JP2002241501A - Curing agent, curable composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing agent and curable composition each providing a cured product having high optical transparency, and to provide a cured product having high optical transparency. SOLUTION: This curing agent has at least two SiH groups in one molecule and is obtained by hydrosilylation reaction of (α) an organic compound having in one molecule at least two carbon - carbon double bonds having reactivity with SiH group and essentially having (1) 1-6 vinyl group(s) in one molecule, (2) <900 molecular weight and (3) <1,000 p viscosity with (β) a linear and/or cyclic polyorganosiloxane(s) having at least two SiH groups in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curing agent, a curable composition using the same, and a cured product obtained by curing the same.

[0002]

2. Description of the Related Art A curable composition comprising a compound containing a carbon-carbon double bond, a compound containing a SiH group, and a hydrosilylation catalyst has been proposed (for example, Japanese Patent Application Laid-Open No. 3-277645). JP-A-7-3030, JP-A-9-302095, JP-A-5-295270, JP-A-7-62103). These are carbon-carbon double bonds and S
It exhibited excellent physical, thermal and electrical properties derived from crosslinking by reaction with iH groups. But,
When a known silicone-based curing agent was used, the compatibility with the organic allyl compound was low, so the reactivity and transparency of the cured product were not sufficient, and the industrial value was limited. was there.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a curing agent, a curable composition, and a high optical transparency which exhibit high compatibility with an organoallyl compound and give a cured product having high optical transparency. Is to provide a cured product having:

[0004]

Means for Solving the Problems In order to solve such problems, the present inventors have conducted intensive studies and as a result, have found that the above problems can be solved by forming a curable composition using a compound having a specific structure. Heading, and led to the present invention.

That is, the present invention relates to (α) (a) that one to six vinyl groups are contained in one molecule, (b) the molecular weight is less than 900, and (c) the viscosity is less than 1,000 poise. An organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule, and (β) at least two SiH groups in one molecule. A curing agent containing at least two SiH groups in one molecule (claim 1), which is obtained by hydrosilylation reaction of a chain and / or cyclic polyorganosiloxane having the component (α), Allyl ether of novolak phenol, vinylcyclohexene,
Divinylbenzene, divinylbiphenyl, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, and

[0006]

Embedded image The curing agent according to claim 1, wherein the component (β) is 1,3,
3. The curing agent according to claim 1 or 2, wherein the curing agent is 5,7-tetramethyltetracyclosiloxane, wherein (A) a carbon-carbon double bond having reactivity with a SiH group is one. A curable composition containing, as essential components, at least two organic compounds contained in a molecule, (B) a curing agent containing a SiH group, and (C) a hydrosilylation catalyst, wherein the component (B) is a component. The curable composition according to claim 1, which is the curing agent according to claim 1 (claim 4), (A)
An organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule, (B) SiH
A curable composition comprising a group-containing curing agent and a (C) hydrosilylation catalyst as essential components, wherein the component (B) is the curing agent according to claim 2. (Claim 5), (A) an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule, (B) a curing agent containing a SiH group, A curable composition containing C) a hydrosilylation catalyst as an essential component, wherein the component (B) is the curing agent according to claim 3 (claim 6). The component (A) described above, (A) contains 1 to 6 vinyl groups in one molecule, (B) the molecular weight is less than 900, (C) the viscosity is less than 1000 poise. 7. A condition as an essential condition. Wherein the component (A) is an allyl ether of novolak phenol, vinylcyclohexene, divinylbenzene, divinylbiphenyl, triallyl isocyanurate, 1,2,4-trivinyl Cyclohexane, and

[0007]

Embedded image A compound represented by the formula:
The curable composition according to any one of claims (claim 8) and (4).
A cured product obtained by curing the curable composition according to any one of (1) to (8) (claim 9).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The curing agent of the present invention comprises (a) (a) one to six vinyl groups per molecule, (b) a molecular weight of less than 900, and (c) a viscosity of 1,000. An organic compound containing at least two carbon-carbon double bonds having reactivity with a SiH group in one molecule, and (β) at least two SiHs in one molecule. It is not particularly limited as long as it is a curing agent containing at least two SiH groups in one molecule, which is obtained by a hydrosilylation reaction of a linear and / or cyclic polyorganosiloxane having a group. Absent.

The component (α) in the present invention will be described.

The component (α) is an organic compound containing at least two carbon-carbon double bonds in one molecule having reactivity with a SiH group, and (a) one vinyl group in one molecule.
Any organic compound can be used without particular limitation as long as the organic compound satisfies the following conditions: (1) it contains at least six, (2) the molecular weight is less than 900, and (3) the viscosity is less than 1,000 poise.

The component (α) is a compound containing 1 to 6 vinyl groups, preferably 2 to 4 vinyl groups in one molecule, in view of the balance between its reactivity and storage stability. .

The component (α) has a molecular weight of 90 from the viewpoint of handleability and heat resistance and electrical properties of the cured product.
Less than 0, preferably less than 700, more preferably 50
Less than 0 compounds.

The component (α) has a viscosity of less than 1000 poise, preferably 3
The compound is less than 00 poise, more preferably less than 30 poise.

Further, the component (α) is selected from the group consisting of availability of raw materials,
From the viewpoints of reactivity with the component (β), heat resistance of the cured product, and transparency, allyl ether of novolak phenol, vinylcyclohexene, divinylbenzene, divinylbiphenyl, triallyl isocyanurate, 1,2,4-trivinyl Cyclohexane, and

[0016]

Embedded image Are preferred. More preferably, vinylcyclohexene, divinylbenzene, divinylbiphenyl, triallyl isocyanurate, 2,2-bis (4
-Hydroxycyclohexyl) diallyl ether of propane, 1,2,4-trivinylcyclohexane, 2,
2′-diallylbisphenol S.

In the component (α), the structure is a carbon-bonded to the skeleton by a covalent bond (possibly through a divalent or higher valent substituent) to the skeleton and having a reactivity with the SiH group. And a group having a carbon double bond (vinyl group).

The skeleton of the organic compound (α) is not particularly limited, and an organic monomer skeleton or an organic polymer skeleton may be used.

As the monomer skeleton, for example, a phenol type,
Examples thereof include aromatic hydrocarbons such as bisphenols, benzene, and naphthalene, aliphatic hydrocarbons, and mixtures thereof. Examples of the organic polymer skeleton include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, polyacrylate, polyamide, phenol-formaldehyde (phenol resin), and polyimide. Can be used.

The vinyl group of the component (α) is not particularly limited as long as it has reactivity with a SiH group.

[0021]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) An alkenyl group represented by the formula ( ¹ ) is preferable from the viewpoint of reactivity. Also, from the availability of raw materials,

[0022]

Embedded image Is particularly preferred.

The vinyl group may be covalently bonded to the skeleton portion of the component (α) via a divalent or higher valent substituent, provided that the divalent or higher valent substituent has 0 to 10 carbon atoms. Although there is no particular limitation, C, H, N, O,
Those containing only S and halogen are preferred. Examples of these substituents include

[0024]

Embedded image

[0025]

Embedded image Is mentioned. Further, two or more of these divalent or more substituents may be connected by a covalent bond to constitute one divalent or more substituent.

Examples of the groups covalently bonded to the above skeleton include vinyl, allyl, methallyl, acryl, methacryl, 2-hydroxy-3- (allyloxy) propyl, and 2-allylphenyl Group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group,
-(Allyloxy) phenyl group, 2- (allyloxy)
Ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0027]

Embedded image Is mentioned.

As the component (α), a low molecular weight compound which is difficult to be divided into a skeleton portion and a vinyl group as described above can be used. Specific examples of these low molecular weight compounds include butadiene, isoprene, octadiene, aliphatic chain polyene compounds such as decadiene, triallyl isocyanurate, aliphatic cyclic polyene compounds such as trivinylcyclohexane, and substitution of vinylcyclopentene and the like. Examples thereof include aliphatic cyclic olefin compounds.

From the viewpoint that the heat resistance can be further improved, the component (α) contains a carbon-carbon double bond reactive with a SiH group in an amount of 0.00 per gram of the component (α).
What is necessary is just to contain 1 mol or more.
Those containing 0.005 mol or more per g are preferable, and those containing 0.008 mol or more are particularly preferable. Specific examples include butadiene, isoprene, decadiene, diallyl phthalate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, and divinylbenzenes (with a purity of 50 to 100%, preferably with a purity of 80 to 100%). 1,3
-Diisopropenylbenzene, 1,4-diisopropenylbenzene, triallyl isocyanurate, trivinylcyclohexane

[0030]

Embedded image And the like.

As the component (α), triallyl isocyanurate and trivinylcyclohexane are preferred from the viewpoint that the obtained cured product is less colored and has higher optical transparency and that the light resistance is less colored.

The number of carbon-carbon double bonds reactive with the SiH group of the component (α) may be at least two per molecule on average, but from the viewpoint that heat resistance can be further improved, It is preferably more than 2, more preferably 3 or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of the component (α) is 1 or less per molecule, even if it reacts with the component (β), only a graft structure is formed and a crosslinked structure is formed. No.

Next, the component (β) will be described. The (β) component of the present invention, at least two S
The chain and / or cyclic polyorganosiloxane having an iH group is not particularly limited, but from the viewpoint of good compatibility with the component (α), the following general formula (II)

[0034]

Embedded image (Wherein, R ² represents an organic group having 1 to 6 carbon atoms, and n represents 3 to
Represents the number 10. )), A cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable. In addition, the substituent R ² in the compound represented by the general formula (II) is preferably composed of C, H, and O, and more preferably a hydrocarbon group.
Further, from the viewpoint of availability and the like, 1,3,5,7-tetramethyltetracyclosiloxane is more preferable.

The above-mentioned various (β) components can be used alone or as a mixture of two or more.

The mixing ratio of the component (α) and the component (β) as described above is not particularly limited. However, when considering the strength of the cured product obtained by hydrosilylation of the component (B) and the component (A). , Component (B) preferably has a large number of SiH groups, so that in general, the number (X) of carbon-carbon double bonds reactive with the SiH groups in component (α) and the number of carbon-carbon double bonds in component (β) The ratio of the number of SiH groups to the number (Y) is preferably 5 ≧ Y / X ≧ 1. It is more preferable that 3.5 ≧ Y / X ≧ 2.

The following catalysts can be used as a catalyst for the hydrosilylation reaction between the component (α) and the component (β). For example, platinum alone, solid platinum supported on a carrier such as alumina, silica or carbon black, chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (for example, Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ ) ₂ , Pt
_{(CH 2 = CH 2) 2} Cl 2), platinum - vinylsiloxane complex (e.g., Pt (ViMe ₂ SiOSiMe ₂ V
i) _n , Pt [(MeViSiO) ₄ ] _m ), a platinum-phosphine complex (eg, Pt (PPh ₃ ) ₄ , Pt (PBu)
₃ ) ₄ ), a platinum-phosphite complex (for example, Pt [P
(OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ ) (where M
e is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph
Represents a phenyl group, and n and m represent integers. ), Dicarbonyldichloroplatinum, Karstedt
dt) catalysts and also the platinum-hydrocarbon complexes described in Ashby U.S. Pat. Nos. 3,159,601 and 3,159,662, and in Lamoreaux U.S. Pat. No. 3,220,972. Platinum alcoholate catalyst. In addition, Modic US Patent No. 3
The platinum chloride-olefin complexes described in 516946 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 , PdC
_{l 2 · 2H 2 O, NiCl} 2, TiCl 4, and the like.

Of these, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst to be added is not particularly limited, but in order to have sufficient curability and to keep the cost of the curable composition relatively low, 10 ^-1 to 1 ^-1 to 1 mol of SiH groups.
It is preferably in the range of ^0-8 mol, more preferably ^10-2 to
It is in the range of 10 ^-6 mol.

The curable composition of the present invention comprises (A) an organic compound containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and (B) a cured compound containing SiH groups. A curable composition containing an agent, (C) a hydrosilylation catalyst as an essential component, wherein the component (B) is the curing agent according to claim 1. .

The component (A) can be used without any particular limitation as long as it is an organic compound containing at least two carbon-carbon double bonds reactive with a SiH group in one molecule. It does not contain siloxane units (Si-O-Si) such as polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, but has a skeleton containing only C, H, N, O, S, and halogen as constituent elements. Preferably, there is. In the case of those containing a siloxane unit, there are problems of gas permeability and repellency.

The component (A) is preferably a compound containing 1 to 6 vinyl groups in one molecule, and more preferably a compound containing 2 to 4 vinyl groups, in view of the balance between the reactivity and the storage stability. preferable.

The component (A) has a molecular weight of 90 from the viewpoint of handleability and heat resistance and electrical properties of the cured product.
Preferably less than 0, more preferably less than 700, particularly preferably less than 500 compounds.

The component (A) is preferably a compound having a viscosity of less than 1000 poise, more preferably less than 300 poise, particularly preferably less than 30 poise, from the viewpoint of handleability and processability.

Further, the component (A) is selected from the group consisting of availability of raw materials,
From the viewpoints of reactivity with the component (B), heat resistance and transparency of the cured product, allyl ether of novolak phenol, vinylcyclohexene, divinylbenzene, divinylbiphenyl, triallyl isocyanurate, 1,2,4-trivinyl Cyclohexane, and

[0047]

Embedded image Are preferred.

In the component (A), the structure is bonded to the skeleton by a covalent bond (possibly via a divalent or higher valent substituent) to the skeleton, and has a reactivity with a SiH group. And a group having a carbon double bond (vinyl group).

The skeleton of the component (A) which is an organic compound is not particularly limited, and an organic monomer skeleton or an organic polymer skeleton may be used.

As the monomer skeleton, for example, a phenol type,
Examples thereof include aromatic hydrocarbons such as bisphenols, benzene, and naphthalene, aliphatic hydrocarbons, and mixtures thereof. Examples of the organic polymer skeleton include polyether, polyester, polyarylate, polycarbonate, saturated hydrocarbon, polyacrylate, polyamide, phenol-formaldehyde (phenol resin), and polyimide. Can be used.

The vinyl group of the component (A) is not particularly limited as long as it has reactivity with a SiH group.

[0052]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) An alkenyl group represented by the formula ( ¹ ) is preferable from the viewpoint of reactivity. Also, from the availability of raw materials,

[0053]

Embedded image Is particularly preferred.

The vinyl group may be covalently bonded to the skeleton portion of the component (A) via a divalent or higher valent substituent, provided that the divalent or higher valent substituent has 0 to 10 carbon atoms. Although there is no particular limitation, C, H, N, O,
Those containing only S and halogen are preferred. Examples of these substituents include

[0055]

Embedded image

[0056]

Embedded image Is mentioned. Further, two or more of these divalent or more substituents may be connected by a covalent bond to constitute one divalent or more substituent.

Examples of the group covalently bonded to the skeleton as described above include vinyl, allyl, methallyl, acryl, methacryl, 2-hydroxy-3- (allyloxy) propyl, and 2-allylphenyl. Group, 3-allylphenyl group, 4-allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group,
-(Allyloxy) phenyl group, 2- (allyloxy)
Ethyl group, 2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0058]

Embedded image Is mentioned.

As the component (A), it is possible to use a low-molecular-weight compound which is difficult to be divided into a skeleton portion and a vinyl group as described above. Specific examples of these low molecular weight compounds, butadiene, isoprene, octadiene, aliphatic chain polyene compound system such as decadiene, triallyl isocyanurate, aliphatic cyclic polyene compound system such as trivinylcyclohexane, vinylcyclopentene,
Substituted aliphatic cyclic olefin compounds such as vinylcyclohexene are exemplified.

From the viewpoint that the heat resistance can be further improved, the component (A) has a carbon-carbon double bond reactive with a SiH group in an amount of 0.00 per g of the component (A).
What is necessary is just to contain 1 mol or more.
Those containing 0.005 mol or more per g are preferable, and those containing 0.008 mol or more are particularly preferable. Specific examples include butadiene, isoprene, vinylcyclohexene, decadiene, diallyl phthalate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, and divinylbenzenes (with a purity of 50 to 100%, preferably a purity of 80 to 100%).
100%), 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, triallyl isocyanurate, trivinylcyclohexane

[0061]

Embedded image And the like.

As the component (A), vinylcyclohexene, triallyl isocyanurate and trivinylcyclohexane are preferred from the viewpoint that the obtained cured product is less colored and has higher optical transparency and that the light resistance is less. Among them, triallyl isocyanurate and trivinylcyclohexane are more preferable.

The number of carbon-carbon double bonds reactive with the SiH group of component (A) should be at least two per molecule on average, but from the viewpoint that heat resistance can be further improved, It is preferably more than 2, more preferably 3 or more. When the number of carbon-carbon double bonds having reactivity with the SiH group of the component (A) is 1 or less per molecule, when the reaction with the component (B) occurs, only a graft structure is formed and a crosslinked structure is formed. No.

The mixing ratio of the component (A) and the component (B) is not particularly limited as long as the required strength is not lost, but generally, the mixing ratio between the SiH group in the component (A) and the carbon -The ratio of the number of carbon double bonds (X) to the number of SiH groups (Y) in the component (B) is 2 ≧ Y / X ≧ 0.
It is preferably 5. Y / X> 2 or 0.5
If> Y / X, sufficient curability cannot be obtained, sufficient strength may not be obtained, and heat resistance may be low. Next, the hydrosilylation catalyst as the component (C) will be described. Here, the hydrosilylation catalyst as the component (C) is
The hydrosilylation catalyst contained in the component (B) can be substituted. That is, when the hydrosilylation catalyst used in synthesizing the component (B) by hydrosilylation has a hydrosilylation activity in the component (B) after the completion of the reaction, the components (A) and (B) It can be used as a component hydrosilylation catalyst. The hydrosilylation catalyst as the component (C) is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. Examples thereof include simple platinum, alumina, silica, and carbon black on which a solid platinum is supported. Chloroplatinic acid, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc.
Olefin complexes (for example, Pt (CH ₂ ＣＨCH ₂ ) ₂ (P
_{Ph 3) 2, Pt (CH} 2 = CH 2) 2 Cl 2), platinum - vinylsiloxane complex (e.g., Pt (ViMe ₂ SiOS
iMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complex (for example, Pt (PPh ₃ ) ₄ , Pt
(PBu ₃ ) ₄ ), a platinum-phosphite complex (for example, P
t [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ ) (where Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are , An integer.), Dicarbonyldichloroplatinum, Karstedt's catalyst, and Ashby (Ash)
by) US Patents 3,159,601 and 31,596
No. 62, as well as the platinum-hydrocarbon complex described in Lamoreaux.
Platinum alcoholate catalysts described in U.S. Pat. No. 2,209,72. In addition, Modic
Platinum chloride-olefin complexes described in U.S. 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 , PdC
_{l 2 · 2H 2 O, NiCl} 2, TiCl 4, and the like.

Among them, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst to be added is not particularly limited ^;
It is preferably in the range of ^0-8 mol, more preferably ^10-2 to
It is in the range of 10 ^-6 mol.

Further, a co-catalyst can be used in combination with the above-mentioned catalyst, and examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, and 2-hydroxy-2- compounds. Examples include acetylene alcohol compounds such as methyl-1-butyne, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine. The addition amount of the co-catalyst is not particularly limited, the catalyst 1 mol, preferably ^10-2 to ² mols, more preferably from 10 ^-1 to 10 mol.

Further, a curing retarder can be used for the purpose of improving the storage stability of the composition of the present invention or for adjusting the reactivity of the hydrosilylation reaction in the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide. These may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, and maleic esters. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, thiazole,
Benzothiazole, benzothiazole disulfide and the like are exemplified. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Among these curing retarders, benzothiazole, thiazole, dimethylmalate, and 3-hydroxy-3-methyl-1-butyne are preferred from the viewpoint of good retarding activity and good raw material availability.

[0071] The addition amount of the storage stability improving agent, compared hydrosilylation catalyst 1mol used, and is preferably from 10 ^-1 to 10 ³ mols, more preferably from 1 to 50 mol.

As the composition of the present invention, various combinations can be used as described above. From the viewpoint of good heat resistance, the cured product obtained by curing the composition has a Tg of 50 ° C. or more. Are preferable, those having a temperature of 100 ° C. or higher are more preferable, and those having a temperature of 150 ° C. or higher are particularly preferable.

The composition of the present invention may optionally contain an inorganic filler. Addition of the inorganic filler is effective in preventing the fluidity of the composition and increasing the strength of the material. As the inorganic filler, those which do not degrade the optical properties and are in the form of fine particles are preferable, and include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica and hydrophobic ultrafine silica, talc, barium sulfate and the like. Can be.

Furthermore, various resins can be added for the purpose of modifying the properties of the composition of the present invention. Examples of the resin include, but are not limited to, polycarbonate resin, polyether sulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, polyimide resin, polyvinyl acetal resin, urethane resin and polyester resin. Not something.

The composition of the present invention can be directly formed into a film or the like, but the composition can be dissolved in an organic solvent to form a varnish. Solvents that can be used are not particularly limited, and if specifically exemplified,
Hydrocarbon solvents such as benzene, toluene, hexane and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; chloroform; methylene chloride; 1,2-dichloroethane; Can be suitably used. Solvent 2
It can also be used as a mixed solvent of more than one kind. As the solvent, toluene, tetrahydrofuran and chloroform are preferred. The amount of the solvent used is preferably in the range of 0 to 10 mL, more preferably in the range of 0.5 to 5 mL, and more preferably in the range of 1 to 3 mL, per 1 g of the reactive (A) component used. Is particularly preferred. If the amount used is small, it is difficult to obtain the effect of using a solvent such as lowering the viscosity, and if the amount used is large, the solvent tends to remain in the material, easily causing problems such as thermal cracks, and also in terms of cost. It is disadvantageous and reduces the industrial use value.

The composition of the present invention further comprises an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a foaming agent, a storage stability improver, an ozone deterioration inhibitor, Light stabilizer, thickener, plasticizer, coupling agent, antioxidant, heat stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus-based peroxide decomposer, lubricant, pigment , A metal deactivator, a physical property modifier and the like can be added within a range not to impair the object and effect of the present invention.

The composition for an optical material of the present invention is mixed in advance and cured by reacting a part or all of the SiH group with a carbon-carbon double bond having reactivity with the SiH group in the composition. It can be an optical material.

As the mixing method, various methods can be employed, but a method of mixing the component (A) with the component (C) and the component (B) is preferable. When the method of mixing the component (C) with the mixture of the component (A) and the component (B), it is difficult to control the reaction. When the method of mixing the component (A) with the mixture of the component (B) with the component (B) is used, the component (B) has a reactivity with moisture in the presence of the component (C), so that it is stored. It may be transformed into

In the case where the composition is reacted and cured, the components (A), (B) and (C) may be mixed at once with the required amounts of the respective components, but may be partially mixed. After the reaction, the remaining amount is mixed to further react, or after the mixing, only a part of the functional groups in the composition is reacted (B-staged by controlling the reaction conditions and utilizing the difference in the reactivity of the substituents). ), Followed by a treatment such as molding and further curing. According to these methods, viscosity adjustment at the time of molding becomes easy.

As a method of curing, the reaction can be carried out simply by mixing, or the reaction can be carried out by heating. From the viewpoint that the reaction is fast and a material having high heat resistance is generally easily obtained, a method of performing the reaction by heating is preferable.

The reaction temperature can be variously set, for example, a temperature of 30 to 300 ° C. can be applied, and a temperature of 100 to 250 ° C.
Is more preferable, and 150 to 200C is further preferable.
When the reaction temperature is low, the reaction time for causing a sufficient reaction is prolonged, and when the reaction temperature is high, molding tends to be difficult.

The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple stages or continuously as required.

The reaction time can be variously set.

The pressure during the reaction can be variously set as required.
The reaction can be performed at normal pressure, high pressure, or reduced pressure.

The shape of the optical material obtained by curing can be various depending on the application, and is not particularly limited. For example, the optical material has a shape such as a film, a sheet, a tube, a rod, a coating, and a bulk. can do.

Various molding methods can be used, including a conventional method for molding a thermosetting resin. For example, a molding method such as a casting method, a pressing method, a casting method, a transfer molding method, a coating method, and a RIM method can be applied. As the molding die, a polishing glass, a hard stainless steel polishing plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like can be used. Further, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be used to improve the releasability from a mold.

Various processes can be performed as necessary at the time of molding. For example, a process of defoaming the composition or a partially reacted composition by centrifugation, decompression, or the like to suppress voids generated during molding, a process of once releasing the pressure during pressing, and the like can be applied.

The cured product obtained by the present invention can be used for various applications including optical materials.

The optical material generally refers to a material used for the purpose of transmitting light such as visible light, infrared light, ultraviolet light, X-ray, and laser through the material.

More specifically, in addition to the LED sealing materials such as the lamp type and the SMD type, the following can be mentioned.

Substrate materials in the liquid crystal display field,
It is a liquid crystal display device peripheral material such as a liquid crystal film such as a light guide plate, a prism sheet, a polarizing plate, a phase difference plate, a viewing angle correction film, an adhesive, and a polarizer protective film. In addition, encapsulants for color PDPs (plasma displays) expected as next-generation flat panel displays, antireflection films, optical correction films, housing materials, front glass protection films, front glass replacement materials, adhesives, and LED displays LED molding material used in equipment, LE
D sealing material, front glass protective film, front glass substitute material, adhesive, and plasma addressed liquid crystal (PAL)
C) Substrate material for display, light guide plate, prism sheet, polarizing plate, retardation plate, viewing angle correction film, adhesive, polarizer protective film, protective film for front glass in organic EL (electroluminescence) display, front glass Alternative materials, adhesives, various film substrates in field emission display (FED), front glass protective films, front glass alternative materials, adhesives.

In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-
R / DVD-RAM, MO / MD, PD (phase change disk), disk substrate material for optical card, pickup lens, protective film, sealing material, adhesive, etc.

In the field of optical instruments, materials for steel camera lenses, finder prisms, target prisms,
The viewfinder cover and light receiving sensor. Also, it is a shooting lens and a finder of a video camera. Further, it is a projection lens of a projection television, a protective film, a sealing material, an adhesive or the like. Materials for optical sensing devices such as lenses, sealing materials, adhesives, and films.

In the field of optical components, there are fiber materials, lenses, waveguides, sealing materials for elements, adhesives, etc. around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. In the case of optical passive components and optical circuit components, there are a lens, a waveguide, an LED sealing material, a CCD sealing material, an adhesive and the like. Substrate materials, fiber materials, sealing materials for elements, adhesives, etc. around the optoelectronic integrated circuit (OEIC).

In the field of optical fiber, it is an optical fiber for industrial use such as illumination / light guide for decorative display, display / sign, etc., and for communication infrastructure and for connecting digital equipment in home.

The semiconductor integrated circuit peripheral material is a resist material for microlithography for LSI and VLSI materials.

In the field of automobiles and transportation equipment, lamp reflectors for automobiles, bearing retainers, gears, corrosion-resistant coatings, switches, headlamps, engine parts, electric parts, various interior and exterior parts, drive engines, brake oil tanks, Rustproof steel plates for automobiles, interior panels,
It is an interior material, protection and bundling wire, fuel hose, car lamp, and glass substitute. Further, it is a double glazing for railway vehicles. Also, a toughening agent for aircraft structural materials,
Peripheral components for the engine, wireness for protection and binding, and corrosion-resistant coating.

In the architectural field, there are materials for interior and processing, electric covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a film for house covering.

As next-generation optical and electronic functional organic materials,
Organic EL element peripheral materials, organic photorefractive elements, light-to-light conversion devices such as optical amplifier elements, optical operation elements, substrate materials around organic solar cells, fiber materials, element sealing materials, adhesives, and the like.

Other uses of the optical material include general uses in which a thermosetting resin such as an epoxy resin is used. For example, adhesives, paints, coating agents, molding materials (sheets, films, FRP And the like, an insulating material (including a printed circuit board, an electric wire covering, and the like), an encapsulant, and additives to other resins and the like.

Examples of the adhesive include adhesives for electronic materials, in addition to adhesives for civil engineering, construction, automobile, general office, and medical use. Among these, adhesives for electronic materials include interlayer adhesives for multilayer boards such as build-up boards,
Die bonding agents, adhesives for semiconductors such as underfills, BGA reinforcing underfills, mounting adhesives such as anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), and the like.

Examples of the sealing agent include potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer molding, COB, COF, TAB of ICs and LSIs.
For example, potting sealing for underfilling, underfill for flip chip and the like, sealing at the time of mounting IC packages such as BGA and CSP (underfill for reinforcement) and the like can be mentioned.

[0103]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited by the following. (Example 1) A magnetic stirrer and a cooling tube were set in a 200 mL two-necked flask. Toluene 50
g, 11.3 μL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum), 5.0 g of triallyl isocyanurate, 37.04 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 90 ° C. The mixture was heated and stirred in an oil bath for 30 minutes. Further, the mixture was heated and refluxed for 2 hours in a 130 ° C. oil bath. 1-ethynyl-
176 mg of 1-cyclohexanol was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ^{By 1} H-NMR,
In this, a part of the SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane reacted with triallyl isocyanurate,

[0104]

Embedded image Was found to be a compound having the structure: This compound is one of the curing agents of the present invention. (Example 2) 2.5 g of triallyl isocyanurate and 3.0 g of the curing agent synthesized in Example 1 were mixed in a cup, and defoamed under reduced pressure of about 1 torr for 30 minutes. Example 1
The curing agent indicated by contains a platinum vinyl siloxane complex as the component (C) of the present invention. This was poured into a cell made by inserting a 3 mm thick silicone rubber sheet as a spacer between two glass plates, and then flowing at 80 ° C. /
Heating was performed for 60 minutes, 100 ° C./60 minutes, and 120 ° C./60 minutes to obtain a visually uniform, colorless and transparent cured product. (Example 3) A magnetic stirrer and a cooling tube were set in a 500 mL two-necked flask. In this flask, 4.8 mg of a xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum), 20.0 g of 1,2,4-trivinylcyclohexane, 236.2 g of 1,3,5,7-tetramethylcyclotetrasiloxane Was added, and the mixture was heated and stirred in a 70 ° C. oil bath for 3 hours. Unreacted 1,3,5
7-Tetramethylcyclotetrasiloxane was distilled off under reduced pressure. ^{According to 1} H-NMR, this was 1,3,5,7-
Some of the SiH groups in tetramethylcyclotetrasiloxane reacted with 1,2,4-trivinylcyclohexane

Embedded image Was found to be a compound having the structure: This compound is one of the curing agents of the present invention. (Example 4) 6.0 g of curing agent 1 synthesized in Example 3
And 0.9 g were mixed in a cup, and the mixture was defoamed under a reduced pressure of about 1 torr for 40 minutes. The curing agent shown in Example 3 contains a platinum vinyl siloxane complex as the component (C) of the present invention. This was flowed through a cell formed by inserting a 3 mm thick silicone rubber sheet as a spacer between two glass plates, and was heated at 65 ° C./20 minutes and 100 ° C./40.
After heating for 120 minutes at 120 ° C. for 40 minutes, a colorless and transparent cured product which was visually uniform and colorless was obtained. (Synthesis Example 1) A stirrer and a condenser were set in a 1 L three-necked flask. In this flask, add bisphenol A1
14 g, potassium carbonate 145 g, allyl bromide 14
0 g and acetone (250 mL) were added, and the mixture was stirred at 60 ° C. for 12 hours. The supernatant was taken, washed with an aqueous sodium hydroxide solution using a separating funnel, and then washed with water. After the oil layer was dried over sodium sulfate, the solvent was distilled off using an evaporator, and 126 g of a pale yellow liquid was obtained. ¹ H-
NMR revealed that bisphenol A was diallyl ether in which the OH group of bisphenol A was allyl etherified. The yield was 82% and the purity was 95% or more. (Example 5) A stirrer, a condenser, and a dropping funnel were set in a 1 L four-necked flask. Toluene 1
50 g, 15.6 μL of a xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum), 1,3,5,7
-500 g of tetramethylcyclotetrasiloxane was added, and the mixture was heated to 70 ° C and stirred in an oil bath. 64 g of bisphenol A diallyl ether produced in Synthesis Example 1 was diluted with 40 g of toluene and added dropwise from a dropping funnel. After stirring at the same temperature for 60 minutes, the mixture was allowed to cool, and 4.74 mg of benzothiazole was added. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain a slightly viscous liquid. ¹ H-NMR revealed that this was a compound in which a part of the SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane had reacted with bisphenol A diallyl ether. This compound is one of the curing agents of the present invention. (Example 6) 1.66 g of triallyl isocyanurate and 2.63 g of the curing agent synthesized in Synthesis Example 2 were mixed in a cup. The curing agent shown in Synthesis Example 2 contains a platinum vinyl siloxane complex as the component (C) of the present invention.
This is poured into a cell formed by inserting a silicone rubber sheet having a thickness of 3 mm as a spacer between two glass plates, and flowing at 80 ° C./60 minutes, 100 ° C./60 minutes, 120 ° C.
The mixture was heated at 60 ° C. for 60 minutes to obtain a visually uniform and colorless and transparent cured product.

[0105]

The cured product prepared from the curable composition containing the curing agent of the present invention as a component has high optical transparency.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Harumi Sakamoto 1-28-28 Torikai Wado, Settsu-shi, Osaka Sunny coat 401 F-term (reference) 4J002 CC072 CP191 DA117 DE177 EA026 EA046 ED026 ED056 EE036 EJ036 EU196 EV216 EW067 EW137 EX037 FD157 FD207 4J035 BA02 CA02M CA02N HA01 HA02 HA06 HB03

Claims (9)

[Claims] (1) (α) (a) 1 to 6 vinyl groups per molecule
(B) having a molecular weight of less than 900, and (c) having a viscosity of less than 1000 poise. A compound obtained by subjecting at least two organic compounds contained in one molecule and (β) a chain and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule to a hydrosilylation reaction; Curing agent containing at least two SiH groups in the molecule. 2. The component (α) comprises allyl ether of novolak phenol, vinylcyclohexene, divinylbenzene, divinylbiphenyl, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, and The curing agent according to claim 1, which is a compound represented by the formula: 3. The curing agent according to claim 1, wherein the component (β) is 1,3,5,7-tetramethyltetracyclosiloxane. 4. An organic compound containing (A) at least two carbon-carbon double bonds reactive with a SiH group in one molecule, (B) a curing agent containing a SiH group, and (C) hydrosilylation. A curable composition containing a catalyst as an essential component, wherein the component (B) is the curing agent according to claim 1. 5. An organic compound containing at least two carbon-carbon double bonds reactive with a SiH group per molecule, (B) a curing agent containing a SiH group, and (C) a hydrosilylation. A curable composition containing a catalyst as an essential component, wherein the component (B) is the curing agent according to claim 2. 6. An organic compound containing (A) at least two carbon-carbon double bonds reactive with a SiH group in one molecule, (B) a curing agent containing a SiH group, and (C) hydrosilylation. A curable composition containing a catalyst as an essential component, wherein the component (B) is the curing agent according to claim 3. 7. The component (A) as described above, (A) it contains 1 to 6 vinyl groups in one molecule, (B) the molecular weight is less than 900, and (C) the viscosity is The curable composition according to any one of claims 4 to 6, wherein the curable composition is less than 1000 poise. (8) The component (A) is an allyl ether of novolak phenol, vinylcyclohexene, divinylbenzene, divinylbiphenyl, triallyl isocyanurate, 1,2,4-trivinylcyclohexane,
And A compound represented by the formula:
The curable composition according to any one of the above. 9. A cured product obtained by curing the curable composition according to claim 4.