples include acid ester derivatives, acridine derivatives, phenazine derivatives, titanocene derivatives, α-aminoalkylphenone compounds, and oxime derivatives. 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.

  When the photosensitive composition according to the present invention contains a photo radical generator, the photo radical generator is preferably contained within a range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the siloxane polymer. More preferably, it is contained within the range of 1 to 15 parts by weight. 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 further contain a sensitizer.

  The sensitizer is not particularly limited. Specific examples of the sensitizer include benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine. Benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylant Quinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7 -Dimethoxycarbonylcoumarin) or coronene.

  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.

  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. Such additives include fillers such as fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers. Agents, plasticizers or sagging inhibitors.

(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, or gravure coating. 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. A commercially available general mask is used as the mask 3.

  In the photosensitive composition layer 1 of the exposed portion 1a irradiated with light, stimulation of acid or the like is generated from a photopolymerization initiator such as a photoacid generator. In the photosensitive composition layer 1 of the unexposed portion 1b that is not irradiated with light, no stimulus is generated from the photopolymerization initiator.

  In the photosensitive composition layer 1 of the exposed portion 1a, the siloxane polymer is cross-linked by the stimulating action generated from the photopolymerization initiator. 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. When developed with a developer, the photosensitive composition layer 1 in the unexposed area 1b is removed by dissolving in the developer. 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.

  In addition, a developing solution is a liquid which melt | dissolves the photosensitive composition layer 1 of the unexposed part 1b, after exposing the photosensitive composition layer 1 partially. 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. When the siloxane polymer which has a carboxyl group is contained, the developability with respect to the alkaline aqueous solution of a photosensitive composition can be improved by presence of this carboxyl group. Since the photosensitive composition containing the siloxane polymer having a carboxyl group has high solubility in a developer, particularly an alkaline solution, the photosensitive composition layer 1 in the unexposed area 1b can be easily removed by development. Therefore, a residue hardly occurs after development. In developing, a relatively low concentration alkaline solution can be used as a developing solution. 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 the photosensitive composition containing the siloxane polymer which has a mercapto group is used, the adhesiveness with respect to the board | substrate 2 of 1 A of pattern films can be improved.

  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. When a photosensitive composition containing a siloxane polymer having a carboxyl group and a siloxane polymer having a cyclic ether group such as an epoxy group is used, by heating the pattern film 1A, the carboxyl group and the cyclic ether group are changed. Can be reacted. For this reason, the amount of carboxyl groups in the patterned film 1A after heating can be reduced. For this reason, the electrical insulation of a pattern film can be improved.

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

(Application of pattern film)
In addition, the pattern film formed with the photosensitive composition concerning this invention is used suitably for forming the pattern film of 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 Z, AA to AZ, BA to BZ, CA to CZ and DA to DP, as the alkoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, 3- (trimethoxysilyl) propyl anhydride succinate Acid trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., X12-967), 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, At least one of 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane It was used.

(Siloxane polymer A)
In a 100 ml flask equipped with a condenser tube, 32.2 g of methyltrimethoxysilane, 6.9 g of trimethoxysilane 3- (trimethoxysilyl) propyl succinate (Shin-Etsu Chemical Co., X12-967), and 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, ethanol and residual water generated by the condensation reaction with water were removed using an evaporator under the conditions of 2000 Pa pressure, 40 ° C. and 1 hour (synthesis conditions). 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. Further, the solid content acid value (KOH mg / g) of the siloxane polymer A was 351.

The ratio of the number of SiOH groups in the siloxane polymer A to the number of Si—O—Si bonds (number of SiOH groups / number of Si—O—Si bonds) is 5.0 to 6.5 ppm of ¹ H-NMR. It was 0.10 as calculated from the ratio of the integrated value of the broad peak and the integrated value of the methyl group. 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 of the siloxane polymer A was 10%. The ratio of the number of cyclic ether groups in the siloxane polymer A to the number of carboxyl groups (number of cyclic ether groups / number of carboxyl groups) was 0.

(Siloxane polymers B to Z, AA to AZ, BA to BZ, CA to CZ and DA to DP)
The siloxane polymers B to Z, AA to AZ, BA to BZ are the same as the siloxane polymer A except that the types and blending amounts of the alkoxysilanes and the synthesis conditions are changed as shown in Tables 1 to 13 below. A solution containing CA to CZ and DA to DP was obtained. The solid content concentration of the solution containing the obtained siloxane polymers B to Z, AA to AZ, BA to BZ, CA to CZ and DA to DP was 50% by weight.

  Further, the weight average molecular weight Mw of the obtained siloxane polymers B to Z, AA to AZ, BA to BZ, CA to CZ and DA to DP and the solid content acid value (KOHmg / g) are shown in the following Tables 1 to 1. It was shown in FIG.

  In addition, the obtained siloxane polymers B to Z, AA to AZ, BA to BZ, CA to CZ, and organic having a carboxyl group in 100% of organic groups in which carbon atoms are directly bonded to silicon atoms of DA to DP The ratio of the group, the ratio of the organic group having a mercapto group, and the ratio of the organic group having an olefin double bond are shown in Tables 1 to 13 below.

  Further, the ratio of the number of cyclic ether groups to the number of carboxyl groups in the obtained siloxane polymers B to Z, AA to AZ, BA to BZ, CA to CZ and DA to DP (number of cyclic ether groups / number of carboxyl groups) And the ratio of the number of SiOH groups to the number of Si—O—Si bonds (number of SiOH groups / number of Si—O—Si bonds) is shown in Tables 1 to 13 below.

((Meth) acrylic compound)
Methyl methacrylate (monofunctional, Mw = 88)
EBECRYL 885 (Trifunctional, Mw = 6000, manufactured by Daicel Cytec)
UN-3320HS (15 functional, Mw = 5000, manufactured by Negami Industrial Co., Ltd.)
BP-4EA (bifunctional, Mw = 560, manufactured by Kyoeisha Chemical Co., Ltd.)
EBECRYL 8402 (bifunctional, Mw = 1000, manufactured by Daicel Cytec)
PETIA (Trifunctional, Mw = 250, manufactured by Daicel Cytec)

(Photopolymerization initiator)
Irgacure 907 (Ciba Specialty Chemicals, photo radical generator, IC907)
Irgacure 819 (Ciba Specialty Chemicals, photo radical generator, IC819)
PAI-101 (manufactured by Midori Chemical Co., photoacid generator)
PAG121 (manufactured by Ciba Specialty Chemicals, photoacid generator)

(Examples 1 to 203 and Comparative Examples 1 to 9)
After mixing each component in the ratio shown to the following Tables 14-35, it was made to melt | dissolve in 500 weight part of tetrahydrofuran which is a solvent, and the photosensitive composition was prepared.

(Evaluation)
(1) Developability A glass substrate having ITO patterned on the surface layer was prepared. Each photosensitive composition was spin-coated at a rotation speed of 1000 rpm on a glass substrate. After coating, it was dried in a hot air oven at 100 ° C. 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 illuminance of 20 mW / cm ² so that the irradiation energy was 100 mJ / cm ² . Thereafter, baking was performed at 80 ° C. for 2 minutes.

  Thereafter, the coating film was immersed in a 2.38 wt% aqueous solution of TMAH (tetramethylammonium hydroxide) (developer type A) or 1 wt% sodium carbonate (developer type B), and developed to expose the unexposed areas. The composition layer was removed. 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]
○: L / S 20 μm pattern was formed Δ: L / S 20 μm pattern was formed, but 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) Adhesion The adhesion of the pattern film to the substrate was evaluated. In accordance with JIS K5400, the pattern film was cut into a size of 1 mm × 1 mm when viewed in plan using a cutter, and the pattern film was divided into 100 pieces. Adhesiveness was evaluated according to the following evaluation criteria by affixing the tape to the divided pattern film and then peeling the tape.

[Evaluation criteria for adhesion]
◯: 90 to 100 pattern films that did not peel out of 100 divided pattern films Δ: 50 to 89 pattern films that did not peel out of 100 divided pattern films ×: Divided 0 to 49 pattern films that were not peeled out of 100 pattern films

(3) Crack resistance The pattern film obtained by the evaluation of developability in (1) above was allowed to stand for 24 hours under the conditions of 120 ° C., relative humidity of 100% and 2 atm. Whether or not cracks occurred in the patterned film after standing was observed with a microscope, and the crack resistance was evaluated according to the following evaluation criteria.

[Evaluation criteria for crack resistance]
○: No cracks were generated. Δ: Cracks were generated in 1 to 3 places within an area of 5 mm × 5 mm. ×: Cracks were generated on the entire surface.

(4) Corrosiveness Using a glass substrate with aluminum deposited on the surface layer, the pattern film produced under the same conditions as in the above (1) evaluation of developability was left for 1000 hours at 85 ° C. and 85% relative humidity. Thus, an evaluation sample was obtained. 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 aluminum pattern △: Change in aluminum pattern

(5) Electrical insulation A glass substrate having aluminum deposited on the surface layer was prepared. Each photosensitive composition was spin-coated on a glass substrate at 1250 rpm for 20 seconds. After coating, it was dried for 2 minutes with a hot plate at 100 ° C. to form a coating film.

Next, using an ultraviolet irradiation device, the coating film was irradiated with ultraviolet rays having a wavelength of 365 nm at an ultraviolet illuminance of 100 mW / cm ² for 0.5 seconds so that the irradiation energy was 500 mJ / cm ² . After irradiating with ultraviolet rays, it was heated on a hot plate at 100 ° C. for 2 minutes. Then, it further heated for 60 minutes with a 200 degreeC hotplate. Next, aluminum was vapor-deposited again on the coating film.

  In the cured photosensitive composition layer, a voltage of 1 MV / cm was applied between the deposited aluminum and the leakage current was measured. Moreover, the electrical insulation was evaluated according to the following evaluation criteria from the measured value of the leakage current.

[Evaluation criteria for electrical insulation]
○: Leakage current is 1 × 10 ⁻⁶ A / cm ² or less Δ: Leakage current exceeds 1 × 10 ⁻⁶ A / cm ^{2 The} results are shown in Tables 14 to 35 below.

1A to 1C are front cross-sectional views schematically showing each step for explaining a method for producing a patterned film according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive composition layer 1a ... Exposure part 1b ... Unexposed part 1A ... Pattern film which consists of hardened | cured material of photosensitive composition 2 ... Board | substrate 3 ... Mask 3a ... Opening part 3b ... Mask part

Claims (14)

A siloxane polymer obtained by polymerizing at least one silane compound represented by the following formula (1), and a photopolymerization initiator,
The at least one silane compound represented by the formula (1) includes a silane compound represented by the following formula (1) and p in the following formula (1) being 2,
The siloxane polymer has a weight average molecular weight in the range of 500 to 60,000;
The photosensitive composition wherein the solid content acid value of the siloxane polymer is in the range of 5 to 800 KOHmg / g.
Si (X) _p (R) _4-p (1)
In said formula (1), X represents a hydrolysable group, R represents a C1-C30 non-hydrolyzable organic group, and p represents the integer of 1-4. When p is 2 to 4, a plurality of X may be the same or different. When p is 1 or 2, the plurality of R may be the same or different.   In 100 mol% of the silane compound represented by the formula (1), the silane compound represented by the formula (1) and having p of 2 in the formula (1) is included within a range of 5 to 60 mol%. The photosensitive composition according to claim 1.   The photosensitive composition of Claim 1 or 2 in which the said siloxane polymer has at least one of a carboxyl group and a mercapto group.   The photosensitive composition according to claim 3, wherein the siloxane polymer 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 according to claim 3 or 4, wherein the siloxane polymer has an organic group in which a carbon atom is directly bonded to a silicon atom, and 1 to 50% of the organic group has a mercapto group.   The siloxane polymer has a ratio of the number of SiOH groups to the number of Si—O—Si bonds (number of SiOH groups / number of Si—O—Si bonds) in the range of 0.02 to 0.2. The photosensitive composition of any one of Claims 1-5 which are these.   The photosensitive composition of any one of Claims 1-6 in which the said photoinitiator contains a photoradical generator. The siloxane polymer has an unsaturated double bond;
The photosensitive composition according to claim 7, wherein the siloxane polymer has an organic group in which a carbon atom is directly bonded to a silicon atom, and 5 to 99% of the organic group has an unsaturated double bond.   The photosensitive composition of Claim 7 or 8 which further contains the compound which has an unsaturated double bond within the range of 10-50 weight part with respect to 100 weight part of said siloxane polymers. The compound having an unsaturated double bond is a (meth) acrylic compound,
The photosensitive composition according to claim 9, wherein the (meth) acrylic compound has 1 to 10 unsaturated double bonds, and the weight average molecular weight of the (meth) acrylic compound is in the range of 100 to 5000. object. The siloxane polymer has at least one of a carboxyl group and a mercapto group;
The photosensitive composition of any one of Claims 6-10 in which the said photoinitiator contains a photo-acid generator. The siloxane polymer has a carboxyl group and a cyclic ether group;
The ratio of the number of cyclic ether groups of the siloxane polymer to the number of carboxyl groups (number of cyclic ether groups / number of carboxyl groups) is in the range of 0.1 to 12. The photosensitive composition as described in any one of. Coating the photosensitive composition according to any one of claims 1 to 12 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 area and obtaining a pattern film made of a cured product of the photosensitive composition. A method for producing a patterned film, which is characterized.   The manufacturing method of the pattern film of Claim 13 further equipped with the process of heating the said pattern film after a image development process.

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