JP2012111864A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of imparting a thin film having high dielectric constant and excellent insulation property, and to provide a thin film transistor showing excellent characteristics by applying a thin film formed by using the composition as a gate insulating film.SOLUTION: The curable composition contains (A) a polysiloxane-based resin, (B) an organic metal compound and (C) an organic solvent as indispensable components, wherein a content rate of the organic metal compound is 10-80 wt% to the polysiloxane-based resin. The thin film transistor using a film comprising the composition as the gate insulating film has excellent characteristics.

Description

  The present invention is a curable composition containing a polysiloxane compound, which can be formed into a thin film having a high dielectric constant and excellent insulating properties, and is useful as a gate insulating film of a thin film transistor.

  As an alternative to aSiTFT, which is currently used mainly in liquid crystal displays, etc., organic thin-film transistors using pentacene, polythiophene compounds, and oxide TFTs using ZnO compounds (Patent Document 1) are next-generation thin film transistors with a view to printing processes and low-temperature processes. As proposed. However, there are various problems for the practical application of devices using organic TFTs, and semiconductor material development and device development aimed at improving mobility, which is one of the problems, are being actively conducted.

  There are a number of factors that contribute to improving the mobility of TFTs. One of them is an increase in the dielectric constant of the gate insulating film. A transistor using such a material as an insulating film has been proposed, but a transistor that satisfies semiconductor characteristics has not yet been obtained.

JP 2007-158147 A JP 2007-43055 A WO2009 / 129912

  In view of the above circumstances, an object of the present invention is to provide a curable composition that can be formed into a thin film having a high dielectric constant and excellent insulating properties.

In view of the above circumstances, as a result of intensive studies by the present inventors, it has been found that the above problems can be solved by using a resin composition having the following features, and the present invention has been completed. That is, the present invention has the following configuration.

  1). A) a polysiloxane resin, B) an organometallic compound, and C) an organic solvent are contained as essential components, and the content of the organometallic compound is 10 to 80% by weight based on the polysiloxane resin. Curable composition.

  2). The curable composition according to 1), wherein the thin film obtained by curing the curable composition has a dielectric constant of 3.5 or more.

  3). The curable composition according to 1) or 2), wherein the organometallic compound is one selected from the group consisting of a titanium compound, an aluminum compound, a zirconium compound, and a hafnium compound.

  4). The curable composition according to any one of 1) to 3), wherein the polysiloxane resin is a hydrosilylation reactive resin.

  5). The polysiloxane resin is represented by the following general formula (I)

(Wherein R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same) and is a compound containing a structure represented by The curable composition as described in any one of 1) to 4) above.

  6). The curable composition according to any one of 1) to 6), wherein the polysiloxane resin has photopolymerizability.

  7). 5. The curable composition according to 5), wherein the polysiloxane resin has at least one group selected from the group consisting of an epoxy group, a crosslinkable silicon group and a (meth) acryloyl group.

  8). The curable composition according to 7), wherein the epoxy group is an alicyclic epoxy group.

  9). The curable composition according to 7), wherein the crosslinkable silicon group is an alkoxyl group.

  10). It has alkali developability, The curable composition in any one of 1) -9) characterized by the above-mentioned.

  11). The polysiloxane resin is represented by the following structural formula (X1) and / or (X2)

The curable composition according to any one of 1) to 10), wherein the curable composition is a compound containing a structure represented by:

  12). A thin film transistor using the curable composition according to any one of 1) to 11) as a material for a gate insulating film.

  ADVANTAGE OF THE INVENTION According to this invention, the thin film excellent in film forming property, high dielectric constant, and insulating property and the thin-film transistor formed using this can be provided.

The details of the invention will be described.
The curable composition of the present invention can be formed into a thin film having excellent film forming properties, high dielectric constant and excellent insulating properties, and the composition is useful as a gate insulating film of a thin film transistor. A thin film transistor using an object as a gate insulating film can give good characteristics.

(About curable composition)
The curable composition of the present invention will be described.
The curable composition of the present invention can be applied in a solution, and a thin film having excellent film forming properties and high dielectric constant and excellent insulating properties can be obtained.

(Component A)
The polysiloxane resin, which is an essential component of the present invention, is preferably a polysiloxane compound from the viewpoint of excellent insulation in the thin film to be formed, and contains a siloxane unit (Si—O—Si). Compounds and polymers are shown and are not particularly limited in structure.

Further, among the siloxane units in these compounds, the cured product obtained with a higher content of T unit (X ₃ SiO _3/2 ) or Q unit (SiO _4/2 ) in the constituent component has higher hardness. The cured product is more flexible and has lower stress as the heat resistance reliability is higher and the content of M unit (X ₃ SiO _1/2 ) or D unit (X ₂ SiO _2/2 ) is higher.

  The obtained thin film preferably has curability from the viewpoint of excellent solvent resistance and heat resistance during the transistor production process. There are also polysiloxane resins with various curing reactivity, such as hydrosilylation reaction with SiH group and alkenyl group, cation polymerization reaction with epoxy group, oxetanyl group, hydrolyzable silicon group, vinyl ether group, acrylic resin, etc. Radical polymerization reaction such as a group or methacryl group, a urethane crosslinking reaction having a hydroxyl group and an isocyanate group, a condensed amide having an amino group or a hydroxyl group and a carboxyl group, and an ester condensation reaction.

  Hydrosilylation reaction, cationic polymerization reaction and radical polymerization reaction are preferred from the viewpoint that the obtained thin film has excellent process resistance, and the hydrosilylation reaction is crosslinked from the viewpoint that an unreacted group is hardly generated and an insulating film is easily obtained. The reaction is preferably a cationic polymerization reaction or a radical polymerization reaction from the viewpoint of curing in a short time by light energy, and a cationic polymerization reaction such as an epoxy group or an oxetanyl group is preferable from the viewpoint of small curing shrinkage.

(Hydrosilylation reactive composition)
The hydrosilylation reactive composition is not particularly limited as long as it is a composition containing an alkenyl group, a SiH group, and a hydrosilylation catalyst.

  The compound having an alkenyl group can be used without particular limitation regardless of a polysiloxane compound or an organic compound. Specific examples of linear polysiloxanes having alkenyl groups include poly or oligosiloxanes whose ends are blocked with dimethylvinylsilyl groups, poly or oligosiloxanes having vinyl groups in the side chains, tetramethyldivinyldisiloxane, hexa Examples of methyltrivinyltrisiloxane and the above cyclic siloxane containing SiH groups include those in which SiH groups are substituted with alkenyl groups such as vinyl groups and allyl groups.

  Examples of the alkenyl group-containing organic compound do not include a siloxane unit (Si—O—Si) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer, and C, H, N, Particularly, if it is a compound composed of atoms selected from the group consisting of O, S and halogen, and is an organic compound having one or more carbon-carbon double bonds having reactivity with SiH group in one molecule It is not limited. Further, the bonding position of the carbon-carbon double bond having reactivity with the SiH group is not particularly limited, and may be present anywhere in the molecule.

  The organic compounds can be classified into organic polymer compounds and organic monomer compounds. Examples of the organic polymer compounds include polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, unsaturated hydrocarbon-based compounds. Hydrogen-based, polyacrylic acid ester-based, polyamide-based, phenol-formaldehyde-based (phenolic resin-based), and polyimide-based compounds can be used. Examples of organic monomer compounds include aromatic hydrocarbons such as phenols, bisphenols, benzene and naphthalene: aliphatic hydrocarbons such as linear and alicyclic: heterocyclic compounds and their A mixture etc. are mentioned.

  Specific examples of the compound include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, 1, 1,2,2-tetraallyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl monobenzyl isocyanurate, 1,2,4-trivinylcyclohexane, 1,4-butanediol Divinyl ether, nonanediol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether, trimethylol propylene Trivinyl ether, pentaerythritol tetravinyl ether, diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantane, 1, 3-bis (vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9- Decadiene, diallyl ether, bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio) 50-100% of those), allyl ether of novolak phenol, and the like allylated polyphenylene oxide is.

  Examples of the compound having an SiH group include poly or oligosiloxanes whose ends are blocked with dimethylhydrosilyl groups, and cyclic or chain poly or oligosiloxanes having SiH groups in the side chains.

  Among them, specific examples of cyclic siloxane include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-methyl-3,5,7-trihydrogen-1, 3,5,7-tetramethylcyclotetrasiloxane, 1,3-dimethyl-5,7-dihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-tri Hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-dipropyl-5,7-dihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 -Trihydrogen-7-hexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3 5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethyl Examples thereof include cyclosiloxane, 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane and the like. In particular, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of availability.

  From the viewpoint of obtaining a tough thin film, it is also preferable to use an oligomer in which polysiloxane compounds or organic compounds and polysiloxane compounds are partially reacted in advance. The partial cross-linking reaction is not particularly limited, but forms an electrically and thermally stable C—Si bond after the reaction as compared with hydrolysis condensation, and the reaction control is easy. It is preferable to apply a hydrosilylation reaction from the viewpoint that a crosslinking group hardly remains.

  The monomer for partial crosslinking is not particularly limited, and the siloxane compound having an SiH group and the siloxane compound or organic compound having an alkenyl group can be used in appropriate combination. As the catalyst for the hydrosilylation reaction, a known hydrosilylation catalyst may be used. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable. Moreover, these catalysts may be used independently and may be used together 2 or more types.

(About photopolymerizable composition)
Those having photopolymerizability can also be suitably used from the viewpoint of being able to be cured in a short time by light energy. Examples of the photopolymerization reaction include a cationic polymerization reaction and a radical polymerization reaction.

  As the cationic polymerizable composition, a curable composition containing a compound having a cationic polymerizable functional group is particularly shown. The cationic polymerizable functional group is not particularly limited, and examples thereof include an epoxy group, an oxetanyl group, a hydrolyzable silicon group, and a vinyl ether group. From the viewpoint of high cationic polymerizability, an alicyclic epoxy group. , An oxetanyl group, an alkoxysilyl group, a SiH group, and the like are preferable, an epoxy group is more preferable from the viewpoint of availability, and an alicyclic epoxy group is preferable from the viewpoint of excellent reactivity.

  Moreover, as a radically polymerizable composition, the curable composition containing the compound which has a radically polymerizable functional group especially is shown. Examples of the radical polymerizable functional group include an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group. From the viewpoint of reactivity, an acryloyl group and a methacryloyl group are preferable.

  In particular, from the viewpoint of high heat resistance and excellent dielectric strength, polysiloxane compounds into which the cationic polymerizable functional groups and radical polymerizable functional groups exemplified above are introduced are preferable. The method to be introduced is not particularly limited. From the viewpoint of forming an electrically and thermally stable C—Si bond after the reaction, and easy control of the reaction and hardly leaving an uncrosslinked group, a hydrosilylation reaction is used. The method of introduction is preferred.

  The compound used for introducing the functional group is not particularly limited, and the polysiloxane compound having the SiH group described above, the alkenyl group having hydrosilylation reactivity and the cationic polymerizable functional group or radical polymerizable functional group on the same molecule. These compounds can be used in appropriate combination.

(Photopolymerization initiator)
In the case of the curable composition of the present invention having photopolymerizability, a radical photopolymerization initiator and a cationic photopolymerization initiator can be appropriately used without particular limitation.
Photocationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds, bis (perfluoroalkylsulfonyl) methane metal salts, bis (perfluoroalkylsulfonyl) methane metal salts, aryldiazonium compounds, group VIa Aromatic onium salts of elements, aromatic onium salts of group Va elements, dicarbonyl chelates of group IIIa to Va elements, thiopyrylium salts, VIa elements in the form of MF6 ^- anions, arylsulfonium complex salts, aromatic iodonium complex salts and aromatics Sulfonium complex salt, bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluorometal salt (for example, phosphate, arsenate, antimonate, etc.), fragrance whose anion is B (C ₆ F ₅ ) ₄ ^— One or more of an aromatic iodonium complex salt and an aromatic sulfonium complex salt are included. The

  Preferred cationic active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, Group V and Group VI elements.

  Some of these salts are FX-512 (3M), UVR-6990 and UVR-6974 (Union Carbide), UVE-1014 and UVE-1016 (General Electric), KI-85 (Degussa) ), SP-152 and SP-172 (Asahi Denka Co., Ltd.), Sun-Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical Industry Co., Ltd.), WPI113 and WPI116 (Wako Pure Chemical Industries, Ltd.), RHODORSIL PI2074 (Rhodia) As a product.

  In the case of photo radical initiators, acetophenone compounds, benzophenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzoin compounds, biimidazole compounds, α-diketone compounds, titanocene compounds, polynuclear compounds Quinone compounds, xanthone compounds, thioxanthone compounds, triazine compounds, ketal compounds, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, thiuram compounds, fluoroamine compounds, etc. Can be used.

  Specific examples of acetophenone compounds include 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- (4′-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2′-hydroxyethoxy) phenyl (2-hydroxy-2) -Propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- (4'-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4′-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2 -Dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propane-1 -ON etc. are mentioned.

  Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  Specific examples of oxime ester compounds include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl 2-benzoylbenzoate and the like.

  Specific examples of the benzophenone compounds include benzyl dimethyl ketone, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.

  Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2 , 2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4 , 6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1, 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1 , 2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2, 4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bi (2,4,6-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

  Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone and the like.

  Specific examples of the xanthone compound include xanthone, thioxanthone, 2-chlorothioxanthone, 2,5-diethyldioxanthone and the like.

  Specific examples of the triazine compound include 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-methoxyphenyl) -s-triazine, 1,3-bis (Trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (2′-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine, 2- (4′-methoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( '-Methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-bromo-4'-methylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2'-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine and the like.

  In particular, from the viewpoint of excellent thin film curability, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- [4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyl) Oxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  In particular, from the viewpoint that the cured product is excellent in transparency, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4′-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2′-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone preferable.

  These polymerization initiators may be used alone or in combination of two or more.

  The amount of the photopolymerization initiator used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin component in the curable composition. When the amount of the photopolymerization initiator is small, curing is insufficient, which is not preferable. When the amount of the initiator is large, storage stability in a liquid state is not preferable.

(Sensitizer)
In the curable composition of the present invention, when cured with light energy, the sensitivity of light is improved, and high wavelengths such as g-line (436 nm), h-line (405 nm), and i-line (365 nm) are called. In order to give sensitivity to light, a sensitizer can be appropriately added. These sensitizers can be used in combination with the above cationic polymerization initiator and / or radical polymerization initiator to adjust the curability. Examples of compounds that can be used include anthracene compounds and thioxanthone compounds.

  Specific examples of the anthracene compound include anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10- Diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di -Tert-butylanthracene and the like.

  Anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like are particularly preferable from the viewpoint of easy availability. Anthracene is preferable from the viewpoint of excellent transparency of the cured product, and 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-diethoxy from the viewpoint of excellent compatibility with the curable composition. Anthracene and the like are preferable.

  Specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2,5-diethyldioxanthone and the like.

These sensitizers may be used alone or in combination of two or more.
In the resin structure, the following general formula (I)

(In the formula, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same). It is preferable from the viewpoint that it can be a fine film and can be a flattened film excellent in chemical resistance and heat resistance.

  A technique for introducing the structure into the curable composition is not particularly limited, and a technique for adding a general-purpose isocyanuric ring-containing compound may be mentioned. Examples of the isocyanuric ring-containing compound include triallyl isocyanurate, diallyl isocyanurate, monoallyl isocyanurate, triglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, tris (2- (meth) acryloyloxyethyl) Examples include isocyanurate and tri (3-mercaptopropionyloxyethyl) isocyanurate, which can be appropriately selected according to the crosslinking reaction of the resin composition.

  In a curable composition having a hydrosilylation reaction as a curing reaction, triallyl isocyanurate having an alkenyl group, diallyl isocyanurate, monoallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, tris (2- ( (Meth) acryloyloxyethyl) isocyanurate is preferred.

  In a curable composition having a cationic polymerization reaction as a curing reaction, triglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and tris (trimethoxysilylpropyl) isocyanurate are preferable.

  In a curable composition having a radical polymerization reaction as a curing reaction, triallyl isocyanurate, diallyl isocyanurate, monoallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, tris (2- (meth) acryloyloxy) Ethyl) isocyanurate and tri (3-mercaptopropionyloxyethyl) isocyanurate are preferred.

  Furthermore, a compound obtained by partially reacting the general-purpose isocyanuric ring-containing compound and other compounds in advance can also be applied. When introduced into a polysiloxane compound, a compound obtained by hydrosilylation of a polysiloxane compound having an SiH group and an isocyanuric ring compound having an alkenyl group in advance, an isocyanuric ring-containing compound having an alkoxysilyl group, or an epoxy group It is possible to use a compound obtained by reacting an isocyanuric ring-containing compound having a polysiloxane and a polysiloxane compound having an alkoxysilyl group in advance by hydrolysis condensation, which is preferable from the viewpoint of compatibility, and the chemical resistance and heat resistance of the resulting cured product. From the viewpoint of excellent properties, those using a compound that has been hydrosilylated in advance are preferred.

  Further, in the case of a composition having photopolymerizability, those having alkali developability are preferred from the viewpoint that fine patterning can be formed by photolithography. In order to develop alkali developability, those having an acidic group such as a carboxyl group, a phenol group, and a sulfonic acid group in the structure can be mentioned. Among them, the following structural formulas (X1) and / or (X2)

Is preferable from the viewpoint of having alkali developability and excellent transparency and heat resistance.

(Component B)
The organometallic compound used in the curable composition of the present invention is not particularly limited and can be used. Specifically, a titanium compound, a zirconium compound, an aluminum compound, a hafnium compound, or the like, which is an organometallic compound that has excellent insulating characteristics and a high dielectric constant, can be used.

  Examples of the titanium compound include titanium (IV) n-butoxide, titanium (IV) t-butoxide, titanium (IV) ethoxide, titanium (IV) 2-ethylhexoxide, titanium (IV) isopropoxide, titanium ( IV) (diisopropoxide) bisacetylacetonate, titanium (IV) oxide bis (acetylacetonate), trichlorotris (tetrahydrofuran) titanium (III), tris (2,2,6,6-tetramethyl-3,5) -Heptanedionate) Titanium (III), (Trimethyl) pentamethylcyclopentadienyl titanium (IV), Pentamethylcyclopentadienyl titanium trichloride (IV), Pentamethylcyclopentadienyl titanium trimethoxy (IV), tetrachlorobis (cyclohexylmercapto) titanium (IV), tetrachlorobis (tetrahydrofuran) titanium (IV), tetrachlorodiaminetitanium (IV), tetrakis (diethylamino) titanium (IV), tetrakis (dimethylamino) Titanium (IV), bis (t-butylcyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) dicarbonyltitanium (II), bis (cyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) Titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (isopropylcyclopentadienyl) titanium dichloride, tris (2,2,6,6-tetramethyl- 3,5-heptanedionate) oxotitanium (IV), chlorotitanium triisopropoxide, cyclopentadienyltitanium trichloride, dichlorobis (2,2,6,6-tetramethyl-3,5-heptanedionate) Titanium (IV), dimethylbis (t-butylcyclopentadienyl) titanium (IV), di (isopropoxide) bis (2,2,6,6-tetramethyl-3,5-heptanedionate) titanium ( IV) and the like can be used.

Examples of the zirconium compound include zirconium (IV) n-butoxide, zirconium (IV) t-butoxide, zirconium (IV) ethoxide, zirconium (IV) isopropoxide, zirconium (IV) n-propoxide, zirconium ( IV) acetylacetonate, zirconium (IV) hexafluoroacetylacetonate, zirconium (IV) trifluoroacetylacetonate, tetrakis (diethylamino) zirconium, tetrakis (dimethylamino) zirconium, tetrakis (2,2,6,6-tetra Methyl-3,5-heptanedionate) zirconium (IV), and the like can be used.

  Examples of the hafnium compound include hafnium (IV) n-butoxide, hafnium (IV) t-butoxide, hafnium (IV) ethoxide, hafnium (IV) isopropoxide, hafnium (IV) isopropoxide monoisopropyrate, hafnium ( IV) Acetylacetate, tetrakis (dimethylamino) hafnium, etc. can be used.

Examples of the aluminum compound include aluminum n-butoxide, aluminum t-butoxide, aluminum sec-butoxide, aluminum ethoxide, aluminum isopropoxide, aluminum acetylacetonate, aluminum hexafluoroacetylacetonate, and aluminum trifluoroacetylacetate. Nalto, tris (2,2,6,6-tetramethyl-3,5-heptanedionate) aluminum and the like can be used.

Among the organometallic compounds, metal alkoxide compounds are preferred because they are highly stable among the compositions, can ensure handling properties, and are excellent in hydrolysis reactivity.
Further, among the alkoxide compounds, an alkoxy group having 2 to 6 carbon atoms is preferable from the viewpoint that a residue is hardly left in the cured product after heating and a good quality film is easily obtained.

  Among these, an aluminum compound is preferable from the viewpoint of easy formation of a thin film having excellent insulating properties and low leakage current, and a titanium compound is preferable from the viewpoint of easily obtaining a thin film having a high dielectric constant. .

  In the organic insulator composition of the present invention, the content of the organometallic compound is preferably 30 to 70% by weight, more preferably 35 to 65% by weight, based on the polysiloxane compound. If the content of the organometallic compound is small, the effect of improving the dielectric constant cannot be obtained, and if the content of the organometallic compound is too large, a composition having a uniform phase cannot be obtained or the leakage current of the manufactured device increases. This is not preferable.

(Component C)
In the curable composition of the present invention, it is preferable to use a solvent in order to uniformly apply the resin composition. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether, and the like. Ether solvents, acetone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, glycol solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), ethylene glycol diethyl ether, chloroform, methylene chloride, , 2-dichloroethane and other halogen-based solvents can be suitably used.

  In particular, from the viewpoint of easily forming a uniform film, toluene, tetrahydrofuran, propylene glycol-1-monomethyl ether-2-acetate, methyl isobutyl ketone, chloroform, and the like are preferable.

  Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferable usage amount with respect to 1 g of the resin composition to be used is 0.1 g, and the upper limit of the preferable usage amount is 10 g. If the amount used is small, it is difficult to obtain the effect of using a solvent such as viscosity reduction, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also in terms of cost. It is disadvantageous and the industrial utility value decreases. These solvents may be used alone or as a mixed solvent of two or more.

(Other additives)
The curable composition of the present invention includes other flame retardants, flame retardant aids, surfactants, antifoaming agents, emulsifiers, leveling agents, anti-fogging agents, ion trapping agents such as antimony-bismuth, and thixotropic agents. , Storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, thermal stabilizer, antistatic agent, radiation blocker, nucleating agent, phosphorus-based excess An oxide decomposing agent, a lubricant, a metal deactivator, a thermal conductivity imparting agent, a physical property adjusting agent and the like can be added within a range not impairing the object and effect of the present invention.

(About thin film transistors)
A thin film transistor using the curable composition obtained in the present invention as a material for a gate insulating film refers to a field effect transistor (FET), which includes a three-terminal type formed from a source, a drain, and a gate electrode, and a back gate. A four-terminal transistor including a thin film transistor in which a current between a source and a drain is controlled by an electric field of a channel generated by applying a voltage to a gate electrode.

  As for the thin film transistor structure, there are various combinations and arrangements depending on the display device structure to be applied, such as bottom gate type, top gate type, and source / drain electrode arrangement with respect to the arrangement of the gate electrode, such as bottom contact type and top contact type. Design is possible, and the structure is not particularly limited.

  Various types of thin film transistor semiconductor layers have been proposed, including silicon-based semiconductors such as amorphous silicon (aSi), polysilicon (pSi), and microcrystalline silicon (μ-cSi), and oxides such as ZnO and InGaZnO. Typical examples include organic semiconductors, organic semiconductors using compounds such as pentacene, oligothiophene, and phthalocyanine, and carbon-based semiconductors using carbon nanotubes, graphene, fullerenes, and the like. Among these, those using an organic semiconductor are preferable from the viewpoint of being a low-temperature process and being easily formed on a plastic film.

  Moreover, regarding the method for forming the semiconductor layer, various methods such as CVD, sputtering, vapor deposition, and coating have been proposed and are not particularly limited. It is preferable that it can be formed by sputtering, vapor deposition, or coating method from the viewpoint of easy formation on a plastic film in a low temperature process, and it is formed by coating method from the viewpoint of cost merit because it can be mass-produced using a simple process such as a printing process. What can be done is more preferable.

  Regarding the electrode material, it can be used without any particular limitation, but it can be easily obtained, such as Au, Al, Pt, Mo, Ti, Cr, Ni, Cu, ITO, PEDOT / PSS, etc., conductive polymer, conductive paste Metal ink or the like is preferably used. Al, Mo, Ti, Cr, Ni, Cu and the like are preferable because of low resistance and high conductivity, and ITO and PEDOT / PSS are preferable from the viewpoint of being applicable to places where transparency is required. Au and Pt are preferable from the viewpoint that the surface is hardly oxidized and excellent in stability, and conductive polymers such as PEDOT / PSS, conductive paste, and metal ink are preferably used because they can be formed by a printing process.

(Method of forming insulating film)
The method for forming the gate insulating film using the curable composition is not particularly limited, and spin coating, dip coating, roll coating, screen coating, spray coating, spin casting, flow coating, screen printing, ink jet or drop casting. The film can be formed by such a method. Further, viscosity adjustment with a solvent and surface tension adjustment with a surfactant may be appropriately performed in accordance with the state of the substrate on which the film is formed. Moreover, in this curable composition, it does not specifically limit, such as thermosetting, photocurability, and moisture curing. At the time of thermosetting, the heating temperature is not particularly limited.

(Dielectric constant, leakage current)
In order to obtain a higher mobility transistor in the thin film transistor, a gate insulating film having a high dielectric constant is preferable. Polysiloxane compounds are often used as gate insulating films because of their excellent insulating properties and voltage resistance, but generally have a low dielectric constant of 3.0 or less because of the properties of the materials. However, in order to function as a good transistor, it is preferably 3.5 or more, and more preferably 4.0 or more from the viewpoint of increasing gate capacitance and exhibiting high mobility.

Further, a transistor having a high ON / OFF current ratio is preferable as a characteristic. A transistor having a lower ON / OFF current ratio can be obtained by reducing the OFF current as the gate insulating film has a lower leakage current. Can be. The leakage current value that can be suitably used as a gate insulating film, it is preferably 5.0 nA / cm ² or less at 5000Å thickness, it is what is more preferably 3.0nA / cm ² or less.

  When the curable composition of the present invention is used as a gate insulating film, it is possible to obtain a gate insulating film satisfying these characteristics. By using the curable composition of the present invention for a gate insulating film, current at ON / OFF is obtained. A thin film transistor having a high ratio and good characteristics can be obtained.

Table 1 shows the results of measuring the capacitance and the leakage current and calculating the dielectric constant for the capacitors prepared in the following examples and comparative examples using the method of the present invention.

  As can be seen from this result, it can be seen that a thin film having a high dielectric constant and excellent insulation is obtained from the curable composition according to the present invention.

(Film thickness measurement)
The film thicknesses of the thin films prepared in Examples and Comparative Examples were measured using a step gauge (Dektak 6M, ULVAC).

(Capacitance measurement)
Using a semiconductor parameter analyzer (Keithley 4200), the electrostatic capacity (F) of the thin films prepared in Examples and Comparative Examples when 1 MHz and 10 V were applied was measured.

(Leakage current measurement)
Using a semiconductor parameter analyzer (Keithley 4200), the amount of leakage current in the thin films prepared in Examples and Comparative Examples when 0 to 30 V was applied was measured, and the current value per unit area when 20 V was applied was measured as the leakage current value (nA / cm ² ).

(Relative permittivity calculation)
The relative dielectric constant was calculated from the following equation from the film thickness and the capacitance obtained from the above measurement.

ε = C × t / ε ₀ × A
C: Capacitance (F)
ε ₀ : Dielectric constant of vacuum (8.85E-12)
t: Film thickness (m)
A: Area (m ² )
(Production Example 1)
A 300 mL four-necked flask was charged with 72.4 g of toluene and 72.4 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen. Then, a mixed solution of 10 g of toluene and 0.0063 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. It was confirmed by ¹ H-NMR that the allyl group had disappeared, and the reaction was terminated by cooling. Solvent toluene was distilled off under reduced pressure to obtain polysiloxane compound A. ^{From the 1} H-NMR measurement, a peak derived from the SiH group is confirmed from the obtained polysiloxane compound A, and it can be seen that the polysiloxane compound has a SiH group.

  1 g of the obtained polysiloxane compound A, 0.73 g of triallyl isocyanurate, 0.0019 g of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), 0.5 g of aluminum tributoxide, 0.0017 g of 1-ethynylcyclohexanol Then, 8.0 g of propylene glycol monomethyl ether acetate (solvent, PGMEA) was mixed to obtain Resin Composition 1.

(Production Example 2)
1 g of polysiloxane compound A obtained in Production Example 1, 0.73 g of triallyl isocyanurate, 0.0019 g of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), 0.5 g of titanium tetrabutoxide, 1-ethynylcyclo The resin composition 2 was obtained by mixing 0.0017 g of hexanol and 8.0 g of propylene glycol monomethyl ether acetate (solvent, PGMEA).

(Production Example 3)
1 g of polysiloxane compound A obtained in Production Example 1, 0.73 g of triallyl isocyanurate, 0.0019 g of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), 0.5 g of zirconium tetrabutoxide, 1-ethynylcyclo The resin composition 3 was obtained by mixing 0.0017 g of hexanol and 8.0 g of propylene glycol monomethyl ether acetate (solvent, PGMEA).

(Production Example 4)
Into a 300 mL four-necked flask, 72.4 g of toluene and 72.4 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the gas phase portion was purged with nitrogen. A mixed solution of 10 g of toluene and 0.0063 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was added dropwise. It was confirmed by ¹ H-NMR that the allyl group had disappeared, and the reaction was terminated by cooling.

Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane was distilled off under reduced pressure, 70 g of toluene was added again, the gas phase was purged with nitrogen, the internal temperature was 105 ° C., 5 g of toluene, and 5 g of vinylcyclohexene oxide. Was added dropwise. It was confirmed by ¹ H-NMR that the vinyl group had disappeared, and the reaction was terminated by cooling. Solvent toluene was distilled off under reduced pressure to obtain polysiloxane compound B. A peak derived from an epoxy group is confirmed by ¹ H-NMR measurement, and it is understood that the polysiloxane compound has an epoxy group.

  1 g of the resulting polysiloxane compound B, 0.04 g of iodonium salt-based cationic polymerization initiator (BBI-102, manufactured by Midori Chemical), 0.5 g of aluminum tributoxide, and 8.0 g of propylene glycol monomethyl ether acetate (solvent, PGMEA) By mixing, Resin Composition 4 was obtained.

(Examples 1-4)
The resin compositions 1 to 4 obtained in Production Examples 1 to 4 were applied on a glass substrate with Mo film (2000 mm) by spin coating under the conditions of 1000 rpm and 20 sec, respectively, and post-baked at 250 ° C. for 1 h to form a thin film. did. Aluminum electrodes 3 having a thickness of 500 mm and 3 mmφ were formed by a vacuum deposition apparatus, and capacitors of Examples 1 to 4 were manufactured.

(Comparative Example 1)
A thin film and a capacitor were produced in the same manner as in Example 1 except that no organometallic compound was added.

Claims (12)

A) a polysiloxane resin, B) an organometallic compound, and C) an organic solvent are contained as essential components, and the content of the organometallic compound is 10 to 80% by weight based on the polysiloxane resin. Curable composition. The curable composition according to claim 1, wherein the thin film obtained by curing the curable composition has a dielectric constant of 3.5 or more. The curable composition according to claim 1 or 2, wherein the organometallic compound is one selected from the group consisting of a titanium compound, an aluminum compound, a zirconium compound, and a hafnium compound. The curable composition according to claim 1, wherein the polysiloxane resin is a hydrosilylation reactive resin. The polysiloxane resin is represented by the following general formula (I)

(Wherein R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and each R ¹ may be different or the same) and is a compound containing a structure represented by The curable composition according to any one of claims 1 to 4, wherein: The curable composition according to claim 1, wherein the polysiloxane resin has photopolymerizability. 6. The curable composition according to claim 5, wherein the polysiloxane resin has at least one group selected from the group consisting of an epoxy group, a crosslinkable silicon group and a (meth) acryloyl group. The curable composition according to claim 7, wherein the epoxy group is an alicyclic epoxy group. The curable composition according to claim 7, wherein the crosslinkable silicon group is an alkoxyl group. It has alkali developability, The curable composition in any one of Claims 1-9 characterized by the above-mentioned. The polysiloxane resin is represented by the following structural formula (X1) and / or (X2)

The curable composition according to any one of claims 1 to 10, wherein the curable composition comprises a structure represented by the formula: A thin film transistor using the curable composition according to claim 1 as a material for a gate insulating film.