JP2011221192A - Curable composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which exhibits excellent patterning property in photo-lithography and a membrane obtained from which provides a cured product with good insulation properties, heatproof and lightproof properties, and a cured product.SOLUTION: A curable composition includes as essential components (A) polysiloxane compound with SiH groups and photopolymerizable functional groups in a molecule, (B) a compound containing alkenyl groups, (C) a photoactive platinum complex catalyst and (D) a curable composition including a photopolymerization initiator. With this composition, a cured product obtained can exhibit excellent isolation properties and heatproof and lightproof properties, which are to be achieved at first.

Description

  The present invention relates to a cured product and a curable composition excellent in photolithography, insulation, and heat and light resistance.

  A curable composition composed of a compound having a functional group such as an acrylic group, an epoxy group, or an oxetane group can be cured easily in a short time by applying light energy. An insulating material, an adhesive, a coating agent, It is used in various industries such as sealants. However, no material has been proposed that has both material reliability such as insulation and heat and light resistance and photocurability.

  An epoxy silicon compound obtained by reacting an alkenyl compound having an epoxy group with a siloxane compound is described in Patent Document 1, and functions as a photocurable resin by blending a photocationic polymerization initiator into the epoxy silicon compound. To do. However, when these compounds are applied to an insulating film of an electric element or the like, there is a lack of insulation, and leakage current becomes a problem. Moreover, discoloration and deterioration occur due to poor heat and light resistance.

  Patent Document 2 discloses a technique related to a curable composition by hydrosilylation of a compound obtained by partially converting a siloxane compound having a SiH group into an epoxy group and a polyene compound. A cured product made of the curable composition has high material reliability but does not function as a photocurable resin, and patterning by photolithography is difficult.

JP 2006-152316 A JP 2006-291044 A

  In view of the above circumstances, an object of the present invention is to provide a curable composition and a cured product that exhibit excellent patterning properties in photolithography, and the obtained film has excellent insulating properties and heat and light resistance.

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

  1). (A) A polysiloxane compound having a SiH group and a photopolymerizable functional group, (B) an alkenyl group-containing compound, (C) a photoactive platinum complex catalyst, (D) a curable composition containing a photopolymerization initiator .

  2). The photopolymerizable functional group of the component (A) is at least one selected from the group consisting of an epoxy group, a crosslinkable silicon group, a (meth) acryloyl group, an oxetanyl group, and a vinyloxy group. Composition.

  3). The curable composition according to 1) or 2), wherein at least one of the photopolymerizable functional groups of component (A) is an alicyclic epoxy group, oxetanyl group or glycidyl group.

  4). The curable composition according to 1) or 2), wherein at least one of the photopolymerizable functional groups of component (A) is an alkoxysilyl group.

  5). Component (B) is represented by the following general formula (I)

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ includes an alkenyl group). The curable composition according to any one of 1) to 4), which is a compound to be produced.

6). The curable composition according to any one of 1) to 5), wherein the component (B) is a compound having a Si—CH═CH ₂ group.

  7). Component (A) is composed of at least two photopolymerizable functional groups and at least two SiH groups, 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), which is a polysiloxane compound having at least one selected from the group consisting of:

8). The curable composition according to any one of 1) to 7), wherein the component (A) is a hydrosilylation reaction product of the following compounds (α) to (γ).
(Α) Organic compound having at least one alkenyl group (β) Organosiloxane compound having at least two SiH groups (γ) Compound having at least one photopolymerizable functional group and at least one alkenyl group 9 ). The compound (α) has a general formula (II) having at least one alkenyl group

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ includes an alkenyl group). The curable composition according to 8), which is a compound to be obtained.

10). The curable composition according to 8) or 9), wherein the compound (α) is a compound having a Si—CH═CH ₂ group.

  11). The compound (α) is selected from the group consisting of at least one alkenyl group in one molecule and each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. It is an organic compound which has at least 1 type, The curable composition in any one of 8) -10) characterized by the above-mentioned.

  12). Compound (β) is represented by the following general formula (III)

(Wherein R ⁴ and R ⁵ represent an organic group having 1 to 10 carbon atoms and may be the same or different, n represents 2 to 10, and m represents a number of 0 to 10)
The curable composition according to any one of 8) to 11), which is a cyclic organopolysiloxane compound having a SiH group represented by the formula:

  13). Compound (γ) is represented by the following general formula (IV)

(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). The curable composition as described in any one of 8-12.

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

  15). Hardened | cured material formed by hardening | curing the curable composition in any one of 1) -14).

  According to this invention, this curable composition has photocurability and can give the hardened | cured material excellent in photolithography property, insulation, and heat-resistant light resistance.

  Details of the present invention will be described.

  The present invention contains (A) a polysiloxane compound having a SiH group and a photopolymerizable functional group, (B) an alkenyl group-containing compound, (C) a photoactive platinum complex catalyst, and (D) a photopolymerization initiator. It is a curable composition, and the resulting composition can be photocured, and the shape after application of the material can be fixed in a short time by light irradiation as compared with a material only by heat curing, and photopatterning is possible. Moreover, the hardened | cured material obtained has the outstanding insulation and heat-and-light resistance.

  The detailed configuration of the present invention will be described below.

(Ingredient (A))
The polysiloxane compound used in the curable composition of the present invention is not particularly limited as long as it has a SiH group and a photopolymerizable functional group.

Here, the polysiloxane compound refers to a compound or polymer composed of a siloxane unit (Si—O—Si) and an organic group X composed of C, H, N, O, and S as constituent elements, The structure is not particularly limited. Among the siloxane units in these compounds, the hardened product obtained with a higher content of T units (XSiO _3/2 ) or Q units (SiO _4/2 ) in the constituent components has higher hardness and more material reliability. The cured product is more flexible and has lower stress as it is more excellent and has a higher content of M units (X ₃ SiO _1/2 ) or D units (X ₂ SiO _2/2 ).

  The photopolymerizable functional group as used herein refers to a functional group that is polymerized and cross-linked by radicals or cationic species generated from a photopolymerization initiator when light energy is applied from the outside, and the reaction / crosslinking mode is particularly limited. It is not a thing.

  Among these, particularly from the viewpoint of reactivity and compound stability, 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, particularly from the viewpoint of availability and stability of the compound. In particular, an alkoxysilyl group is 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 polysiloxane compound preferably has at least two photopolymerizable functional groups, more preferably 3 or more, and particularly preferably 5 or more. If it is three or more, there exists an advantage that the hardened | cured material with a high crosslinking density is obtained and it is excellent in heat resistance and light resistance. When there are a plurality of photopolymerizable functional groups, each photopolymerizable functional group may be the same, or may have two or more different functional groups.

  In the component (A) contained in the curable composition of the present invention, each structure represented by the following formulas (X1) to (X3);

  At least one selected from the 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” is referred to as an “acidic group”). In the same molecule, the curable composition obtained by having this structure can be dissolved in an alkaline aqueous solution, and has an industrially useful lithographic composition. Can be a thing.

  Among these organic structures, when the curable composition of the present invention is cured, the cured product is less colored at high temperatures, among these organic structures, the structure represented by the carboxyl group and the following formula,

It is preferable to have a structure selected from the following formulas from the viewpoint of obtaining a cured product having low thermal decomposition at high temperatures.

As a suitable component (A) used in the curable composition of the present invention, the following embodiments may be mentioned.
Hydrosilylation reaction products of the following compounds (α) to (γ):
(Α) An organic compound having at least one alkenyl group in one molecule.
(Β) An organosiloxane compound having at least two SiH groups in one molecule.
(Γ) A compound having at least one photopolymerizable functional group and at least one alkenyl group in one molecule.

Hereinafter, preferred embodiments of the component (A) will be described.
(Compound (α))
The compound (α) will be described.

The compound (α) is not limited as long as it is a compound having at least one alkenyl group in one molecule, and in particular, the same compound as the component (B) can be used.
Among them, from the viewpoint of excellent insulation of the obtained cured product,
The following general formula (II)

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ includes an alkenyl group). It is preferable that
Further, from the viewpoint of availability, triallyl isocyanurate, diallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monobenzyl isocyanurate, diallyl monopropyl isocyanurate can be mentioned.

Moreover, the polysiloxane type compound which has an alkenyl group can apply preferably from the transparency and sclerosis | hardenability viewpoint of the cured | curing material obtained. Among these, from the viewpoint of 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.

  In the component (α), each structure represented by the following formulas (X1) to (X3);

  It is preferable to have at least one selected from the group consisting of a phenolic hydroxyl group and a carboxyl group in the same molecule, and by having this structure, it can be dissolved in an alkaline aqueous solution and has an industrially useful lithography property. It can be a curable composition.

  Among these compounds, those having an isocyanuric acid structure are preferable from the viewpoint of excellent heat resistance and light resistance, and diallyl isocyanuric acid, monoallyl isocyanuric acid and the like are specifically mentioned from the viewpoint of availability.

  Further, it can be used in combination with an alkenyl compound having no acidic group, and in particular from the viewpoint of heat and light resistance, alkenyl compounds having an isocyanuric ring structure are triallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl. The combined use with isocyanurate or the like is preferable.

  Further, from the viewpoint of excellent transparency of the obtained cured product, it is preferable to use it together with a polysiloxane compound having an alkenyl group. Particularly, from the viewpoint of availability, a poly or oligosiloxane whose end is blocked with a dimethylvinylsilyl group, 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethylcyclotetra Siloxane, 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-he Cyclic siloxane compounds such as methylated cyclosiloxane is preferred.

(Compound (β))
The compound (β) will be described.
The compound (β) is not particularly limited as long as it is a polysiloxane compound having at least two SiH groups in one molecule. For example, the compound described in International Publication WO96 / 15194 is at least two in one molecule. Those having a SiH group can be used.

  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 and light resistance, and are preferably phenyl groups from the viewpoint of increasing the strength of the cured product.

  Further, from the viewpoint of high heat resistance and light resistance of the cured product, organopolysiloxane having a T unit or a Q unit in the molecule is preferable, and specific examples include the following compounds.

(Wherein, R ^15, R ¹⁶ represents an organic group having 1 to 6 carbon atoms, n represents a number from 0 to 50.)
An organopolysiloxane having at least two SiH groups in one molecule and having T units or Q units in the molecule is preferred, and R ¹⁵ and R ¹⁶ are from the viewpoints of availability and heat and light resistance. Particularly preferred is a methyl group.

  From the viewpoint of availability and reactivity with the compounds (α) and (γ), the following general formula (III)

(Wherein R ⁴ and R ⁵ represent an organic group having 1 to 6 carbon atoms and may be the same or different, n represents 3 to 10, and m represents a number of 0 to 10). Cyclic organopolysiloxanes having at least 3 SiH groups per molecule are preferred.

The substituents R ⁴ and R ⁵ 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 at least one photopolymerizable functional group and at least one alkenyl group in one molecule. In addition, the photopolymerizable functional group here is the same as the photopolymerizable functional group of the polysiloxane compound, and a preferable embodiment is also preferable.

  In particular, as a photopolymerizable functional group, from the viewpoint of reactivity and stability of the compound, 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. 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 the following general formula (IV) from the viewpoint of availability and heat and light 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.

  As the compound (γ) having a (meth) acryloyl group as a photopolymerizable functional group, allyl (meth) acrylate, vinyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Acrylate, (meth) acrylic acid modified allyl glycidyl ether (manufactured by Nagase ChemteX Corp., trade name: Denacol acrylate DA111), vinyl group or allyl group and the following general formula (IX)

(R ¹⁷ in the formula represents a hydrogen atom or a methyl group) A compound having at least one organic group represented by the same molecule in the same molecule, for example, in the above-mentioned general formula (II), R ³ in the formula In which at least one of the groups is a group represented by the above general formula (IX) and at least one of R ³ has an alkenyl group such as a vinyl group or an allyl group. 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)
As a catalyst for the hydrosilylation reaction of the compound (α), the compound (β) and the compound (γ), for example, the following can be used. Platinum simple substance, alumina, silica, carbon black or the like supported on solid platinum, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone or the like, platinum-olefin complex (for example, Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ]) _m ), platinum-phosphine complexes (eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ), platinum-phosphite complexes (eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄₎ (in the formula, Me represents a methyl group, Bu a butyl group, Vi is vinyl group, Ph represents a phenyl group, n, m is an integer.), dicarbonyl dichloroplatinum, Karushuteto Karstedt catalyst, as well as the platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3,159,601 and 3,159,622, and Lamoreaux, US Pat. No. 3,220,972. And platinum alcoholate catalysts. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , RhAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _4. , Etc.

  Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. 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 addition amount is preferably an alkenyl group of the compound (α) and the compound (γ) in order to have sufficient reactivity and keep the cost of the curable composition relatively low. 10 ^-8 mol relative to 1 mol, more preferably 10 ^-6 moles, the upper limit of the preferable amount is 10 ^-1 mol per alkenyl group 1 mole of the compound, 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 of compound (α), compound (β) and compound (γ))
As described above, the polysiloxane compound that can be used in the curable composition of the present invention is obtained by reacting the compound (α), the compound (β), and the compound (γ) in the presence of a hydrosilylation catalyst. The compound which can be mentioned is mentioned.

  There are various reaction sequences and methods, but from the viewpoint that the synthesis process is simple, the compound (α), the compound (β), and the compound (γ) are hydrosilylated in one pot and finally unreacted. A method of removing the compound of the reaction is preferable, and from the viewpoint that it is difficult to contain a low molecular weight substance, an excess of the compound (α) and the compound (β), or an excess of the compound (β) and the compound (α) After the hydrosilylation reaction, an unreacted compound (α) or compound (β) is once removed, and the obtained reaction product and the compound (γ) are subjected to a hydrosilylation reaction.

  The ratio of reacting each compound is not particularly limited, but if the total amount of SiH groups in compound (β) is small on the basis of the total amount of alkenyl groups in compound (α) and compound (γ), unreacted alkenyl groups will be present in the composition. Since it remains, it causes coloring, and in the case of a large amount, a large amount of the compound (β) is used, which is not preferable from the viewpoint of increasing the production cost. Therefore, when the total alkenyl group amount of the compound (α) and the compound (γ) is A and the total SiH group amount of the compound (β) is B, it is preferable that 1 ≦ B / A ≦ 30, and further 1 ≦ It is preferable that B / A ≦ 10.

  In addition, regarding the ratio of reacting the compound (α) and the compound (γ), when the alkenyl group of the compound (α) is A1, and the alkenyl group of the compound (γ) is A2, A1 + A2 = 1 and 0.01 ≦ The reaction can be appropriately selected within the range of A1 ≦ 0.99 and 0.01 ≦ A2 <0.99.

  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. In view of promoting the hydrosilylation reaction effect by the addition of oxygen, the oxygen volume concentration in the gas phase is preferably at least 0.1%, more preferably at least 1%.

  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. Specific examples include 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.

  After the compound (α), the compound (β) and the compound (γ) are subjected to a hydrosilylation reaction, the solvent and / or the unreacted compound can also be removed. By removing these volatile components, the reaction product obtained does not have volatile components. Therefore, when a cured product is produced using the reaction product, problems of voids and cracks due to volatilization of volatile components are unlikely to occur. Tend. Examples of the removal method include vacuum devolatilization. When devolatilizing under reduced pressure, it is preferable to treat at a low temperature. The upper limit of the preferable temperature in this case is 100 ° C, more preferably 80 ° C. When treated at high temperatures, it tends to be accompanied by alterations such as thickening.

(Ingredient (B))
The component (B) used in the curable composition of the present invention is not particularly limited as long as it has an alkenyl group, and is used without any limitation regardless of a polysiloxane compound or an organic compound. Can do.

From the viewpoints of transparency and curability of a cured product obtained by curing the curable composition of the present invention, a polysiloxane compound having an alkenyl group can be preferably applied. Among these, from the viewpoint of 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 at least one alkenyl group. Further, the bonding position of the alkenyl group is not particularly limited, and may be present anywhere in the molecule as long as it has reactivity with the SiH group.

  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 organic compound include butadiene, isoprene, 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, pentaerythris Tall tetravinyl ether, diallyl ether of bisphenol S, divinylbenzene, divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-bis (allyloxy) adamantane, 1,3-bis ( Vinyloxy) adamantane, 1,3,5-tris (allyloxy) adamantane, 1,3,5-tris (vinyloxy) adamantane, dicyclopentadiene, vinylcyclohexene, 1,5-hexadiene, 1,9-decadiene, diallyl ether Bisphenol A diallyl ether, 2,5-diallylphenol allyl ether, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%) , Novola Allyl ether of phenol, allylated polyphenylene oxide, and other, such as those obtained by replacing the allyl group all glycidyl groups of a conventionally known epoxy resins.

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

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ includes an alkenyl group). Are preferred.

As R < ³ > 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 and light resistance of the hardened | cured material obtained can become higher, and C1 Is more preferably a monovalent organic group having from 1 to 10 carbon atoms, and even more preferably a monovalent organic group having from 1 to 4 carbon atoms. 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.

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

  The component (C) used in the present invention is a photoactive platinum complex catalyst, and a catalyst that promotes an addition reaction between the component (A) and the component (B) when activated by irradiating light to the curable composition. Examples thereof include platinum complexes having a β-diketone compound or a cyclic diene compound as a ligand.

  Platinum complexes in which hydrosilylation proceeds by thermal activity, such as chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, dicarbonyldichloroplatinum, Karstedt catalyst, etc. Is not applicable.

  Examples of β-diketone platinum complexes include bis (2,4-pentanedionate) platinum complexes, bis (2,4-hexanedionate) platinum complexes, and bis (2,4-heptanedionate) platinum complexes. Bis (3,5-heptanedionate) platinum complex, bis (1-phenyl-1,3-butanedionate) platinum complex, bis (1,3-diphenyl-1,3-propanedionate) platinum complex, Examples include a trimethyl (acetylacetonate) platinum complex, a trimethyl (2,4-pentanedionate) platinum complex, a trimethyl (3,5-heptanedionate) platinum complex, and a trimethyl (methylacetoacetate) platinum complex.

  Examples of the platinum complex having a cyclic diene compound as a ligand include (1,5-cyclooctadienyl) dimethylplatinum complex, (1,5-cyclooctadienyl) diphenylplatinum complex, and (1,5-cyclohexane). Octadienyl) dipropylplatinum complex, (2,5-norboradiene) dimethylplatinum complex, (2,5-norboradiene) diphenylplatinum complex, (cyclopentadienyl) dimethylplatinum complex, (methylcyclopentadienyl) diethylplatinum complex (Trimethylsilylcyclopentadienyl) diphenylplatinum complex, (methylcycloocta-1,5-dienyl) diethylplatinum complex, (cyclopentadienyl) trimethylplatinum complex, (cyclopentadienyl) ethyldimethylplatinum complex, (Pentadienyl) acetyldimethylplatinum complex, (methylcyclopentadienyl) trimethylplatinum complex, (Tylcyclopentadienyl) trihexylplatinum complex, (trimethylsilylcyclopentadienyl) trimethylplatinum complex, (dimethylphenylsilylcyclopentadienyl) triphenylplatinum complex, (cyclopentadienyl) dimethyltrimethylsilylmethylplatinum complex, etc. It is done.

  Among the β-diketone platinum complexes and cyclic diene platinum complexes, β-diketone platinum complexes are preferable, and among these compounds, bis (2,4-pentanedionate) platinum complexes are particularly preferable from the viewpoint of availability.

  These photoactive platinum complex catalysts may be used alone or in combination of two or more. The amount of photoactive platinum complex catalyst used depends on the amount and type of photopolymerization initiator, and cannot be specified unconditionally. However, the effects such as low lithographic properties, insulating properties, and coloring properties due to the hydrosilylation reaction by light. Is preferably about 0.01 to 5 parts by weight, and more preferably 0.05 to 3 parts by weight with respect to the total weight of component (A) and component (B).

(Component (D))
In the curable composition of the present invention, a photopolymerization initiator is an essential component. The type is preferably selected as appropriate depending on the type of the photopolymerizable functional group. For example, a cationic polymerization initiator is preferably used in the case of an epoxy group, an alkoxysilyl group, or the like, and a photo radical initiator is preferably used in the case of a radical polymerizable group such as an allyloxy or methacryloxy group.

(Cationic polymerization initiator)
As the cationic polymerization initiator, an active energy ray cationic polymerization initiator that generates a cationic species or a Lewis acid by active energy rays, or a thermal cationic polymerization initiator that generates a cationic species or a Lewis acid by heat can be used.

Active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds as described in US Pat. No. 3,379,653; bis (perfluoroalkyls as described in US Pat. No. 3,586,616). Sulfonyl) methane metal salts; aryldiazonium compounds as described in US Pat. No. 3,708,296; aromatic onium salts of group VIa elements as described in US Pat. No. 4,058,400; described in US Pat. Aromatic onium salts of Group Va elements such as: dicarbonyl chelates of Group IIIa to Va elements as described in US Pat. No. 4068091; thiopyrylium salts as described in US Pat. No. 4,139,655; US Pat. No. 4,161,478 such as those described in JP MF6 ^- anions (this And M is selected from phosphorus, antimony and arsenic); arylsulfonium complex salts as described in US Pat. No. 4,231,951; aromatic iodonium complex salts as described in US Pat. No. 4,256,828 and Aromatic sulfonium complex salts; R. Bis [4- (diphenylsulfonio) phenyl] sulfide-bishexafluoro as described by Watt et al. In “Journal of Polymer Science, Polymer Chemistry Edition”, Vol. 22, page 1789 (1984). Metal salts (eg, phosphates, arsenates, antimonates, etc.); one or more of aromatic iodonium complex salts and aromatic sulfonium complex salts whose anion is B (C ₆ F ₅ ) ₄ ^— are included.

  Preferred cationic active energy ray cationic polymerization initiators include arylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, and aromatic onium salts of Group II, Group V and Group VI elements. Some of these salts are FX-512 (manufactured by 3M), UVR-6990 and UVR-6974 (manufactured by Union Carbide), UVE-1014 and UVE-1016 (manufactured by General Electric), KI-85. (Degussa), SP-152 and SP-172 (Asahi Denka), Sun-Aid SI-60L, SI-80L and SI-100L (Sanshin Chemical), WPI113 and WPI116 (Wako Pure Chemical Industries) Manufactured), RHODORSIL PI2074 (manufactured by Rhodia), and BBI-103 (manufactured by Midori Chemical).

  These cationic polymerization initiators may be used alone or in combination of two or more. The amount of the cationic polymerization initiator used depends on the amount and type of the photoactive platinum complex catalyst and cannot be specified unconditionally. However, the curing time, the point of remaining cationic polymerization initiator in the cured product, the surface of the cured product, From the viewpoints of colorability, colorability, heat and light resistance, etc., it is preferably about 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polysiloxane compound. .

(Radical polymerization initiator)
Any active energy ray radical polymerization 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-propane-1 -ON etc. are mentioned.

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

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

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

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

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

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

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

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

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

  From the viewpoint of excellent thin film curability, acylphosphine oxide compounds, acetophenone compounds, and oxime ester compounds are preferred. Specifically, 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-propane-1- ON, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Yl] -1- (O-acetyloxime).

  In particular, an acetophenone compound is preferable from the viewpoint that the cured product is excellent in transparency. Specifically, 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 and 2,2-dimethoxyacetophenone.

  These radical polymerization initiators may be used alone or in combination of two or more. The amount of radical polymerization initiator used depends on the amount and type of photoactive platinum complex catalyst, and cannot be specified unconditionally. However, the curing time, the point of residual radical polymerization initiator in the cured product, the surface of the cured product, In terms of properties, colorability, heat and light resistance, etc., it is preferably about 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane compound. .

  The polysiloxane compound used in the curable composition of the present invention can be obtained by various methods such as condensation reaction, addition reaction and ring-opening polymerization by hydrolysis. 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. .

  In the polysiloxane compound of the present invention and / or in the curable composition, various additives may be used depending on the purpose.

(About additives)
(Sensitizer)
In the curable composition of the present invention, when cured with light energy, light sensitivity is improved and light having a high wavelength such as g-line (436 nm), h-line (405 nm), and i-line (365 nm) is used. In order to impart sensitivity to the sensitizer, a sensitizer can be appropriately added. These sensitizers can be used in combination with the above-mentioned photoactive platinum complex catalyst, photopolymerization initiator, and the like to adjust 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. From the viewpoint of availability, anthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 9 , 10-Diphenylan Spiral, and the like are 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, 9,10-diphenylanthracene 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. The addition amount of the sensitizer is approximately 0.1 to 10 parts by weight with respect to 100 parts by weight of the polysiloxane compound from the viewpoints of curing time, sensitizer remaining in the cured product, and colorability. Is preferably 0.1 to 5 parts by weight.

(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 organopolysiloxanes (cyclic and chain), glycidyl group-containing organopolysiloxanes ( 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 Corporation, 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 glyco Le system (meth) acrylate, bisphenol A di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and (meth) acrylate group-containing organopolysiloxanes.

  Although the amount of the 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 with respect to 100 parts by weight of the polysiloxane 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.

(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 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 which can be exemplified.

  These coupling agents, silane coupling agents, epoxy compounds and the like may be used alone or in combination of two or more. The addition 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 0 with respect to 100 parts by weight of the polysiloxane 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.

  In the present invention, carboxylic acids and / or acid anhydrides can be used to enhance the effect of the coupling agent and the epoxy compound, and the adhesion can be improved and / or stabilized. Such carboxylic acids and acid anhydrides are not particularly limited, but 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylhymic acid, Norbornene dicarboxylic acid, hydrogenated methyl nadic acid, maleic acid, acetylenedicarboxylic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenecarboxylic acid Examples include acids, naphthalenedicarboxylic acids, and single or complex acid anhydrides thereof.

  Among these carboxylic acids and / or acid anhydrides, preferred carboxylic acids and / or acid anhydrides include, for example, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and the like in that the properties of the resulting cured product are not easily impaired. Examples thereof include acids and their single or complex acid anhydrides.

The amount of addition in the case of using carboxylic acids and / or acid anhydrides can be variously set, but the preferred range of addition amount with respect to 100 parts by weight of the coupling agent and / or epoxy compound is 0.1 to 50 parts by weight, More preferably, it is 1-10 weight part. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.
Further, these carboxylic acids and / or acid anhydrides may be used alone or in combination of two or more.

(Phosphorus compound)
In the case where the curable composition of the present invention is cured by light or heat and used in an application requiring transparency, a phosphorus compound may be used to improve the hue after curing by light or heat. preferable. Specific examples of phosphorus compounds include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, tris (2,4-di-t-butyl). Phenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentane tetrayl bis (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis (2, Phosphites such as 6-di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite An antioxidant selected from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa Coloring agents selected from oxaphosphaphenanthrene oxides such as -10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are preferable. used.

  The addition amount of the phosphorus compound is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polysiloxane compound. When the addition amount of the phosphorus compound is less than 0.01 parts by weight, the effect of improving the hue is reduced. When the addition amount exceeds 10 parts by weight, the curability and the physical properties of the cured product may be adversely affected.

(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 an alkenyl group and / or SiH group in a molecule | numerator. From the viewpoint that the obtained cured product tends to be tougher, it is preferable to have at least one alkenyl group and / or SiH group in the molecule on average.

  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. In view that the heat and light resistance of the resulting cured product tends to be high, it is preferable to have at least one crosslinkable group per molecule on average.

  The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is preferably 10,000 or less and more preferably 5000 or less in that the compatibility with the polysiloxane compound is likely to be good. preferable. 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 addition 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 and light resistance and the elastic modulus at high temperatures tend 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 polysiloxane compound and mixed in a uniform state, may be pulverized and mixed in a particle state, or may be dispersed by dissolving in a solvent and mixing. . In the point that the obtained hardened | cured material tends to become more transparent, it is preferable to melt | dissolve in a polysiloxane type compound and to mix as a uniform state. Also in this case, the thermoplastic resin may be dissolved directly in the polysiloxane compound, or may be mixed uniformly using a solvent, etc., and then the solvent is removed to obtain a uniform dispersed state or / and mixed state. Also 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. 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-based filler, generally used and / or proposed fillers can be mentioned.

(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 carboxylates, sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothioacids, polythioacids, thioamides, and sulfoxides.
These anti-aging agents may be used alone or in combination of two or more.

(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, α-naphthylamine, N, N′-secondary butyl-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 polysiloxane 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 preferable amount used for 1 g of the curable composition to be used is 0.1 mL, and the upper limit of the preferable 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 viscosity reduction. If the amount used is large, the solvent remains in the material, which tends to cause problems such as thermal cracks.
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 An imparting agent, an antistatic agent, a radiation blocking agent, a nucleating agent, a phosphorus peroxide decomposing agent, a lubricant, a pigment, a metal deactivator, a thermal conductivity imparting agent, a physical property adjusting agent, a storage stabilizer, etc. It can be added as long as the purpose and effect are not impaired.

(Use)
The curable composition or cured product of the present invention can be used for various applications. It can be applied to various uses where conventional acrylic resins and epoxy resins are used.

  For example, 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.

  Among these, the curable composition of the present invention is a material that can be used as an alkali-developable transparent resist, and is particularly suitable as an FPD material. More specifically, a passivation film for TFT, a gate insulating film for TFT, an interlayer insulating film for TFT, a transparent planarizing film for TFT, a binder resin for color filter, a transparent planarizing material for color filter, a binder resin for black matrix, Examples thereof include a photospacer material for liquid crystal cells and a transparent sealing material for OLED elements.

(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 light having an absorption wavelength of a polymerization initiator or a sensitizer to be used may be used. 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 it may not be cured when the exposure amount is small, and since a pattern may not be formed when the exposure amount is large, the preferable exposure amount range is 1 to 5000 mJ / cm ² , more preferably. Is 1 to 1000 mJ / cm ² .

  For the purpose of improving curability and patterning properties, pre-bake and PEB may be performed before and after photocuring. A preferred temperature range is 50 to 200 ° C, more preferably 50 to 150 ° C. The preferred time is 0.1 to 30 minutes, more preferably 0.1 to 10 minutes.

  The developer can be used without particular limitation as long as it is a commonly used alkaline developer, but specific examples include organic alkali aqueous solutions such as tetramethylammonium hydroxide aqueous solution and choline aqueous solution, and potassium hydroxide aqueous solution. Inorganic aqueous alkali solutions such as sodium hydroxide aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution and lithium carbonate aqueous solution, and those obtained by adding alcohol or surfactant to these aqueous solutions for adjusting 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.

Moreover, in order to improve the characteristics of the cured product after patterning, further baking and exposure may be performed. A preferable temperature range of the baking is 80 to 300 ° C, more preferably 100 to 250 ° C. Preferred time 1 to 120 minutes, more preferably the preferred range is also exposed 10 to 90 minutes 1~10000mJ / cm ^2, more preferably 10~5000mJ / cm ^2.

(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 electrical 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. Therefore, the insulating film is required to have high insulating properties. However, it cannot be applied to an insulating film formed from a resin composition that can be formed by solution coating, because the amount of leakage current when a voltage is applied to the thin film is too large. In the thin film having a thickness of 0.5 μm or less, it is essential that the amount of leakage between electrodes when a 30 V voltage is applied is 20 nA / cm ² or less. Furthermore, considering the reliability of the electronic component, it is preferably 10 nA / cm ² or less, more preferably 5 nA / cm ² .

  In addition, as the thickness of the insulating film increases, the insulation reliability increases and the amount of leakage current between the electrodes tends to decrease, but 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 0.5 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, it is desirable that this insulating film is also excellent in environmental resistance, and is 50% to 100% at a low temperature condition of -60 ° C to 0 ° C, a high temperature condition of 20 ° C to 100 ° C, and further 20 ° C to 90 ° C. Even when stored for a long time under the RH condition, it is desirable that the insulation is 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 preferably a low leakage current amount of the above level at any voltage value between -50V, more preferably 0-100V, and even more preferably between 0-200V regardless of AC voltage or DC voltage. It is preferable that the insulating property is maintained.

  Examples and Comparative Examples of the present invention are shown below, but the present invention is not limited to the following.

(Examples 1-3, Comparative Examples 1-4)
The curable compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4 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 curable material which has the outstanding patternability, insulation, and heat-and-light resistance compared with the composition of the comparative example.

(Patternability evaluation)
The following patterning evaluation samples were prepared using the resin compositions obtained in the following examples and comparative examples. A glass substrate spin-coated with a resin composition is heated on a hot plate heated to 65 ° C. for 1 to 5 minutes, and 20 μm using an exposure apparatus (high-pressure mercury lamp, mask alignment apparatus MA-10 manufactured by Mikasa). Each corner is exposed to an optimal integrated light quantity through a pattern mask (proximity exposure, gap 12 μm), and heated on a hot plate heated to 65 ° C. for 1 to 5 minutes to become an alkaline developer (TMAH 2.38% aqueous solution). After dipping for 60 seconds, it was washed with water for 60 seconds, and moisture on the surface was removed with compressed air or compressed nitrogen to form a pattern.

  Thereafter, the sample was heated for 1 hour on a hot plate heated at 150 ° C. to obtain an evaluation sample. The pattern shape of the obtained evaluation sample was observed using a 3D measurement laser microscope (manufactured by LEXT OLS4000 Olympus) and a stylus type surface shape measuring instrument (manufactured by Dektak 150 Veeco), and the state around the 20 μm square hole was as follows. Evaluation was made according to criteria.

<Evaluation criteria>
○: There is no dent in the film within 50 μm from the side of the hole ×: There is a dent in the film within 50 μm from the side of the hole XX: Hole cannot be formed (insulation evaluation)
The following insulation evaluation samples were prepared using the resin compositions obtained in the following examples and comparative examples. A SUS plate whose surface was # 400 polished and spin-coated with the resin composition was exposed to an integrated light amount of 200 mJ / cm ² . Then, it heated on the hotplate heated at 150 degreeC for 1 hour, and formed the thin film. Further, an Al electrode (6 mmφ) was formed on the thin film by sputtering.

  For insulation, a precision semiconductor parameter analyzer measuring device (4156C Agilent) was used, and a voltage of 0 to 50 V was applied in steps of 0.5 V between the electrodes sandwiching the insulating film (SUS-Al), The leakage current amount per electrode unit area when 30 V was applied was measured and evaluated. The film thickness at this time was measured with a stylus type surface shape measuring instrument.

(Heat and light resistance evaluation)
The following heat and light resistance evaluation samples were prepared using the resin compositions obtained in the following examples and comparative examples. A glass plate on which a resin composition was spin-coated was exposed to an integrated light amount of 150 mJ / cm ² . Then, it heated on the hotplate heated at 200 degreeC for 30 minutes, and formed the thin film.

The heat light resistance, using a metering weather meter (manufactured by M6T Suga Test Instruments Co., Ltd.), BPT85 ℃, irradiated with integrated light quantity of 50 MJ / m ² at an irradiation intensity 0.7 kW / m ^2, and the film thickness before the test The film thickness after the test was measured with a stylus type surface shape measuring instrument, and the film thickness reduction rate at that time was evaluated.

(Synthesis Example 1)
In a 500 mL four-necked flask, 57.5 g of toluene and 57.5 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the gas phase portion was purged with nitrogen, and then heated and stirred at an internal temperature of 105 ° C. 30 g of a mixed solution of 3.2 g of triallyl isocyanurate, 6.0 g of diallyl isocyanuric acid, 42.1 g of 1,4-dioxane, and 18.7 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) It was added dropwise over a period of 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 a colorless and transparent liquid “Reactant A”.

40 g of toluene and 10 g of “Reactant A” were placed in a 100 mL four-necked flask, and the gas phase was purged with nitrogen and heated at an internal temperature of 105 ° C., where 1.7 g of vinylcyclohexene oxide and 1.7 g of toluene were added. 3 hours after the addition, it was confirmed by ¹ H-NMR that the reaction rate of the vinyl group was 95% or more. The reaction solution was cooled to obtain “Reaction product 1”. ¹ H-NMR measurement confirmed that the polysiloxane compound had SiH groups of 5.0 mmol / g and epoxy groups of 1.0 mmol / g in terms of equivalents when the standard substance was dibromoethane.

(Synthesis Example 2)
40 g of toluene and 10 g of “Reactant A” obtained in Synthesis Example 1 were placed in a 100 mL four-necked flask, and the gas phase was purged with nitrogen and heated at an internal temperature of 105 ° C. A mixed solution of 3 g and 3.3 g of toluene was added, and 3 hours after the addition, it was confirmed by ¹ H-NMR that the reaction rate of the vinyl group was 95% or more. The reaction solution was cooled to obtain “Reaction product 2”. ¹ H-NMR measurement confirmed that the polysiloxane compound had 4.0 mmol / g SiH groups and 2.0 mmol / g epoxy groups in terms of equivalents when the standard substance was dibromoethane.

(Synthesis Example 3)
In a 500 mL four-necked flask, 57.5 g of toluene and 57.5 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the gas phase portion 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 18.7 mg of a xylene solution of platinum vinylsiloxane complex (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 a colorless and transparent liquid “Reactant C”.

40 g of toluene and 10 g of “Reactant C” were placed in a 100 mL four-necked flask, and the gas phase was replaced with nitrogen and heated at an internal temperature of 105 ° C., where 1.7 g of vinylcyclohexene oxide and 1.7 g of toluene were added. 3 hours after the addition, it was confirmed by ¹ H-NMR that the reaction rate of the vinyl group was 95% or more. The reaction solution was cooled to obtain “Reaction product 3”. ¹ H-NMR measurement confirmed that the polysiloxane compound had 4.5 mmol / g SiH groups and 0.9 mmol / g epoxy groups in terms of equivalents when the standard substance was dibromoethane.

Example 1
0.5 g of “Reactant 1” as component (A), 0.166 g of triallyl isocyanurate as component (B), and 0 of bis (2,4-pentanedionate) platinum (II) as component (C) .67 mg, 26.6 mg of BBI-103 as the component (D), 2.0 mg of xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) as the catalyst, and 13.10 of 9,10-diphenylanthracene as the sensitizer. A 20% PGMEA solution with 3 mg added was prepared.

(Example 2)
0.5 g of “Reactant 1” as component (A), 0.166 g of triallyl isocyanurate as component (B), and 6 of bis (2,4-pentanedionate) platinum (II) as component (C) 0.7 mg, 13.3 mg of BBI-103 as component (D), 2.0 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) as a catalyst, and 13.10 of 9,10-diphenylanthracene as a sensitizer. A 20% PGMEA solution with 3 mg added was prepared.

(Example 3)
0.5 g of “Reactant 3” as component (A), 0.166 g of triallyl isocyanurate as component (B), and 3 of bis (2,4-pentanedionate) platinum (II) as component (C) .3 mg, 26.6 mg of BBI-103 as component (D), 2.0 mg of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) as a catalyst, and 13 of 9,10-diphenylanthracene as a sensitizer A 20% PGMEA solution with 3 mg added was prepared.

(Comparative Example 1)
0.5 g of “Reactant 1” as component (A), 0.166 g of triallyl isocyanurate as component (B), 26.6 mg of BBI-103 as component (D), xylene of platinum vinylsiloxane complex as catalyst A 20% PGMEA solution was prepared by adding 2.0 mg of the solution (containing 3 wt% as platinum) and 13.3 mg of 9,10-diphenylanthracene as the sensitizer.

(Comparative Example 2)
0.5 g of “Reactant 2” as component (A), 0.083 g of triallyl isocyanurate as component (B), 23.3 mg of BBI-103 as component (D), xylene of platinum vinylsiloxane complex as catalyst A 20% PGMEA solution was prepared by adding 1.7 mg of a solution (containing 3 wt% as platinum) and 11.7 mg of 9,10-diphenylanthracene as a sensitizer.

(Comparative Example 3)
A 20% PGMEA solution containing 0.5 g of “Reactant 2” as component (A), 23.3 mg of BBI-103 as component (D), and 11.7 mg of 9,10-diphenylanthracene as a sensitizer was added. It was adjusted.

(Comparative Example 4)
0.5 g of “Reactant 3” as component (A), 0.166 g of triallyl isocyanurate as component (B), and 6 of bis (2,4-pentanedionate) platinum (II) as component (C) A 20% PGMEA solution prepared by adding 0.7 mg and 13.3 mg of 9,10-diphenylanthracene as a sensitizer was prepared.

Claims (15)

  (A) A polysiloxane compound having a SiH group and a photopolymerizable functional group, (B) an alkenyl group-containing compound, (C) a photoactive platinum complex catalyst, (D) a curable composition containing a photopolymerization initiator .   The curing according to claim 1, wherein the photopolymerizable functional group of the component (A) is at least one selected from the group consisting of an epoxy group, a crosslinkable silicon group, a (meth) acryloyl group, an oxetanyl group, and a vinyloxy group. Sex composition.   The curable composition of Claim 1 or 2 whose at least 1 of the photopolymerizable functional group of a component (A) is an alicyclic epoxy group, an oxetanyl group, or a glycidyl group.   The curable composition according to claim 1 or 2, wherein at least one of the photopolymerizable functional groups of component (A) is an alkoxysilyl group. Component (B) is represented by the following general formula (I)

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ includes an alkenyl group). The curable composition as described in any one of Claims 1-4 which is a compound made. Component (B) The curable composition according to any one of claims 1 to 5 which is a compound having a Si-CH = CH ₂ group. Component (A) is composed of at least two photopolymerizable functional groups and at least two SiH groups, each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. It is a polysiloxane type compound which has at least 1 type chosen from the group which consists of. The curable composition as described in any one of Claims 1-6.

The curable composition according to any one of claims 1 to 7, wherein the component (A) is a hydrosilylation reaction product of the following compounds (α) to (γ).
(Α) Organic compound having at least one alkenyl group (β) Organosiloxane compound having at least two SiH groups (γ) Compound having at least one photopolymerizable functional group and at least one alkenyl group The compound (α) has a general formula (II) having at least one alkenyl group

(Wherein R ³ represents a monovalent organic group having 1 to 50 carbon atoms, and each R ³ may be different or the same, and at least one R ³ includes an alkenyl group). The curable composition according to claim 8, wherein the curable composition is a compound. The curable composition according to claim 8 or 9, wherein the compound (α) is a compound having a Si—CH═CH ₂ group. The compound (α) is selected from the group consisting of at least one alkenyl group in one molecule and each structure represented by the following formulas (X1) to (X3), a phenolic hydroxyl group, and a carboxyl group. It is an organic compound which has at least 1 type, The curable composition as described in any one of Claims 8-10 characterized by the above-mentioned.

Compound (β) is represented by the following general formula (III)

(Wherein R ⁴ and R ⁵ represent an organic group having 1 to 10 carbon atoms and may be the same or different, n represents 2 to 10, and m represents a number of 0 to 10)
The curable composition according to any one of claims 8 to 11, which is a cyclic organopolysiloxane compound having a SiH group represented by the formula: Compound (γ) is represented by the following general formula (IV)

(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). The curable composition as described in any one of 8-12. The curable composition according to any one of claims 1 to 13, wherein the component (C) is a β-diketone platinum complex.   Hardened | cured material formed by hardening | curing the curable composition as described in any one of Claims 1-14.