JP6021866B2 - Photocurable composition and insulating thin film and thin film transistor using the same - Google Patents

Description

The present invention relates to a curable composition containing a modified polyorganosiloxane compound having a specific structure.

In general, photocurable materials are applied to various applications, but most of the resist materials that are one of the materials are resin materials such as novolak resins, acrylic acid copolymers, and polyamic acids, especially in the field of electronic materials. It is widely used in the center and is shown in Patent Documents 1 to 3 and the like.

However, these representative materials also lack high reliability (thermal decomposition, cracking, peeling, etc.) and transparency at high temperatures exceeding 200 ° C., so that high temperatures such as photosensitivity, heat resistance, transparency, etc. No satisfactory material has been obtained in terms of both time and reliability.

Japanese Patent No. 3203843 JP 2005-266673 A JP-A-4-218051

In view of the above circumstances, an object of the present invention is to provide a curable composition that provides a cured product having photocurability and excellent heat-resistant transparency.

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). As an essential component, (A) a compound having an alkenyl group, (B) a SiH group, and each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group A curable composition comprising a modified polyorganosiloxane compound having at least one selected from the group in the same molecule, and (C) a photoactive platinum complex curing catalyst.

2). (A) a compound having an alkenyl group, (B) (α1) having a alkenyl group and represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group Curability comprising a SiH group-containing modified polyorganosiloxane obtained by reacting a compound having at least one selected with (β) a polyorganosiloxane compound having two or more SiH groups, and (C) a photoactive platinum complex curing catalyst. Composition.

3). The curable composition as described in 1) or 2), wherein the component (A) is an organic compound having an alkenyl group.

4). Component (A) is represented by the following general formula (I)

(Wherein R ³ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, each R ³ may be different or the same, and at least one R ³ may be a SiH group; The curable composition according to any one of 1) to 3), which includes a reactive carbon-carbon double bond).

5). The curable composition according to any one of 1), 3) and 4), wherein the component (B) is a hydrosilylation reaction product of the following compounds α1 and β:
(Α1) Organic having an alkenyl group and at least one selected from the group consisting of each structure represented by formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group in the same molecule Compound,
(Β) A polyorganosiloxane compound having two or more SiH groups in one molecule.

6). (Β) is a linear and / or cyclic polyorganosiloxane compound having two or more SiH groups in one molecule, and the curable composition according to any one of 2) to 5).

7). Compound (β) is represented by the following general formula (II)

(Wherein R ² and R ³ represent an organic group having 1 to 10 carbon atoms, n represents 1 to 10, m represents 0 to 10, and m + n ≧ 3 represents an SiH group) The curable composition according to any one of 2) to 6), which is a cyclic polyorganosiloxane compound.

8). The same molecule having at least one selected from the group consisting of (A) an alkenyl group as an essential component and each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group Modified polyorganosiloxane compound, (B) a compound having two or more SiH groups in one molecule,
(C) A curable composition containing a photoactive platinum complex curing catalyst.

9). (A) (α1) a compound having an alkenyl group and having 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 ( β) a modified polyorganosiloxane having a group obtained by reacting a polyorganosiloxane compound having two or more SiH groups, (B) a compound having two or more SiH groups in one molecule, (C) a photoactive type A curable composition containing a platinum complex curing catalyst.

10). The curable composition according to 8), wherein the component (A) is a hydrosilylation reaction product of the following compounds α1 and β:
(Α1) has an alkenyl group and has 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 in the same molecule. Organic compounds,
(Β) A polyorganosiloxane compound having two or more SiH groups in one molecule.

11). (Β) is a linear and / or cyclic polyorganosiloxane compound having two or more SiH groups in one molecule, 9) or 10) curable composition according to 10).

12). The curable composition according to any one of 8) to 11), wherein the component (B) is a hydrosilylation reaction product of the following compounds α2 and β:
(Α2) an organic compound having an alkenyl group,
(Β) A linear and / or cyclic polyorganosiloxane compound having 3 or more SiH groups in one molecule.

13). The curable composition according to any one of 1) to 12), wherein the component (C) is a β-diketone platinum complex.

14). An insulating film obtained using the curable composition according to any one of 1) to 13).

15). 14) A thin film transistor, wherein the insulating film according to 14) is a passivation film of a semiconductor layer.

16). 14) A thin film transistor, wherein the insulating film according to 14) is a gate insulating film.

According to the present invention, it is a curable composition containing a modified polyorganosiloxane compound, and can provide a photocurable material having excellent optical transparency.

The details of the invention will be described.

The resin composition of the present invention can provide a novel modified polyorganosiloxane compound capable of photocuring, and can provide a cured product and a thin film excellent in optical transparency and heat resistance after curing.
(Component A)
The component (A) of the present invention will be described.

It is a compound having an alkenyl group used in the curable composition of the present invention and can be used 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-tetramethylcyclo Tetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, 1,3,5,7,9 -Pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane, etc. Compounds.

Further, as the alkenyl group-containing polysiloxane compound, an alkenyl compound obtained by partially reacting a polysiloxane compound and an organic alkenyl compound can also be used. Specifically, a SiH group-containing polysiloxane compound and an organic alkenyl compound described later can be partially reacted by a hydrosilylation reaction, and can be used without any particular limitation.

Next, the alkenyl group-containing organic compound will be described. 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 one or more carbon-carbon double bonds having reactivity with SiH groups 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, and other like are replaced with an allyl group all glycidyl groups of a conventionally known epoxy resins.

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 viewpoint of high transparency, heat resistance, and light resistance.

(Wherein R ³ represents a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, each R ³ may be different or the same, and at least one R ³ may be a SiH group; A compound represented by (including a reactive carbon-carbon double bond) is preferable.

R ^{3 in the} general formula (I) is preferably a monovalent organic group having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. 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 ³ include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group and allyl group.

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.
(Component B)
Next, the component (B) of the present invention will be described.

The modified polyorganosiloxane compound, which is an essential component of the curable composition of the present invention, has each structure represented by the following formulas (X1) to (X3),

A group consisting of a phenolic hydroxyl group and a carboxyl group (hereinafter, “each structure represented by the above formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group” may be referred to as an “acidic group”). By having it in the same molecule, it can be dissolved in an aqueous alkali solution and can also be applied as a resist material capable of alkali development.

The modified polyorganosiloxane compound which is an essential component of the curable composition of the present invention is composed of a siloxane unit (Si—O—Si) and an organic group X composed of C, H, N, O and S as constituent elements. And a group consisting of each structure represented by the formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group (hereinafter referred to as “the above formulas (X1) to (X3)”). Each structure represented, phenolic hydroxyl group and carboxyl group "may be referred to as" acidic group ".) Alkaline aqueous solution by using a reaction product of a compound having at least one selected from the group and an organopolysiloxane compound Therefore, it can be applied as a resist material that can be developed with an alkali.

From the viewpoint that the resulting cured product is less colored at high temperatures, the structure contained in the compound is preferably at least one selected from a carboxyl group and the above formulas (X1) to (X3). From the viewpoint of obtaining a cured product having a low thermal decomposability, those having at least one structure selected from below are preferred.

In addition, among the siloxane units in the organopolosiloxane compound, the cured product obtained has a higher hardness as the content of T units (X ₃ SiO _3/2 ) or Q units (SiO _4/2 ) in the constituent components increases. Higher and more heat-resistant, and the higher the content of M units (X ₃ SiO _1/2 ) or D units (X ₂ SiO _2/2 ), the harder the cured product is. It is done.

The modified polyorganosiloxane compound used in the curable composition of the present invention can be obtained by various methods such as condensation reaction by hydrolysis, addition reaction, and ring-opening polymerization. There is no particular limitation on the method for introducing into the compound structure, but it is preferable to use hydrosilylation that can be introduced by a Si—C bond, which is a regioselective and chemically stable bond. .

As a suitable modified polyorganosiloxane compound for use in the curable composition of the present invention, the following two embodiments may be mentioned.

As a first preferred embodiment, hydrosilylation reaction products of the following compounds (α1) and (β) can be mentioned.
(Α1) Each structure having at least one carbon-carbon double bond having reactivity with a SiH group in one molecule and represented by the following formulas (X1) to (X3);

An organic compound having at least one selected from the group consisting of a phenolic hydroxyl group and a carboxyl group in the same molecule,
(Β) An organosiloxane compound having at least two SiH groups in one molecule.

(Compound α1)
The compound (α1) will be described.

Compound (α1) has each structure represented by the above formulas (X1) to (X3) in the molecule,
An organic compound having at least one carbon-carbon double bond having the structure of any of the group consisting of a phenolic hydroxyl group and a carboxyl group and having reactivity with a SiH group in the same molecule is used. .

The organic compound preferably contains only those selected from the group consisting of C, H, N, O, S and halogen as constituent elements.

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 carbon-carbon double bond having reactivity with the SiH group of the compound (α1) is not particularly limited and can be used. Vinyl, allyl, methallyl, acryl, methacryl, 2-hydroxy-3 -(Allyloxy) propyl group, 2-allylphenyl group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2 Examples include-(allyloxy) ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group, and vinyl ether group. In particular, a vinyl group and an allyl group are preferable from the viewpoint of reactivity.

The compound (α1) may have at least one carbon-carbon double bond having reactivity with the SiH group in one molecule. However, since the resulting cured product has a high crosslinking density, it has high heat reliability. Two or more are preferable, and three or more are more preferable.

The compound (α1) is a compound represented by the following general formula (III) having an isocyanuric ring from the viewpoint of less coloring at high temperatures.

(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 has reactivity with a SiH group. It is preferable to use a compound having at least one of the structures 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,

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 (α1) can be used singly or in combination of two or more kinds, and further, the compound (α1) and other alkenyl group compounds can be used in combination for the hydrosilylation reaction. The alkenyl compound applicable here is not particularly limited as long as it is a compound listed as the component (A).

As a second preferred embodiment, hydrosilylation reaction products of the following compounds (α2) and (β) can be mentioned.

(Compound α2)
The compound (α2) will be described.

As the component (B) of the present invention, a hydrosilylation reaction product of a compound having an alkenyl group (compound α2) and an organopolysiloxane compound having at least two SiH groups in one molecule (compound β) is used. Is preferable because the compatibility with the component (A) can be improved.

The compound (α2) mentioned here can be used without particular limitation as long as it is a compound having at least one alkenyl group in one molecule, and those listed as the component (A) are particularly limited. It can be used without.

(Compound β)
The compound (β) will be described.
The compound (β) is not particularly limited as long as it is an organopolysiloxane compound having at least two SiH groups in one molecule.

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 1-50, 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 particularly 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.

Among these, from the viewpoint that the heat resistance of the cured product is high,

^{(Wherein, R 15} represents an organic group having 1 to 6 carbon atoms, n represents a number from 0 to 50.)
Or

(Wherein R ^{1 to} R ⁸ are an epoxy group, a mercapto group, an organic group containing an amino group, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, An aryl group such as a phenyl group, a tolyl group, or the like, or a chloromethyl group, a trifluoropropyl group, a cyanoethyl group, etc. in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, etc. It is the same or different selected, preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

However, at least one of R ^{1 to} R ⁸ is an organic group containing a SiH group which is a crosslinking reaction of the present composition)

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

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

Among these, from the viewpoint of availability and reactivity with the compound (α1), the following general formula (II)

(Wherein R ² and R ³ represent an organic group having 1 to 6 carbon atoms and may be the same or different, n is 1 to 10, and m is a number of 0 to 10). Cyclic organopolysiloxanes having at least 3 SiH groups per molecule are preferred.

The substituents R ² and R ³ in the compound represented by the general formula (II) 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 (II) 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.

(Hydrosilylation catalyst)
A known hydrosilylation catalyst may be used as a catalyst when the compound (α1), the compounds (α1) and (α2), or (α2) is hydrosilylated with (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 may be referred to as an “alkenyl group.”) 10 ⁻⁸ mol, more preferably 10 ⁻⁶ mol per 1 mol, and the upper limit of the preferable addition amount is 10 ⁻¹ per 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 relative 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 ratio with which each compound is reacted is a compound having an alkenyl group and having at least one selected from the group consisting of each structure represented by formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. When obtaining a SiH group-containing modified polyorganosiloxane using a polyorganosiloxane compound having a SiH group, when the total amount of alkenyl groups of the compound to be reacted is A and the total amount of SiH groups of the compound to be reacted is B, 1 ≦ B / A ≦ 30 is preferable, and 1 ≦ B / A ≦ 15 is more preferable. When this value is small, unreacted alkenyl groups remain in the composition, causing coloring, and when it is large, many unreacted SiH groups remain, causing foaming and cracking during curing of the composition. It may become. In this case, it is preferable that the SiH group-containing modified polyorganosiloxane is less than 5 mol% of the alkenyl group used and further substantially free of alkenyl groups.

The reaction temperature can be variously set. In this case, the lower limit of the preferable temperature range is 30 ° C., more preferably 50 ° C., and the upper limit of the preferable 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.

Further, it can be used as Component A of the present invention by a method using a hydrosilylation reaction of the compounds (α1), (α2) and (β).

Polyorganosiloxane compound having an alkenyl group and a compound having at least one selected from the group consisting of each structure represented by formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group, and a SiH group When the alkenyl group-containing modified polyorganosiloxane is obtained using A, the total alkenyl group amount of the compound to be reacted is A, and the total SiH group amount of the compound to be reacted is B, 1 ≦ A / B ≦ 30 It is preferable that 1 ≦ A / B ≦ 10. When this value is small, the alkenyl group in the composition disappears due to the reaction and gelation may occur in some cases, which is not preferable, and when it is large, many unreacted alkenyl groups remain. Is not preferred because it causes problems such as being easily colored. In this case, it is preferable that the alkenyl group-containing modified polyorganosiloxane is less than 5 mol% of the SiH group used and further substantially free of SiH group.

Polyorganosiloxane compound having an alkenyl group and a compound having at least one selected from the group consisting of each structure represented by formulas (X1) to (X3), a phenolic hydroxyl group and a carboxyl group, and a SiH group Depending on the group (alkenyl group or SiH group) contained in the modified polyorganosiloxane obtained by reacting, it can be used as the component (A) or the component (B) of the present application.

Although the compounds obtained as described above for the present application (A) and component (B) may be used, it is preferable to use a component obtained by either of them.
When used as the component (A) of the present application, as the component (B), the modified organopolysiloxane shown in the second preferred embodiment described above can be used.

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

Component (C) used in the present invention is a photoactive platinum complex catalyst, and when activated by irradiating light to the curable composition, a catalyst that promotes an addition reaction between component (A) and component (B). Has an effect. For example, a platinum complex having a β-diketone compound or a cyclic diene compound as a ligand can be mentioned.

Here, as the β-diketone platinum complex, for example, bis (2,4-pentanedionate) platinum complex, bis (2,4-hexanedionate) platinum complex, bis (2,4-heptanedionate) ) Platinum complex, bis (3,5-heptanedionate) platinum complex, bis (1-phenyl-1,3-butanedionate) platinum complex, bis (1,3-diphenyl-1,3-propanedionate) Platinum complexes, trimethyl (acetylacetonato) platinum complexes, trimethyl (2,4-pentanedionate) platinum complexes, trimethyl (3,5-heptanedionate) platinum complexes, trimethyl (methylacetoacetate) platinum complexes, and the like. .

Examples of the platinum complex having a cyclic diene compound as a ligand include (1,5-cyclooctadienyl) dimethylplatinum complex, (1,5-cyclooctadienyl) diphenylplatinum complex, (1,5 -Cyclooctadienyl) dipropylplatinum complex, (2,5-norboradiene) dimethylplatinum complex, (2,5-norboradiene) diphenylplatinum complex, (cyclopentadienyl) dimethylplatinum complex, (methylcyclopentadienyl) diethyl Platinum complex, (trimethylsilylcyclopentadienyl) diphenylplatinum complex, (methylcycloocta-1,5-dienyl) diethylplatinum complex, (cyclopentadienyl) trimethylplatinum complex, (cyclopentadienyl) ethyldimethylplatinum complex, (Cyclopentadienyl) acetyldimethylplatinum complex, (methyl Lopentadienyl) trimethylplatinum complex, (methylcyclopentadienyl) trihexylplatinum complex, (trimethylsilylcyclopentadienyl) trimethylplatinum complex, (dimethylphenylsilylcyclopentadienyl) triphenylplatinum complex, (cyclopentadienyl) dimethyl A trimethylsilylmethyl platinum complex etc. are mentioned.

Among these, bis (2,4-pentanedionate) platinum complex is preferable from the viewpoint of availability.

The content of the component (C) may be an effective amount as a catalyst, but is preferably 0.1 to 10 parts by weight with respect to the total weight of the components (A) and (B). More preferably, it is 1 to 5 parts by weight. If the content exceeds 10 parts by weight, it is not preferable from the viewpoint of the storage stability of the curable composition, and if it is less than 0.1 parts by weight, the curability may be too low to be cured.

(Additive)
(Storage stability improver)
In order to improve the storage stability of the curable composition of the present invention, a storage stability improver can be used. As the storage stability improver, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, etc. can be used, and these may be used in combination. Absent.

From the viewpoint of raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1-cyclohexanol, and triphenylphosphine are preferable.

Although the addition amount of the storage stability improver can be variously set, the lower limit of the preferable addition amount with respect to 1 mol of the hydrosilylation catalyst to be used is 10 ⁻¹ mol, more preferably 1 mol, and the upper limit of the preferable addition amount is 10 ³ mol. , more preferably 10 ² moles. If the amount added is small, the desired storage stability improving effect cannot be obtained. Moreover, when there is much addition amount, it can become a hardening inhibitor at the time of hardening reaction.

Moreover, these storage stability improving agents may be used independently and may be used together 2 or more types.

(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. Can do.

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, α1-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 adhesiveness 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 having 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, still more preferably 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.

As a thermoplastic resin, you may have the carbon-carbon double bond and / or SiH group which have a reactivity with SiH group in a molecule | numerator. In the point that the obtained cured product tends to be tougher, the molecule has one or more carbon-carbon double bonds and / or SiH groups having reactivity with SiH groups in the molecule on average. It is preferable.

The thermoplastic resin may have other crosslinkable groups. 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. Also in this case, the thermoplastic resin may be directly dissolved in the modified polyorganosiloxane compound, or may be mixed uniformly using a solvent or the like, and then the solvent is removed to obtain a uniform dispersed state and / or mixed state. It is good.

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. The particle size may be distributed, and may be monodispersed or have a plurality of peak particle sizes. However, 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.

(Radical inhibitor)
A radical inhibitor may be added to the curable composition of the present invention. Examples of the radical inhibitor include 2,6-di-t-butyl-3-methylphenol (BHT), 2,2′-methylene-bis (4-methyl-6-t-butylphenol), tetrakis (methylene- Phenol radical inhibitors such as 3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane, phenyl-β-naphthylamine, α1-naphthylamine, N, N′-secondarybutyl-p- Examples include amine radical inhibitors such as phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine, and the like. Moreover, these radical inhibitors may be used alone or in combination of two or more.

(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, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, 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 with respect to 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.

(Regarding photolithographic properties)
When forming a pattern with a thin film using the composition of the present invention for the purpose of forming a contact hole or the like, it can be carried out by a method similar to a developing method of a normal resist material, and is not particularly limited. As a light source for sensitization, a light source that emits an absorption wavelength of a polymerization initiator or a sensitizer to be used may be used, and a light source usually containing a wavelength in the range of 200 to 450 nm, for example, a high-pressure mercury lamp, an ultra-high pressure Mercury lamps, metal halide lamps, high power metal halide lamps, xenon lamps, carbon arc lamps, light emitting diodes, and 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, a pattern may not be formed due to overexposure.

Further, for the purpose of removing the solvent and improving the physical properties of the cured product, pre-baking and after-baking may be performed by applying heat before and after photocuring. Various curing temperatures can be set, but a preferable temperature range is 60 to 300 ° C, more preferably 80 to 200 ° C.

The developer can be used without particular limitation as long as it is a commonly used alkaline developer, but specific examples include organic alkaline aqueous solutions such as tetramethylammonium hydroxide aqueous solution and choline aqueous solution, and potassium hydroxide. Examples thereof include an aqueous solution, an aqueous solution of sodium hydroxide, an aqueous solution of potassium carbonate, an aqueous solution of sodium carbonate, an aqueous solution of lithium carbonate and the like, and an aqueous solution containing alcohol or a surfactant added to adjust the dissolution rate.

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.

(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.

Using the composition, the following alkali development characteristics evaluation and heat resistance evaluation of the cured product were performed. Table 1 shows the results of evaluating the characteristics of the curable compositions obtained in Examples , Reference Examples and Comparative Examples.

As can be seen from the results, it can be seen that a cured product having alkali developability and excellent in optical transparency and heat resistance is obtained by the present invention.

(Alkali developability)
A simple mask that covers the coated surface partially by applying the composition obtained from the curable compositions obtained in Examples , Reference Examples and Comparative Examples to a glass plate (50 × 100 × 0.7 mm) by spin coating. An attached sample 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 (TMAH 2.38% aqueous solution) for 60 seconds and then washed with water, and a development contrast is obtained (the exposed portion resin remains and the unexposed portion is removed). Those not attached were evaluated as alkali developability with x.

(Heat resistance evaluation)
A glass plate coated with the curable composition obtained in Examples 1 to 4, Reference Example 5 and Comparative Examples 1 and 2 to have a thickness of about 50 μm was used to measure an integrated light amount of 200 mJ / cm using the conveyor type exposure apparatus. ² exposures. Thereafter, the sample on the glass substrate heated as a post-baking at 150 ° C. for 30 minutes in a circulating hot air oven was stored in the same circulating hot air oven at 200 ° C. for 24 hours and subjected to a heat resistance test. The composition coating film appearance and light transmittance before and after the heat resistance test were measured to evaluate heat resistant transparency. The light transmittance here was measured using a U-3300 manufactured by Hitachi, Ltd. under a scan speed of 300 nm / min.

(Synthesis Example 1)
A 500 mL four-necked flask was charged with 100 g of toluene and 57.49 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 solution of 10.0 g of diallyl isocyanuric acid, 70.0 g of 1,4-dioxane and 0.0186 g of a platinum vinylsiloxane complex in xylene (containing 3 wt% as platinum) was added dropwise over 30 minutes. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain polysiloxane compound A.

^{From the 1} H-NMR measurement, peaks derived from the SiH group and the NH group are confirmed from the obtained polysiloxane compound A, and it is understood that the polysiloxane compound has a SiH group and an isocyanuric acid group.

(Synthesis Example 2)
175 g of toluene and 86.23 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed in a 500 mL four-necked flask, and the gas phase was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixture of 7.5 g of diallyl isocyanuric acid, 5.95 g of triallyl isocyanurate, 70.0 g of 1,4-dioxane and 0.0280 g of a platinum vinylsiloxane complex in xylene (containing 3 wt% as platinum) is added dropwise over 30 minutes. did. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain polysiloxane compound B.

^{From the 1} H-NMR measurement, peaks derived from SiH groups and NH groups are confirmed from the obtained polysiloxane compound B, and it can be seen that the polysiloxane compounds have SiH groups and isocyanuric acid groups.

(Synthesis Example 3)
A 1 L four-necked flask is charged with 34.8 g of diallyl isocyanuric acid, 250 g of 1,4-dioxane and 0.0649 g of a platinum vinylsiloxane complex xylene solution (containing 3 wt% as platinum), and 50 g of toluene, 1,3,5,7 -A mixed liquid of 50 g of tetramethylcyclotetrasiloxane was dropped over 30 minutes. The gas phase was replaced with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. It was confirmed by ¹ H-NMR that the SiH group had disappeared, and the reaction was terminated by cooling. The solvent dioxane and toluene were distilled off under reduced pressure to obtain polysiloxane compound C.

(Synthesis Comparative Example 1)
A 500 mL four-necked flask was charged with 150 g of toluene and 72.36 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. A mixed liquid of 10.0 g of triallyl isocyanurate, 10.0 g of toluene and 0.0038 g of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) was dropped over 30 minutes. Six hours after the completion of the dropwise addition, it was confirmed by ¹ H-NMR that the reaction rate of the allyl group was 95% or more, and the reaction was terminated by cooling. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain polysiloxane compound D.

^{From the 1} H-NMR measurement, a peak derived from the SiH group is confirmed from the obtained polysiloxane compound D, which indicates that the polysiloxane compound has a SiH group.

Example 1
Resin composition by adding 0.7 g of triallyl isocyanurate, 34 mg of platinum (II) bisacetylacetonate, 6.8 g of propylene glycol monomethyl ether acetate (solvent, PGMEA) to 1 g of the polysiloxane compound A obtained in Synthesis Example 1. It was a thing.

(Example 2)
To 1 g of the polysiloxane compound A obtained in Synthesis Example 1, 2.4 g of MQV7 (manufactured by Clariant Japan, vinyl group-containing siloxane compound), 34 mg of platinum (II) bisacetylacetonate, propylene glycol monomethyl ether acetate (solvent, PGMEA 13.6 g was added to obtain a resin composition.

(Example 3)
0.7 g of triallyl isocyanurate, 34 mg of platinum (II) bisacetylacetonate and 6.8 g of PGMEA were added to 1 g of the polysiloxane compound B obtained in Synthesis Example 2 to obtain a resin composition.

Example 4
To 1 g of the polysiloxane compound B obtained in Synthesis Example 2, 2.4 g of MQV7 (manufactured by Clariant Japan, vinyl group-containing siloxane compound), 34 mg of platinum (II) bisacetylacetonate, and 13.6 g of PGMEA are added to obtain a resin composition. did.

( Reference Example 5)
1 g of MQH-8 (manufactured by Clariant Japan, hydrosilyl group-containing siloxane compound), 40 mg of platinum (II) bisacetylacetonate and 8 g of PGMEA were added to 1 g of the polysiloxane compound C1 obtained in Synthesis Example 3 to obtain a resin composition.

(Comparative Example 1)
0.71 g of triallyl isocyanurate, 34 mg of platinum (II) bisacetylacetonate and 7.0 g of PGMEA were added to 1 g of the polysiloxane compound D obtained in Synthesis Comparative Example 1 to obtain a resin composition.

(Comparative Example 2)
0.01 g of a cationic polymerization initiator (Rhodia, product name: RHODORSIL PI2074) and 4.0 g of PGMEA were added to 1 g of a photocurable epoxy compound (Daicel Chemical, product name: Celoxide 2021P) to obtain a resin composition.

Claims (11)

(A) Compound having alkenyl group, (B) Modified polyorganosiloxane having SiH group and having at least one selected from the structures represented by the following formulas (X1) to (X3) in the same molecule A resist material capable of alkali development using a curable composition containing a compound (provided that the component also corresponds to the component (A)), (C) a photoactive platinum complex curing catalyst.

(A) a compound having an alkenyl group, (B) a compound having an (α1) alkenyl group and having at least one selected from the group consisting of structures represented by the following formulas (X1) to (X3): (Β) SiH group-containing modified polyorganosiloxane obtained by hydrosilylation reaction of a polyorganosiloxane compound having two or more SiH groups (except for those corresponding to the component (α1)) (however, (A And (C) a resist material capable of alkali development using a curable composition containing a photoactive platinum complex curing catalyst.

3. The alkali-developable resist material according to claim 1, wherein component (A) is an organic compound having an alkenyl group. Component (A) is represented by the following general formula (I)

(In the formula, R ³ represents a hydrogen atom or a hydrocarbon group optionally having 1 to 10 carbon atoms, and each R ³ may be different or the same, and at least 1 The alkali-developable resist material according to claim 1, wherein each R ³ is represented by a carbon-carbon double bond having reactivity with a SiH group. The alkali-developable resist material according to any one of claims 1, 3, and 4, wherein the component (B) is a hydrosilylation reaction product of the following compounds α1 and β:
(Α1) an organic compound having an alkenyl group and having in the same molecule at least one selected from the group consisting of structures represented by formulas (X1) to (X3),
(Β) A polyorganosiloxane compound having two or more SiH groups in one molecule (excluding those corresponding to the component (α1)). 6. The alkali developable according to claim 2, wherein (β) is a linear and / or cyclic polyorganosiloxane compound having two or more SiH groups in one molecule. Resist material. Compound (β) is represented by the following general formula (II)

(In the formula, R ² and R ³ each represents a hydrocarbon group having 1 to 10 carbon atoms and optionally having an O atom, n is 2 to 10, m is 0 to 10, provided that m + n ≧ 3. The resist material capable of alkali development as claimed in any one of claims 2 to 6, which is a cyclic polyorganosiloxane compound having a SiH group represented by: 8. The alkali-developable resist material according to claim 1, wherein the component (C) is a β-diketone platinum complex. An insulating film obtained using the alkali-developable resist material according to claim 1. A thin film transistor, wherein the insulating film according to claim 9 is a passivation film of a semiconductor layer. A thin film transistor, wherein the insulating film according to claim 9 is a gate insulating film.