JP5749446B2 - Photocurable composition - Google Patents

Description

  The present invention relates to a photocurable composition that gives a cured product excellent in optical transparency and insulation.

  Currently, it is widely used as a photocurable resin in various fields such as acrylic resin and epoxy resin. The photo-curing resin undergoes a cross-linking reaction instantaneously by light energy and can be cured in a short time and at a low temperature, so that the process can be saved and the heat-sensitive peripheral agent is less damaged. It has been widely applied for parts. However, with regard to these general-purpose photo-curing resins, cured products obtained by photopolymerization of acrylic groups and epoxy groups but with a high reaction rate, but are difficult to complete, such as electrical elements and semiconductors. In applications that require extremely high material reliability, such as an insulating film, a material that does not function effectively due to a large leak current and satisfies the characteristics has not been found (Patent Documents 1, 2, and 3).

JP 2006-152326 A JP-A-9-157316 JP2010-6949

  In view of the above circumstances, an object of the present invention is to provide a curable composition and a cured product that have photocurability, are preferably lithographic, and give a cured product having 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) Compound having alkenyl group and photopolymerizable functional group in the same molecule as essential components, (B) Compound having SiH group, (C) Photopolymerization initiator (D) Curable composition containing hydrosilylation catalyst object.

  2). The curable composition according to 1), wherein the photopolymerizable functional group of component (A) is at least one selected from the group consisting of an epoxy group, a crosslinkable silicon group, and a (meth) acryloyl group. object.

  3). 2. The curable composition according to 2), wherein the photopolymerizable functional group of component (A) is an epoxy group.

  4). 2. The curable composition according to 2), wherein the photopolymerizable functional group of component (A) is an alkoxylyl group.

  5). The curable composition according to any one of 1) to 4), wherein the component (A) is a polysiloxane compound.

  6). Component (A) or Component (B) 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). The curable composition according to any one of 1) to 5).

  7). Component (A) or Component (B) contains at least one selected from the group consisting of each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. The curable composition according to any one of 1) to 6).

  8). A thin film transistor obtained by using a thin film obtained from the curable composition according to any one of 1) to 7) as a passivation film for a semiconductor layer.

  9). A thin film transistor obtained by using a thin film obtained from the curable composition according to any one of 1) to 7) as a gate insulating film of a semiconductor layer.

  According to the present invention, it is possible to provide a curable composition and a cured product that have photocurability, are preferably lithographic, and give a cured product having excellent insulating properties.

  The details of the invention will be described.

  The curable composition of the present invention can provide a cured product or a thin film having photocurability, preferably capable of photolithography, and having excellent insulating properties.

  In the present invention, the photopolymerization reaction by the photopolymerizable functional group of the component (A) and the component (C) and the hydrosilylation reaction by the alkenyl group of the component (A), the component (B) and the component (D) are carried out. As a result of this, the insulating property superior to the general-purpose photocurable resin is exhibited while having photocurability. Further, since the material has photo-curing properties, the shape after application of the material can be fixed by light irradiation in a short time as compared with a material having only heat curing, and there is an advantage that photo-patterning is possible. Details of the invention will be described below.

(Component A)
The component (A) is not particularly limited as long as it is a compound having an alkenyl group and a photopolymerizable functional group in the same molecule.

  The alkenyl group here is not particularly limited as long as the hydrosilylation reaction with the SiH group proceeds. An allyl group and a vinyl group are preferable from the viewpoint that the hydrosilylation reaction easily proceeds, and a vinyl group is preferable from the viewpoint of excellent heat resistance.

The photopolymerizable functional group in the component (A) may be any functional group that is polymerized and crosslinked by radicals or cationic species generated from the photopolymerization initiator when light energy is applied from the outside. The form of crosslinking is not limited.
Among them, particularly from the viewpoint of reactivity and stability of the compound, at least one of the photopolymerizable functional groups is preferably an epoxy group, a crosslinkable silicon group, a (meth) acryloyl group, an oxetanyl group, or a vinyloxy group.

  Among the epoxy groups, an alicyclic epoxy group and a glycidyl group are preferable from the viewpoint of stability, and an alicyclic epoxy group is particularly preferable from the viewpoint of excellent cationic polymerization by light and heat.

  Examples of the crosslinkable silicon group include hydrolyzable silicon groups such as an alkoxysilyl group, an acetoxysilyl group, a phenoxysilyl group, a silanol group, and a chlorosilyl group. From the viewpoint, an alkoxysilyl group is particularly preferable. Examples of the alkoxysilyl group include those in which the functional group bonded to silicon is a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, or a tert-butoxy group, A methoxy group and an ethoxy group are particularly preferable from the viewpoint that residual components after curing hardly remain. The modified polyorganosiloxane compound preferably has at least two photopolymerizable functional groups, and each photopolymerizable functional group may be the same or may have two or more different functional groups.

  Specific examples of the compound include compounds having an epoxy group as a photopolymerizable functional group, such as vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and photopolymerization reaction. From the viewpoint of excellent properties, vinylcyclohexene oxide, which is a compound having an alicyclic epoxy group, is particularly preferable.

Examples of the compound having an oxetanyl group include allyl oxetanyl ether and vinyl oxetanyl ether. When using the compound which has an oxetanyl group, it is preferable from a viewpoint that the toughness of hardened | cured material improves.
In the case of a compound having a crosslinkable silicon group as a photopolymerizable functional group, from the viewpoint of availability and heat resistance, the following general formula (II)

(Wherein R ⁶ and R ⁷ represent an organic group having 1 to 6 carbon atoms, n represents 1 to 3, and m represents a number of 0 to 10) and have a crosslinkable silicon group. In view of easy removal of by-products after the reaction, trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, methoxydimethylvinylsilane, and ethoxydimethylvinylsilane are particularly preferable.

  Moreover, as a component (A), it is preferable that it is a polysiloxane type compound from a viewpoint that the hardened | cured material obtained is excellent in heat resistance.

The polysiloxane compound is a compound containing a repeating unit of siloxane in the structure, and among the siloxane units in these compounds, T unit (X ₃ SiO _3/2 ) or Q unit ( The higher the content of SiO _4/2 ), the higher the cured product, the higher the hardness and the better the heat resistance reliability, and the M unit (X ₃ SiO _1/2 ) or D unit (X ₂ SiO _2/2 ). As the content of is higher, the cured product is more flexible and less stressed.

The polysiloxane compound used in the curable composition of the present invention can be obtained by various techniques such as condensation reaction by hydrolysis, addition reaction, and ring-opening polymerization, and there is no particular limitation. Among these, a method obtained by using hydrosilylation in which an alkenyl group and a photopolymerizable functional group can be introduced regioselectively and can be introduced by a chemically stable bond is more preferable.
Examples of the modified polyorganosiloxane compound suitable for use in the curable composition of the present invention include the following.

Hydrosilylation reaction products of the following compounds (α), (β), (γ):
(Α) Compound having alkenyl group (β) Compound having two or more SiH groups (γ) Compound having one or more alkenyl groups and one or more photopolymerizable functional groups.

(Compound (α))
The compound (α) will be described.
The compound (α) is not particularly limited as long as it is a compound having an alkenyl group, and can be used without particular limitation regardless of a polysiloxane compound or an organic compound.

In particular, polysiloxane having an alkenyl group can be preferably applied from the viewpoint of transparency and curability of the cured product. Among these, from the viewpoint of compound availability, a polysiloxane compound having a vinyl group (Si—CH═CH ₂ group) bonded to a silicon group is preferable. Specific examples include poly or oligosiloxanes end-capped with dimethylvinylsilyl groups, poly or oligosiloxanes having vinyl groups in the side chains, tetramethyldivinyldisiloxane, hexamethyltrivinyltrisiloxane, SiH groups Examples of the cyclic siloxane include those in which the hydrogen atom of the SiH group is substituted with an alkenyl group such as a vinyl group or an allyl group. Specifically, 1,3,5,7-vinyl-1,3,5,7- Tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5, 7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 1,3,5,7, -Pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane, etc. Compounds.

  Examples of the alkenyl group-containing organic compound do not include a siloxane unit (Si—O—Si), but are composed of atoms selected from the group consisting of C, H, N, O, S and halogen as constituent elements. The compound is not particularly limited as long as it is an organic compound having a carbon-carbon double bond having reactivity with a SiH group in one molecule. 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, 1,2,4-trivinylcyclohexane, 1,4-butanediol diallyl ether, nonanediol diallyl ether, 1,4 -Cyclohexane dimethanol diallyl ether, triethylene glycol diallyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, vinyl Phenol S diallyl ether, 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 Ethers, 2,5-diallylphenol allyl ether, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), novolak phenol Allyl ether Le polyphenylene oxide,
Other examples include those in which all of the glycidyl groups of conventionally known epoxy resins are replaced with allyl groups.

  Further, as the compound, a low molecular weight compound that is difficult to express by dividing into a skeleton portion and an alkenyl group (a carbon-carbon double bond having reactivity with the SiH group) can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene, fats such as cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Examples thereof include aromatic cyclic polyene compound systems and substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.

  In particular, triallyl isocyanurate represented by the following general formula (I) and derivatives thereof are particularly preferable from the viewpoints of transparency, heat resistance, light resistance, and insulation.

(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).

As R < ¹ > of the said general formula (I), it is preferable that it is a C1-C20 monovalent organic group from a viewpoint that the heat resistance of the hardened | cured material obtained can become higher, and C1-C1 10 monovalent organic groups are more preferable, and monovalent organic groups having 1 to 4 carbon atoms are more preferable. Examples of these preferable R ¹ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group and the like.

  Specific examples of these compounds include triallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monopropyl isocyanurate, and triallyl isocyanurate from the viewpoint of availability. It is done.

(Compound (β))
The compound (β) will be described.
As for the compound (β), any compound having at least two SiH groups in one molecule can be used without any particular limitation.

  From the viewpoint that flexibility is imparted to the cured product,

(In formula, R < ¹³ >, R < ¹⁴ > represents a C1-C6 organic group, and may be same or different, l is 0-50, n is 2-50, m is the number of 0-10. Represents.)
A linear organopolysiloxane having at least two SiH groups in one molecule represented by R ¹³ and R ¹⁴ are preferably methyl groups from the viewpoints of availability and heat resistance, and are preferably phenyl groups from the viewpoint of increasing the strength of the cured product.
From the viewpoint that the heat resistance of the cured product is high,

(Wherein R ^{1 to} R ⁸ are an organic group containing a group selected from an epoxy group, a mercapto group, and an amino group, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, a cyclohexyl group, etc. Aryl group such as cycloalkyl group, phenyl group, tolyl group, etc., or chloromethyl group, trifluoropropyl group, cyanoethyl in which some or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atom or cyano group An unsubstituted or substituted monovalent hydrocarbon group selected from the same or different, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, of R ^{1 to} R ⁸ At least two of these are organic groups containing SiH groups that are cross-linking reactions of the composition)

(Wherein R ^{9 to} R ³² are an organic group containing a group selected from an epoxy group, a mercapto group, and an amino group, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, and a cyclohexyl group. A cycloalkyl group such as a cycloalkyl group, a phenyl group, a tolyl group or the like, or a chloromethyl group or a trifluoropropyl group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom or a cyano group , The same or different organic groups selected from cyanoethyl groups, provided that at least two of these R ^{9 to} R ³² are organic groups containing SiH groups),

(In the formula, R represents an organic group containing a group selected from an epoxy group, a mercapto group and an amino group, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, and a cycloalkyl such as a cyclohexyl group. An aryl group such as a group, a phenyl group, a tolyl group, or the like, or a chloromethyl group, a trifluoropropyl group, or a cyanoethyl group in which some or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom or a cyano group. Selected from the same or different organic groups, provided that at least two of these R are organic groups containing SiH groups), and each molecule has at least two SiH groups. An organopolysiloxane having a T or Q structure in the molecule is preferred.

  Of these, from the viewpoint of availability and reactivity with the compound (α), the following general formula (III)

(Wherein R ² and R ³ represent an organic group having 1 to 6 carbon atoms and may be the same or different, n represents 2 to 10 and m represents a number of 0 to 10)
A cyclic organopolysiloxane having at least 2 and preferably 3 SiH groups in one molecule is preferred.

The substituents R ² and R ³ in the compound represented by the general formula (III) are preferably selected from the group consisting of C, H and O, and are preferably hydrocarbon groups. More preferably, it is a methyl group.

The compound represented by the general formula (III) is preferably 1,3,5,7-tetramethylcyclotetrasiloxane from the viewpoint of availability and reactivity.
The various compounds (β) described above can be used alone or in combination of two or more.

(Compound (γ))
The compound (γ) will be described.

  The compound (γ) is not particularly limited as long as it is a compound having an alkenyl group and a photopolymerizable functional group, and can be used without particular limitation regardless of a polysiloxane compound or an organic compound. In addition, the photopolymerizable functional group here is the same as the above-mentioned photopolymerizable functional group, and a preferable aspect is also preferable.

  In particular, as a photopolymerizable functional group, at least one of the photopolymerizable functional groups is an epoxy group, a crosslinkable silicon group, a (meth) acryloyl group, an oxetanyl group, or a vinyloxy group from the viewpoint of reactivity and stability of the compound. preferable.

  Specific examples of the compound (γ) having an epoxy group as a photopolymerizable functional group include vinylcyclohexene oxide, allyl glycidyl ether, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, and the like. From the viewpoint of superiority, vinylcyclohexene oxide, which is a compound having an alicyclic epoxy group, is particularly preferable.

  Specific examples of the compound (γ) having an oxetanyl group include allyl oxetanyl ether and vinyl oxetanyl ether. When using the compound which has an oxetanyl group, it is preferable from a viewpoint that the toughness of hardened | cured material improves.

  Specific examples of the compound (γ) having a crosslinkable silicon group as a photopolymerizable functional group include those represented by the following general formula (II) from the viewpoint of availability and heat resistance.

(Wherein R ⁶ and R ⁷ represent an organic group having 1 to 6 carbon atoms, n represents 1 to 3, and m represents a number of 0 to 10) and have a crosslinkable silicon group. In view of easy removal of by-products after the reaction, trimethoxyvinylsilane, triethoxyvinylsilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, methoxydimethylvinylsilane, and ethoxydimethylvinylsilane are particularly preferable.

  Examples of the compound (γ) having an acryloyl group or a methacryloyl group as a photopolymerizable functional group include allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth). Acrylate, (meth) acrylic acid-modified allyl glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol acrylate DA111).

Further, from the viewpoint of high selectivity for hydrosilylation, a compound in which a methacryloyl group coexists with an allyl or vinyl group in the same molecule is preferable, and allyl methacrylate, vinyl methacrylate, and the like are particularly preferable in terms of availability.
Moreover, in the case of hydrosilylation reaction, 2 or more types of compounds ((gamma)) can also be used together regardless of the kind of photopolymerizable functional group.

(Hydrosilylation catalyst)
A known hydrosilylation catalyst may be used as a catalyst for the hydrosilylation reaction of the compounds (α) and (β).

  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.

The addition amount of the catalyst is not particularly limited, but the lower limit of the preferred addition amount is a carbon-carbon double bond having reactivity with the SiH group charged at the time of the reaction (hereinafter simply referred to as “additional amount”). It is sometimes referred to as an “alkenyl group.”) 10 ⁻⁸ mol, more preferably 10 ⁻⁶ mol, relative to 1 mol, and the preferred upper limit of the amount added is 10 ^{−1 with} respect to 1 mol of the alkenyl group of the above compound. Mol, more preferably 10 ^-2 mol.

In addition, a cocatalyst can be used in combination with the above catalyst. Examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, 2-hydroxy-2-methyl-1 Examples include acetylene alcohol compounds such as butyne and 1-ethynyl-1-cyclohexanol, and sulfur compounds such as simple sulfur. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ⁻² mol, more preferably 10 ⁻¹ mol, and the upper limit of the preferable addition amount is 10 ^2. Mol, more preferably 10 mol.

(Reaction method of hydrosilylation)
The proportion of each compound to be reacted is not particularly limited. When the total alkenyl group amount of the compound (α) to be reacted is A and the total SiH group amount of the compound (β) to be reacted is B, 1.5 ≦ A / B ≦ 20 is preferable, and 1.5 ≦ A / B ≦ 10 is more preferable. When this value is small, there is a possibility of gelation, and when it is large, a large amount of unreacted alkenyl compound is contained, which may cause coloring of the composition and white turbidity.

  Although various reaction temperatures can be set, in this case, the lower limit of the preferred temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferred temperature range is 200 ° C., more preferably 150 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required.

  Various reaction times and pressures during the reaction can be set as required. Oxygen can be used during the hydrosilylation reaction. The hydrosilylation reaction can be promoted by adding oxygen to the gas phase portion of the reaction vessel. From the point of setting the amount of oxygen to be below the lower limit of explosion limit, the oxygen volume concentration in the gas phase must be controlled to 3% or less. The oxygen volume concentration in the gas phase is preferably 0.1% or more, more preferably 1% or more, from the viewpoint that the effect of promoting the hydrosilylation reaction by addition of oxygen is observed.

  A solvent may be used during the hydrosilylation reaction. Solvents that can be used are not particularly limited as long as they do not inhibit the hydrosilylation reaction. Specifically, hydrocarbon solvents such as benzene, toluene, hexane, heptane, tetrahydrofuran, 1,4-dioxane, 1, Ether solvents such as 3-dioxolane and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent can also be used as a mixed solvent of two or more types. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable. The amount of solvent to be used can also be set as appropriate.

  In the above production method of the polysiloxane compound of the present invention, various additives can be used depending on the purpose.

(Ingredient (B))
The component (B) of the present invention will be described.

  The component (B) is not particularly limited as long as it is a compound having a SiH group. It is the same as the above-mentioned compound (β), and preferred embodiments are also preferred.

  Moreover, the hydrosilylation reaction product of the above-mentioned compound ((alpha)) and a compound ((beta)) is preferable from a viewpoint that it is excellent in compatibility with a component (A). In order to obtain the component (B) by hydrosilylation reaction, 1.5 ≦ B / A ≦ 20, where A is the total alkenyl group amount of the compound to be reacted and B is the total SiH group amount of the compound to be reacted. It is preferable that 1.5 ≦ B / A ≦ 10. When this value is small, there is a possibility of gelation, and when it is large, a large amount of unreacted SiH compound is contained, which causes separation and white turbidity.

(About alkali-developable groups)
In the component (A) and component (B) of the present invention, any structure in the group consisting of each structure represented by the following formulas (X1) to (X3) in the molecule, a phenolic hydroxyl group, and a carboxyl group It is preferable to use a material having a photo-resisting property because it can be dissolved in an alkaline aqueous solution and can provide a photoresist function capable of alkali development.

As a method for easily obtaining a polysiloxane compound having the following specific structure, it can be obtained by using the following compound (α2) in place of the above-mentioned compound (α).
(Α2) each structure having an alkenyl group and represented by the following formulas (X1) to (X3);

Compound having at least one selected from the group consisting of phenolic hydroxyl group and carboxyl group in the same molecule From the viewpoint that the resulting cured product is less colored at high temperature, among these organic structures, the carboxyl group and the above A structure selected from formulas (X1) to (X3) is preferable.

  Although it does not necessarily limit as a compound ((alpha) 2), From a viewpoint with few coloring at the time of high temperature, following general formula (IV) which has an isocyanuric ring

(In the formula, R ² represents a monovalent organic group having 1 to 50 carbon atoms, and each R ² may be different or the same, and at least one R ² represents reactivity with the SiH group. It is preferable to use at least one compound represented by (including a carbon-carbon double bond having).

  Examples of the organic group include a hydrocarbon group (which may be partially substituted with oxygen) and an epoxy group. From the viewpoint of availability, a phenyl group, a methyl group, an ethyl group, a propyl group, a benzyl group, and a glycidyl group. Group, and the organic group having a carbon-carbon double bond having reactivity with the SiH group is preferably an allyl group or a vinyl group.

  From the viewpoint of availability, diallyl isocyanuric acid, monoallyl isocyanuric acid, vinylphenol, allylphenol, diallyl bisphenol A, diallyl bisphenol S,

Butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid and undecylenic acid are preferred. Among these, diallyl isocyanuric acid, monoallyl isocyanuric acid, diallyl bisphenol A, diallyl bisphenol S, vinyl phenol, and allyl phenol are preferable from the viewpoint of particularly high heat resistance, and diallyl isocyanuric acid from the viewpoint of transparency of the cured product, Monoallyl isocyanuric acid is particularly preferred.

  In addition, the compound (α2) can be used singly or in combination of two or more types, and can also be hydrosilylated in combination with the compound (α).

  In the use ratio of the component (A) to the component (B) in the present invention, when the total alkenyl group amount of the component (A) is A and the total SiH group amount of the component (B) is B, 0.5 ≦ B /A≦5.0 is preferable, and in the case of 0.5> B / A, the number of unreacted alkenyl groups increases so that the heat resistance of the resulting cured product is lowered, which is not preferable. Further, in the case of B / A> 5.0, the amount of unreacted SiH groups increases too much, and the resulting cured product becomes brittle and cracks, foaming and the like are not preferable.

(Component C)
The component (C) of the present invention will be described.

  About the component (C) of this invention, it is necessary to select suitably according to the kind of photopolymerization functional group, and in the case of an epoxy group, an alkoxysilyl group, etc., a cationic polymerization initiator is used, allyloxy, a methacryloxy group, etc. In the case of the radical polymerizable group, a photo radical initiator is used.

(Cationic polymerization initiator)
The cationic polymerization initiator is particularly limited as long as it is an active energy ray cationic polymerization initiator that generates a cationic species or Lewis acid by active energy rays, or a thermal cationic polymerization initiator that generates a cationic species or Lewis acid by heat. It can be used without being.

Active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds, bis (perfluoroalkylsulfonyl) methane metal salts, aryldiazonium compounds, aromatic onium salts of group VIa elements, group Va elements aromatic onium salts of, dicarbonyl chelate, thiopyrylium salts IIIa~Va group element, MF6 ^- form of VIa elements anion (wherein M is selected from phosphorus, antimony and arsenic), arylsulfonium complex salts, aromatic Iodonium complex salt and aromatic sulfonium complex salt, bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluorometal salt (for example, phosphate, arsenate, antimonate, etc.); anion is B (C ₆ F ₅ ) ₄ ^- it can be one or more wraps of the aromatic iodonium complex salts and aromatic sulfonium complex salt It is.

  Preferred 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) ), BBI-102, BBI-103, and BBI-105 (Midori Chemical).

  The amount of the cationic polymerization initiator used is preferably an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, with the total amount of component (A) + component (B) being 100 parts by weight. When the amount of the cationic polymerization initiator is small, it takes a long time for curing or a cured product that is sufficiently cured cannot be obtained. When the amount of the initiator is large, the color of the initiator remains in the cured product, coloring or bulging due to rapid curing, or the heat and light resistance of the cured product is impaired.

  (Photo radical initiator) Any radical energy initiator that generates radical species by active energy rays can be used without any particular limitation.

  Active energy ray radical polymerization initiators include 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-propan-1-one Etc.

  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-benzoyloxime) )], 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 radical polymerization initiators may be used alone or in combination of two or more. The amount of radical polymerization initiator used is preferably 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total weight of component (A) + component (B). It is. When the amount of the cationic polymerization initiator is small, there is a tendency that the curing is insufficient and a contrast cannot be obtained during alkali development. A large amount of initiator is not preferable because the cured film itself is colored.

(Component (D))
The component (D) of the present invention will be described.
About the component (D) of this invention, the thing similar to an above-mentioned hydrosilylation catalyst can be used as a catalyst in the case of hydrosilylating a compound ((alpha)) and ((beta)).

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.
The amount of component (D) used is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the total weight of (A) + component (B). is there. When the addition amount is small, there is a tendency that curing is insufficient and sufficient insulation cannot be obtained. Moreover, when there is much addition amount, since the stability at the time of the storage of a curable composition will fall and handleability will worsen, it is unpreferable.

(Method for adjusting curable composition and curing method)
The preparation method of a curable composition is not specifically limited, It can prepare with various methods. Various components may be mixed and prepared immediately before curing, or may be stored at a low temperature in a one-component state in which all components are mixed and prepared in advance.

  The method of using the curable composition of the present invention is not particularly limited, and can be used by spin coating, slit coating, dispensing potting, or the like. Further, viscosity adjustment with a solvent and surface tension adjustment with a surfactant may be appropriately performed according to the state of the substrate.

Moreover, the resin composition of this invention can be made into hardened | cured material by making a crosslinking reaction advance by light irradiation. As a light source that can be used at that time, a light source that emits light having an absorption wavelength of a polymerization initiator or a sensitizer to be used may be used, and a light source having a wavelength in the range of 200 to 450 nm is preferable. Specifically, for example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a carbon arc lamp, a light emitting diode, or the like can be used. The exposure amount is not particularly limited, but a preferable exposure amount range is 1 to 5000 mJ / cm ² , more preferably 1 to 1000 mJ / cm ² . If the exposure is small, it will not cure. If the exposure amount is large, the color may change due to rapid curing. A preferred curing time range is 1 to 120 seconds, more preferably 1 to 60 seconds. When the curing time is long, the characteristics of rapid curing of photocuring are not utilized.

  The heating temperature after the film formation is not particularly limited, but is preferably 250 ° C. or less, and preferably 200 ° C. or less from the viewpoint that the influence on the peripheral low heat-resistant member is small. When using a resin substrate or the like, the temperature is preferably 160 ° C. or lower in consideration of dimensional stability and the like.

(About photolithography)
The curable composition of the present invention can be finely patterned by development. The patterning formation is not particularly limited, and a desired pattern can be formed by dissolving / removing the unexposed portion by a commonly used developing method such as an immersion method or a spray method.

  In particular, in the components (A) and (B) of the present invention, any structure in the group consisting of each structure represented by the formulas (X1) to (X3) in the molecule, a phenolic hydroxyl group, and a carboxyl group It is preferable to use a material having a photo-resisting property because it can be dissolved in an alkaline aqueous solution and can provide a photoresist function capable of alkali development.

  Moreover, the structure chosen from Formula (X1)-(X3) in these organic structures from a viewpoint that the hardened | cured material obtained has little coloring at the time of high temperature is preferable.

  Alkaline development enables the formation of large areas using photolithographic equipment used in general semiconductor manufacturing and display manufacturing, and the improvement of pattern accuracy uniformity. This is preferable because it is advantageous in terms of cost.

  The developer used for development can be used without particular limitation as long as it is generally used. Specific examples include organic solvents that are available at low cost, for example, ketone solvents such as acetone, MEK, and MIBK. And alcohol solvents such as methanol and ethanol, and ester solvents such as ethyl acetate and butyl acetate. In the case of alkaline development, an organic alkaline aqueous solution such as tetramethylammonium hydroxide aqueous solution or choline aqueous solution, or an inorganic alkaline aqueous solution such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution or lithium carbonate aqueous solution. And those obtained by adding an alcohol or a surfactant to these aqueous solutions in order to adjust the dissolution rate and the like.

  The aqueous solution concentration is preferably 25% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less from the viewpoint that the contrast between the exposed part and the unexposed part is easily obtained. preferable.

(About insulation)
The cured product obtained from the composition of the present invention can be applied to electronic components that require high insulation. The thin film of the present invention and any of the above semiconductor layers can be applied as an insulating film without any particular limitation. For example, the present invention can be applied to a gate insulating film such as a TFT insulating film and a passivation film, which are thin and require high insulating properties.

When an electric device such as a thin film transistor is formed, if there is a leakage current or the like in the insulating layer, it leads to signal response delay, malfunction, and device failure, so that the insulating film is required to have high insulating properties. However, an insulating film formed from a conventional resin composition that can be formed by solution coating cannot be applied because the amount of leakage current when a voltage is applied to the thin film is too large. Insulation requires that the amount of leakage between electrodes when a voltage of 30 V is applied to a thin film of 0.5 μm or less formed between electrodes is 20 nA / cm ² or less, but further considers the reliability of electronic components Then it is preferably 12Na / cm ² or less, and more preferably 6 nA / cm ² or less.

  In particular, in the components (A) and (B) of the present invention, any structure in the group consisting of each structure represented by the formulas (X1) to (X3) in the molecule, a phenolic hydroxyl group, and a carboxyl group Among these organic structures, it is particularly preferable to have a structure selected from the formulas (X1) to (X3) because the insulating properties of the thin film made of the composition used are improved.

  As for the film thickness of the insulating film, the thicker the film, the higher the insulation reliability and the smaller the amount of leakage current between the electrodes. However, when applied to insulating films such as LSI elements and TFTs, In order to make the device finer and thinner, it is preferable to have a high insulation property with a thinner film thickness, and the thickness of the insulating film is also preferably 1.0 μm or less, more preferably 0.6 μm or less. More preferably, the inter-electrode leakage current amount is as shown above at a film thickness of 0.3 μm or less. Further, in order to obtain a multilayer structure in the formation of a transistor, it is preferable that the insulation is maintained with a thinner film thickness, and more preferably the inter-electrode leakage current amount as described above in a thin film of 0.2 μm or less. It is preferable.

  Furthermore, this insulating film is also excellent in environmental resistance. It is 20 ° C. to 90 ° C., preferably 20 ° C. to 90 ° C., preferably 20 ° C. to 90 ° C. Even when it is stored for a long time under high temperature and high humidity conditions of -100% RH, preferably 50-100% RH, its insulating properties can be maintained.

  The applied voltage is not a problem as long as the leakage current at a voltage applied as a normal TFT drive voltage is small, but it is preferably 0 in consideration of long-term reliability and instantaneous overvoltage immediately after application. It is preferable that the level of low leakage current is at any voltage value between 10V and 10V, and more preferably, the insulation at the level shown above is maintained at 0-25V regardless of AC voltage or DC voltage. Is preferred.

(Additive)
(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 the compound to be added 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, and 9,10-di. Ethoxyanthracene, 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 can be mentioned, and from the viewpoint of easy availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene and the like preferable.

  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 series include thioxanthone, 2-chlorothioxanthone, 2,5-diethyldioxanthone and the like.
These sensitizers may be used alone or in combination of two or more.

(Reactive diluent)
A reactive diluent can be appropriately added to the curable composition of the present invention in order to adjust workability, reactivity, adhesiveness, and strength of the cured product. The compound to be added can be selected according to the curing reaction mode and used without any particular limitation, and a compound having a polymerization group such as an epoxy compound, an oxetane compound, an alkoxysilane compound, or a (meth) acrylate compound is used.

  Specific examples of epoxy compounds and oxetane compounds include novolak phenol type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, cyclohexyl epoxy group-containing polyorganosiloxanes (cyclic and chain), glycidyl group-containing polyorganosiloxanes ( Cyclic, chain), bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxysilane) Rohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, 1,4-bis {(3-ethyl-3-oxetanyl) methoxy } Methyl} benzene, bis {1-ethyl (3-oxetanyl)} methyl ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, etc. be able to.

  Specific examples of the alkoxysilane compound include tetramethoxy (ethoxy) silane and its condensate, methyltrimethoxy (ethoxy) silane and its condensate, dimethyldimethoxy (ethoxy) silane and its condensate.

  Specific examples of (meth) acrylate compounds include allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and (meth) acrylic acid. Modified allyl glycidyl ether (manufactured by Nagase ChemteX, trade name: Denacol acrylate DA111), urethane (meth) acrylates, epoxy (meth) acrylates, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Ditrimethylolpropane (meth) tetraacrylate, dipentaerythritol hexa (meth) acrylate, butanediol di (meth) acrylate, nonanediol di (meth) acrylate, polypropylene glycol System (meth) acrylate, bisphenol A di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and (meth) acrylate group-containing polyorganosiloxane.

  Although the amount of reactive diluent added can be variously set, the preferred amount added is 1 to 50 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight of the modified polyorganosiloxane compound. If the addition amount is small, the addition effect does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  In addition, in order to advance the photocrosslinking reaction of these reactive diluents, when adding an epoxy or alkoxylane compound, respectively, a photocationic polymerization initiator represented by an onium salt is used, and when an acrylate compound is added. In addition, a radical photopolymerization initiator such as an acetophenone compound, a benzophenone compound, or an acyl phosphine oxide compound may be added.

(Adhesion improver)
An adhesion improver can also be added to the curable composition of the present invention. In addition to commonly used adhesives as adhesion improvers, for example, various coupling agents, epoxy compounds, oxetane compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, α-methylstyrene -Vinyl toluene copolymer, polyethyl methyl styrene, aromatic polyisocyanate, etc. can be mentioned.

  An example of the coupling agent is a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.

  The amount of the silane coupling agent can be variously set, but is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, and still more preferably, with respect to 100 parts by weight of the modified polyorganosiloxane compound. 0.5 to 5 parts by weight. When the addition amount is small, the effect of improving the adhesiveness does not appear, and when the addition amount is large, the curability and the physical properties of the cured product may be adversely affected. These coupling agents, silane coupling agents, epoxy compounds, etc. may be used alone or in combination of two or more.

(Thermoplastic resin)
Various thermoplastic resins may be added to the curable composition for the purpose of modifying the properties. Various thermoplastic resins can be used. For example, a homopolymer of methyl methacrylate or a polymethyl methacrylate resin such as a random, block or graft polymer of methyl methacrylate and other monomers (for example, Hitachi Chemical) Optretz, etc.), acrylic resins represented by polybutyl acrylate resins such as butyl acrylate homopolymers or random, block or graft polymers of butyl acrylate and other monomers, bisphenol A, 3, A polycarbonate resin such as a polycarbonate resin containing 3,5-trimethylcyclohexylidenebisphenol or the like as a monomer structure (for example, APEC manufactured by Teijin Limited), a norbornene derivative, a vinyl monomer, or the like is copolymerized alone or copolymerized. Cycloolefin resins such as fat, norbornene derivative ring-opening metathesis polymer, or hydrogenated products thereof (for example, APEL manufactured by Mitsui Chemicals, ZEONOR, ZEONEX manufactured by Nippon Zeon, ARTON manufactured by JSR, etc.), ethylene and Olefin-maleimide resins such as maleimide copolymers (eg TI-PAS manufactured by Tosoh Corporation), bisphenols such as bisphenol A and bis (4- (2-hydroxyethoxy) phenyl) fluorene, and diols such as diethylene glycol Polyester resins such as polyester obtained by polycondensation of phthalic acids and aliphatic dicarboxylic acids such as terephthalic acid and isophthalic acid (eg O-PET manufactured by Kanebo Co., Ltd.), polyethersulfone resins, polyarylate resins, polyvinyl acetal resins, Polyethylene resin Polypropylene resins, polystyrene resins, polyamide resins, silicone resins, other like fluorine resin, not natural rubber, but the rubber-like resin is exemplified such EPDM is not limited thereto.

  The thermoplastic resin may have a crosslinkable group. Examples of the crosslinkable group in this case include an epoxy group, an amino group, a radical polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, and an alkoxysilyl group. From the viewpoint that the heat resistance of the obtained cured product tends to be high, it is preferable to have one or more crosslinkable groups in one molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10000 or less, and preferably 5000 or less in that the compatibility with the modified organosiloxane compound is likely to be good. More preferred. On the contrary, the number average molecular weight is preferably 10,000 or more, and more preferably 100,000 or more in that the obtained cured product tends to be tough. The molecular weight distribution is not particularly limited, but the molecular weight distribution is preferably 3 or less, more preferably 2 or less, in that the viscosity of the mixture tends to be low and the moldability tends to be good. More preferably, it is as follows.

  Although there is no limitation in particular as a compounding quantity of a thermoplastic resin, the range of the preferable usage-amount is 5 to 50 weight% of the whole curable composition, More preferably, it is 10 to 30 weight%. If the amount added is small, the resulting cured product tends to be brittle. If the amount added is large, the heat resistance (elastic modulus at high temperature) tends to be low. A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

  The thermoplastic resin may be dissolved in the modified polyorganosiloxane compound and mixed in a uniform state, pulverized and mixed in a particle state, or dissolved in a solvent and mixed to be in a dispersed state. Good. From the viewpoint that the resulting cured product tends to be more transparent, it is preferable to dissolve in the modified polyorganosiloxane compound and mix in a uniform state. In this case as well, the thermoplastic resin may be directly dissolved in the modified polyorganosiloxane compound, or may be mixed uniformly using a solvent, etc., and then the solvent is removed to obtain a uniform dispersed state and / or mixture. It is good also as a state.

  When the thermoplastic resin is dispersed and used, the average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 10 μm. There may be a distribution of the particle system, which may be monodispersed or have a plurality of peak particle sizes, but from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good, The diameter variation coefficient is preferably 10% or less.

(Filler)
You may add a filler to a curable composition as needed. Various fillers are used. For example, silica-based fillers such as quartz, fume silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, silicon nitride, silver powder, etc. Inorganic fillers such as alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloon As a filler for a conventional sealing material such as an epoxy type, a filler that is generally used or / and proposed can be used.

(Anti-aging agent)
An aging inhibitor may be added to the curable composition of the present invention. Examples of the anti-aging agent include citric acid, phosphoric acid, sulfur-based anti-aging agent and the like in addition to the anti-aging agents generally used such as hindered phenol type. As the hindered phenol-based anti-aging agent, various types such as Irganox 1010 available from Ciba Specialty Chemicals are used.

  Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides. Moreover, these anti-aging agents may be used independently and may be used together 2 or more types.

(UV absorber)
An ultraviolet absorber may be added to the curable composition of the present invention. Examples of the ultraviolet absorber include 2 (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. Can be mentioned. Moreover, these ultraviolet absorbers may be used independently and may be used together 2 or more types.

(solvent)
When the modified polyorganosiloxane compound used in the curable composition of the present invention has a high viscosity, it can be used by dissolving in a solvent. Solvents that can be used are not particularly limited. 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, ketone 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, A halogen-based solvent such as 1,2-dichloroethane can be preferably used.

  As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane, propylene glycol-1-monomethyl ether-2-acetate, and chloroform are preferable.

  Although the amount of solvent to be used can be set as appropriate, the lower limit of the preferred amount of use for 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferred amount of use is 10 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as a low viscosity, and if the amount used is large, the solvent tends to remain in the material, causing problems such as thermal cracks, and also from a cost standpoint. 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 ions such as a colorant, a release agent, a flame retardant, a flame retardant aid, a surfactant, an antifoaming agent, an emulsifier, a leveling agent, an anti-fogging agent, and antimony-bismuth. Trapping agent, thixotropic agent, tackifier, storage stability improver, ozone degradation inhibitor, light stabilizer, thickener, plasticizer, reactive diluent, antioxidant, heat stabilizer, conductivity The purpose and effect of the present invention include an imparting agent, an antistatic agent, a radiation shielding agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent, and a physical property modifier. It can be added as long as it is not impaired.

(Application)
The curable composition of the present invention can easily form fine contact holes and the like by photolithography, and the obtained cured product is excellent in insulation in a thin film, and thus high insulation is required. The present invention can be applied to an electronic component such as a passivation film or a gate insulating film of a thin film transistor.

  In addition, transparent materials, optical materials, optical lenses, optical films, optical sheets, optical component adhesives, optical waveguide coupling optical adhesives, optical waveguide peripheral member fixing adhesives, DVD bonding adhesives, adhesives, Dicing tape, electronic materials, insulating materials (including printed circuit boards, wire coatings, etc.), high-voltage insulating materials, interlayer insulating films, TFT passivation films, TFT gate insulating films, TFT interlayer insulating films, TFT transparent flattening Membrane, insulating packing, insulation coating material, adhesive, high heat resistant adhesive, high heat dissipation adhesive, optical adhesive, LED element adhesive, various substrate adhesive, heat sink adhesive, paint, UV powder Body paint, ink, colored ink, UV inkjet ink, coating material (hard coat, sheet, film, release paper coat, optical disc coat, optical fabric ), Molding materials (including sheets, films, FRP, etc.), sealing materials, potting materials, sealing materials, light-emitting diode sealing materials, optical semiconductor sealing materials, liquid crystal sealing agents, display devices Sealing material, sealing material for electrical materials, sealing material for various solar cells, high heat resistant sealing material, resist material, liquid resist material, colored resist, dry film resist material, solder resist material, binder resin for color filter, color Transparent flattening material for filter, binder resin for black matrix, photo spacer material for liquid crystal cell, transparent sealing material for OLED element, stereolithography, solar cell material, fuel cell material, display material, recording material, vibration proof material , Waterproof materials, moisture-proof materials, heat-shrinkable rubber tubes, O-rings, photoconductor drums for copying machines, battery fixing The electrolyte can be applied to a gas separation membrane.

  Further, concrete protective materials, linings, soil injection agents, cold storage heat materials, sealing materials for sterilization treatment devices, contact lenses, oxygen permeable membranes, additives to other resins, and the like can be mentioned.

Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.
(Examples 1-6, Comparative Examples 1 and 2)
The curable compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated using the following methods. The results are shown in Table 1.

  The hardened | cured material obtained by hardening | curing the curable composition of this invention functions as a photocurable material which has the outstanding insulation compared with the composition of a comparative example.

(Photolithography)
A sample with a simple mask was applied to a glass plate (50 × 100 × 0.7 mm) by spin coating the curable composition obtained in Examples and Comparative Examples and partially covering the coated surface. It was prepared and exposed to an integrated light amount of 200 mJ / cm ² using a conveyor type exposure apparatus (high pressure mercury lamp, LH6 manufactured by Fusion).

  The exposed sample is immersed in an alkaline developer (tetramethylammonium hydroxide, 2.38% aqueous solution of TMAH) or acetone for 60 seconds and then washed with water to give a development contrast (exposed portion resin remains and unexposed portions are removed). ) Was evaluated as ◯, and a sample having no development contrast was evaluated as x.

(Insulation evaluation)
The following insulation evaluation samples were prepared using the resin compositions obtained in the above Examples and Comparative Examples. Using a conveyor type exposure apparatus (high pressure mercury lamp, LH6 manufactured by Fusion), a resin substrate spin-coated (rotation speed: 2000 rpm, 30 seconds) on a glass substrate on which a Mo film is formed in 2000 mm, is used for an integrated light quantity of 200 mJ / cm ^2. Exposed. Then, it heated on the hotplate heated at 150 degreeC for 1 hour, and formed the thin film. Further, an Al electrode (3 mmφ) was formed on the thin film by sputtering.

  For insulation, a semiconductor parameter measurement device (Agilent 4156C) is used to apply a voltage of 0 to 50 V in steps of 0.5 V between the electrodes (Mo-Al) sandwiching the insulating film. The leakage current amount per electrode unit area was measured and evaluated.

(Film thickness measurement)
The thin film formed on the substrate was calculated by measuring the UV-vis spectrum. A thin film prepared using the resin composition of the present invention has excellent insulating properties and can be applied as a thin film insulating material that can be formed by solution coating.

(Synthesis Example 1)
A 500 mL four-necked flask was charged with 100 g of toluene and 50 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed liquid of 6.9 g of triallyl isocyanurate, 6.9 g of toluene, and 0.0043 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped. After dropping, the disappearance of the SiH group-derived peak was confirmed by ¹ H-NMR, and the reaction was completed. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a colorless and transparent liquid “Reactant A”. ¹ H-NMR measurement confirmed that the polysiloxane compound had 9.0 mmol / g of SiH groups in terms of equivalents when the standard substance was dibromoethane.

(Synthesis Example 2)
A 500 mL four-necked flask was charged with 100 g of toluene, 15 g of triallyl isocyanurate, 7.48 g of vinylcyclohexene oxide, and 0.0078 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), and the gas phase portion was purged with nitrogen The mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 4.8 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 4.8 g of toluene was dropped. After dropping, the disappearance of the SiH group-derived peak was confirmed by ¹ H-NMR, and the reaction was completed. Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product B”. ¹ H-NMR measurement confirmed that the polysiloxane compound had an alkenyl group of 5.5 mmol / g and an epoxy group of 2.0 mmol / g in terms of equivalent when the standard substance was dibromoethane.

(Synthesis Example 3)
A 500 mL four-necked flask was charged with 100 g of toluene, 15 g of triallyl isocyanurate, 6.96 g of trimethoxyvinylsilane, and 0.0078 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), and the gas phase was replaced with nitrogen. The mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 4.8 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 4.8 g of toluene was dropped. After dropping, the disappearance of the SiH group-derived peak was confirmed by ¹ H-NMR, and the reaction was completed. Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product C”. ¹ H-NMR measurement confirmed that the polysiloxane compound had an alkenyl group of 5.0 mmol / g and an alkoxysilyl group of 5.5 mmol / g in terms of equivalent when the standard substance was dibromoethane.

(Synthesis Example 4)
A 500 mL four-necked flask was charged with 100 g of toluene, 20 g of diallyl isocyanuric acid, 7.48 g of vinylcyclohexene oxide and 0.0234 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), and the gas phase portion was purged with nitrogen. The mixture was heated and stirred at an internal temperature of 105 ° C. A mixed solution of 4.8 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 4.8 g of toluene was dropped. After dropping, the disappearance of the SiH group-derived peak was confirmed by ¹ H-NMR, and the reaction was completed. Toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid “Reaction product D”. ¹ H-NMR measurement confirmed that the polysiloxane compound had an alkenyl group of 4.5 mmol / g and an epoxy group of 1.5 mmol / g in terms of equivalent when the standard substance was dibromoethane.

(Examples 1-5)
Reaction products obtained in Synthesis Examples 1 to 4, hydrosilylation catalyst (xylene solution of platinum vinylsiloxane complex), photopolymerization initiator (iodonium salt-based initiator, manufactured by Rhodia, trade name: PI2074), solvent (PGMEA) Were prepared at a ratio shown in Table 1 to prepare a photocurable composition.

(Comparative Example 1)
A 100 mL four-necked flask was charged with 15 g of toluene and 7.5 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase was purged with nitrogen and heated at an internal temperature of 105 ° C., where vinylcyclohexene oxide 5 0.0 g was added and stirred for 2 hours. Two hours after the addition, the reaction rate of the vinyl group was confirmed to be 95% or more by ¹ H-NMR. The reaction solution was cooled to obtain “Comparative Reaction Product 1”.

  A 20% PGMEA solution was prepared by adding 0.5 g of the obtained “Comparative Reaction Product 1” and 0.01 g of PI2074 (manufactured by Rhodia, photocationic polymerization initiator).

(Comparative Example 2)
A 20% PGMEA solution was prepared by adding 0.015 g of Irgacure 184 (manufactured by Ciba Specialty Chemicals, photo radical initiator) to 0.5 g of ditrimethylolpropane tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., DA-TMP).

Claims (8)

As essential components, (A) a polysiloxane compound having an alkenyl group and a photopolymerizable functional group in the same molecule (excluding polyhedral polysiloxane compounds), (B) having a SiH group, component (A) A compound different from the compound of (C), (C) a photopolymerization initiator and (D) a hydrosilylation catalyst,
Alkenyl groups with component (A) is an allyl group or a vinyl group, a photopolymerizable functional group is an epoxy group, a crosslinkable silicon group, Tsu least one Der selected from the group consisting of oxetanyl group and vinyloxy group And
Component (A) is
(Α) a compound having an alkenyl group,
(Β) a compound having two or more SiH groups, and
(Γ) Compound having at least one alkenyl group and one or more photopolymerizable functional groups
A curable composition characterized by being a hydrosilylation reaction product . The total alkenyl group amount of the compound (alpha) A, when the total SiH content of the compound (beta) and by B, according to claim 1, wherein it is 1.5 ≦ A / B ≦ 20 Curable composition. The curable composition according to claim 1 or 2 , wherein the photopolymerizable functional group of the component (A) is an epoxy group. The curable composition according to claim 1 or 2 , wherein the photopolymerizable functional group of the component (A) is an alkoxylyl group. Component (A) or Component (B) 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: Component (A) or Component (B) contains at least one selected from the group consisting of each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. The curable composition according to any one of claims 1 to 5 .

A thin film transistor characterized by using a thin film obtained by curing composition according to any one of claims 1 to 6 as a passivation film of a semiconductor layer. A thin film transistor characterized by using a thin film obtained by curing composition according to any one of claims 1 to 6 as a gate insulating film of the semiconductor layer.