JP2003262701A - Composition for optical material, optical material, liquid crystal display device and light emitting diode obtained by using the same, and method for manufacturing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an optical material suppressing cracks in a thermal shock test for a thermosetting resin which uses hydrosilylation reaction as the hardening reaction, and to provide the optical material, a liquid crystal display device and a light emitting diode obtained by using the material, and a method for manufacturing them. <P>SOLUTION: The composition for an optical material comprises as essential components (A) an organic compound having an allyloxy group and/or a methallyloxy group in total of at least two groups in one molecule, (B) a compound which can be prepared by hydrosilylation of allylglycidylether and/or methallylglycidylether (α) and a chain and/or cyclic polyorganosiloxane (β) having at least three SiH groups in one molecule and which contains at least two SiH groups in one molecule, and (C) a hydrosilylation catalyst. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition for optical materials, and more particularly to a composition for optical materials having high light resistance and thermal shock resistance, an optical material, a liquid crystal display device using the same, and a light emitting diode. And their manufacturing methods.

[0002]

2. Description of the Related Art Conventionally, a transparent epoxy resin has been used as a thermosetting resin used for optical materials, but its use is limited because it is colored with time at a high temperature.

As a new thermosetting resin, a composition for optical materials using a hydrosilylation reaction as a curing reaction has been proposed (International Publication WO01-81475). Even in these, the thermal shock resistance under specific conditions is not sufficient,
Occurrence of cracks was sometimes a problem.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composition for an optical material, which is capable of suppressing the occurrence of cracks in a thermal shock test in a thermosetting resin using a hydrosilylation reaction as a curing reaction, and an optical composition. The object is to provide a material, a liquid crystal display device using the same, a light emitting diode, and a manufacturing method thereof.

[0005]

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the thermosetting resin using a hydrosilylation reaction as a curing reaction has the above-mentioned problems. The inventors have found that they can be solved and have reached the present invention.

That is, the present invention provides (A) an organic compound containing at least two allyloxy groups and / or metalyloxy groups in one molecule, (B) allyl glycidyl ether and / or methallyl glycidyl ether (α). And a chain and / or cyclic polyorganosiloxane (β) having at least 3 SiH groups in one molecule, which can be obtained by a hydrosilylation reaction, and at least 2 in one molecule. SiH
A composition for optical materials (Claim 1) containing a group-containing compound and a (C) hydrosilylation catalyst as essential components, wherein the (A) component is an allylated phenolic compound and / or a methallylated phenolic compound. The optical material composition according to claim 1 (claim 2), wherein the component (β) is represented by the following general formula (I):

[0007]

[Chemical 2] (In the formula, R ¹ represents an organic group having 1 to 6 carbon atoms, and n is 3 to
Represents the number 10. (3) A composition for an optical material (claim 3) according to claim 1 or 2, which is a cyclic polyorganosiloxane having at least 3 SiH groups in one molecule. An optical material (Claim 4) using the composition for optical material according to any one of Claims 1 to 3, and a liquid crystal display device (Claim 5) using the optical material according to Claim 4. And a light emitting diode (claim 6) using the optical material according to claim 4.
A method for manufacturing a liquid crystal display device using the optical material according to claim 4 (claim 7) and a method for manufacturing a light emitting diode using the optical material according to claim 4 (claim 8).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. (Component (A)) First, the component (A) in the present invention will be described.

The component (A) is not particularly limited as long as it is an organic compound containing at least two allyloxy groups and / or metalyloxy groups in one molecule.

The allyloxy group and / or the metalyloxy group in the component (A) is represented by the following general formula (II)

[0011]

[Chemical 3] (In the formula, R ² represents a hydrogen atom or a methyl group.).

The component (A) is preferably an organic compound containing at least two allyloxy groups in one molecule from the viewpoint that the composition obtained has good curability.

As the organic compound as the component (A), a siloxane unit (Si-) such as a polysiloxane-organic block copolymer or a polysiloxane-organic graft copolymer is used.
O-Si) is not included, but C as a constituent element,
It preferably contains only H, N, O, S and halogen. In the case of containing a siloxane unit, there are problems of gas permeability and repellency.

In the component (A), the bonding position of the allyloxy group and / or the metalyloxy group is not particularly limited,
It may exist anywhere in the molecule.

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

The allyloxy group and / or metalryloxy group of the component (A) may be directly bonded to the skeleton of the component (A) or may be covalently bonded via a divalent or higher valent substituent. The divalent or higher valent substituent has 0 to 10 carbon atoms.
The substituent is not particularly limited as long as it is a substituent of, but those containing only C, H, N, O, S, and halogen as constituent elements are preferable. Examples of these substituents include:

[0017]

[Chemical 4] Is mentioned. Further, two or more of these divalent or higher valent substituents may be connected by a covalent bond to form one divalent or higher valent substituent.

Specific examples of the component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2,- Tetraallyloxyethane, novolacphenol allyl ether, novolacphenol methallyl ether,

[0019]

[Chemical 5]

[0020]

[Chemical 6] In addition to the above, epoxy resins in which a glucidyloxy group of a conventionally known epoxy resin is replaced with an allyloxy group and / or a metalryloxy group may be used.

As the component (A), a low molecular weight compound which is difficult to be expressed by dividing the skeleton portion and the carbon-carbon double bond as described above can also be used. Specific examples of these low molecular weight compounds include diallyl ether and diallyl carbonate.

As the component (A), from the viewpoint that the heat resistance can be further improved, an allyloxy group and / or a metalryloxy group is added in an amount of 0.001 mol per 1 g of the component (A).
1 or more is preferable, and 0.005 per 1 g
It is more preferable that the content is at least mol, and 0.007 m
It is more preferable that the content of ol or more is contained.

The number of allyloxy groups and / or metallyloxy groups of the component (A) should be at least 2 per molecule on average, but if it is desired to further improve the mechanical strength, it should exceed 2. Is preferable, and it is more preferable that the total number is 3 or more. When the total number of allyloxy groups and / or metallyloxy groups of the component (A) is 1 or less per molecule, the reaction with the component (B) results in only a graft structure and not a crosslinked structure.

The component (A) is preferably an allylated phenolic compound and / or a methallylated phenolic compound from the viewpoint of higher heat resistance. The allylated phenolic compound and / or the methallylated phenolic compound are represented by the following general formula (II
I)

[0025]

[Chemical 7] (In the formula, R ³ represents a hydrogen atom or a methyl group).

The component (A) has a molecular weight of 900 from the viewpoints of high mechanical heat resistance, low stringiness of the raw material liquid, and good moldability and handleability.
Less than 700, more preferably less than 700, even more preferably less than 500.

As the component (A), those having fluidity at a temperature of 100 ° C. or lower are preferable in order to obtain uniform mixing with other components and good workability. The viscosity at 23 ° C. is preferably less than 1000 poise, more preferably less than 300 poise, even more preferably less than 30 poise.

The compounds of component (A) as described above can be used alone or in admixture of two or more. (Component (B)) Next, the component (B) will be described.

The component (B) of the present invention comprises allyl glycidyl ether and / or methallyl glycidyl ether (α) and a chain and / or cyclic polyorganosiloxane (having at least 3 SiH groups in one molecule). β)
And a compound which can be obtained by a hydrosilylation reaction of and which contains at least two SiH groups in one molecule. (Component (α)) The component (α) is allyl glycidyl ether and / or methallyl glycidyl ether,
The following general formula (IV)

[0030]

[Chemical 8] (In the formula, R ⁴ represents a hydrogen atom or a methyl group).

The component (α) is preferably allyl glycidyl ether from the viewpoint of good reactivity with the component (β). ((Β) component) (β) component contains at least 2 in one molecule.
It is a chain and / or cyclic polyorganosiloxane having one SiH group.

Specifically, for example,

[0033]

[Chemical 9]

[0034]

[Chemical 10] Is mentioned.

Here, from the viewpoint that the compatibility with the component (α) is good and that the resulting component (B) is likely to have good compatibility with the component (A), the following general formula (I) is used.

[0036]

[Chemical 11] (In the formula, R ¹ represents an organic group having 1 to 6 carbon atoms, and n is 3 to
Represents the number 10. The cyclic polyorganosiloxane having at least 3 SiH groups in one molecule represented by the formula (1) is preferable.

The substituent R ¹ in the compound represented by the general formula (I) is preferably one composed of C, H and O, more preferably a hydrocarbon group, and a methyl group. It is more preferable that there is.

The component (β) is easy to obtain,
1,3,5,7-Tetramethylcyclotetrasiloxane is preferred.

The various (β) components as described above can be used alone or in combination of two or more. (Reaction of (α) component and (β) component) The component (B) of the present invention is a compound which can be obtained by hydrosilylation reaction of the (α) component and the (β) component.

When the component (α) and the component (β) are hydrosilylated, a mixture of a plurality of compounds containing the component (B) of the present invention may be obtained, from which the component (B) is separated. It is also possible to prepare the curable composition of the present invention without using the mixture as it is.

When the component (α) and the component (β) are hydrosilylated, the mixing ratio of the component (α) and the component (β) is not particularly limited, but the obtained component (B) and component (A) are used.
Considering the strength of the cured product obtained by hydrosilylation with the component, it is preferable that the component (B) has a large number of SiH groups. Therefore, in general, a carbon-carbon double bond having reactivity with the SiH group in the component (α) is used. The number of bonds (X) and S in the component (β)
The ratio with the number (Y) of iH groups is preferably Y / X ≧ 2, and more preferably Y / X ≧ 3. Further, from the viewpoint that the compatibility of the component (B) with the component (A) tends to improve, it is preferable that 10 ≧ Y / X, and 5
It is more preferable that ≧ Y / X.

When the component (α) and the component (β) are hydrosilylated, a suitable catalyst may be used. For example, the following can be used as the catalyst.
Platinum simple substance, solid platinum supported on a carrier such as alumina, silica, carbon black, chloroplatinic acid, a complex of chloroplatinic acid with an alcohol, an aldehyde, a ketone, or a platinum-olefin complex (for example, Pt (CH ₂ = CH ₂ ) _{2
(PPh 3) 2, Pt (} CH 2 = CH 2) 2 Cl 2), Platinum -
Vinyl siloxane complex (for example, Pt (ViMe ₂ Si
OSiMe ₂ Vi) _n , Pt [(MeViSi
O) ₄ ] _m ), a platinum-phosphine complex (for example, Pt (P
_{Ph 3) 4, Pt (PBu} 3) 4), platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OB
u) ₃ ] ₄ ) (wherein Me is a methyl group, Bu is a butyl group,
Vi represents a vinyl group, Ph represents a phenyl group, and n and m are
Indicates an integer. ), Dicarbonyldichloroplatinum, Karstedt catalyst, and Ashby US Pat. Nos. 3,159,601 and 31.
Included are the platinum-hydrocarbon complexes described in 59662, as well as the platinum alcoholate catalysts described in Lamoreaux, US Pat. No. 3,209,972. In addition, Modic
The platinum chloride-olefin composites described in US Pat. No. 3,516,946 of c) 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 these, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. Further, these catalysts may be used alone or in combination of two or more kinds.

The addition amount of the catalyst is not particularly limited, but the preferable lower limit of the addition amount is S of the component (β) in order to have sufficient curability and to keep the cost of the curable composition relatively low.
10 ^-8 mol, more preferably 10 -10 mol, per 1 mol of iH group
^-6 mol, and the preferable upper limit of the addition amount is S of the component (β)
10 ⁻³ mol, more preferably 10 ⁻³ mol, per 1 mol of iH group
^-5 mol. Here, a cocatalyst can be used in combination with the above catalyst, and examples thereof include phosphorus compounds such as triphenylphosphine and 1, such as dimethyl maleate.
Examples thereof include 2-diester compounds, acetylene alcohol compounds such as 2-hydroxy-2-methyl-1-butyne, sulfur compounds such as sulfur alone, and amine compounds such as triethylamine. The amount of the cocatalyst added is not particularly limited, but the lower limit of the amount of the cocatalyst added is preferably 10 ^-2 mol, and more preferably 10 ^{-1 with} respect to 1 mol of the hydrosilylation catalyst.
The upper limit of the addition amount is 10 ² mol, and more preferably 10 mol.

Various methods can be used to mix the component (α), the component (β) and the catalyst in the case of reaction, but the mixture of the component (α) and the catalyst is (β).
The method of mixing the components is preferred. (Α) component, (β)
It is difficult to control the reaction if the catalyst is mixed with the mixture of components. When the method of mixing the component (α) with the mixture of the component (β) and the catalyst is used, the component (β) may be deteriorated in the presence of the catalyst because it has reactivity with the mixed water. .

The reaction temperature can be variously set, but 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. When the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and when the reaction temperature is high, it is not practical. The reaction may be carried out at a constant temperature,
The temperature may be changed in multiple stages or continuously if necessary.

The reaction time and the pressure during the reaction can be variously set as required.

A solvent may be used in the hydrosilylation reaction. The solvent that can be used is not particularly limited as long as it does not inhibit the hydrosilylation reaction, and specific examples thereof include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, 1, An ether solvent such as 3-dioxolane and diethyl ether, a ketone solvent such as acetone and methyl ethyl ketone, and a halogen solvent such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used. The solvent may be used as a mixed solvent of two or more kinds. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.
The amount of solvent used can also be set appropriately.

In addition, various additives may be used for the purpose of controlling reactivity.

After reacting the component (α) with the component (β), the solvent or / and the unreacted component (α) or / and the component (β) can be removed. By removing these volatile components, the resulting component (B) does not have volatile components, so that when curing with the component (A), problems such as voids and cracks due to volatilization of volatile components are less likely to occur. Examples of the removing method include devolatization under reduced pressure, treatment with activated carbon, aluminum silicate, silica gel, and the like. In the case of devolatilization under reduced pressure, it is preferable to treat at low temperature. The upper limit of the preferable temperature in this case is 100 ° C, and more preferably 60 ° C. When it is treated at high temperature, it is likely to be accompanied by alteration such as thickening. (Component (C)) Next, the hydrosilylation catalyst which is the component (C) will be described.

The hydrosilylation catalyst is not particularly limited as long as it has a catalytic activity for the hydrosilylation reaction. For example, simple substance of platinum, alumina, silica, carbon black or the like on which solid platinum is supported, chloroplatinic acid chloride. , Complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg Pt (CH ₂ ═C
H ₂ ) ₂ (PPh ₃ ) ₂ , Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ),
Platinum-vinyl siloxane complex (for example, Pt (ViMe
₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSi
O) ₄ ] _m ), a platinum-phosphine complex (for example, Pt (P
_{Ph 3) 4, Pt (PBu} 3) 4), platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ] 4, Pt [P (OB
u) ₃ ] ₄ ) (wherein Me is a methyl group, Bu is a butyl group,
Vi represents a vinyl group, Ph represents a phenyl group, and n and m are
Indicates an integer. ), Dicarbonyldichloroplatinum, Karstedt catalyst, and Ashby US Pat. Nos. 3,159,601 and 3.
Platinum-hydrocarbon complexes described in 159662, as well as platinum alcoholate catalysts described in Lamoreaux, U.S. Pat. No. 3,209,972. In addition, Modic (Mo
The platinum chloride-olefin composites described in U.S. Pat. No. 3,516,946 to Dic) 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 these, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. Further, these catalysts may be used alone or in combination of two or more kinds.

The addition amount of the catalyst is not particularly limited, but the lower limit of the addition amount is preferable in order to have sufficient curability and to keep the cost of the curable composition relatively low.
10 ^-8 mol, more preferably 10 -10 mol, per 1 mol of iH group
^-6 mol, and the preferable upper limit of the addition amount is S of the component (β)
10 ⁻¹ mol, more preferably 10 ⁻¹ mol, relative to 1 mol of iH group
^-2 mol.

A cocatalyst may be used in combination with the above catalyst, and examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl maleate, and 2-hydroxy-2-. Examples thereof include acetylene alcohol compounds such as methyl-1-butyne, sulfur compounds such as elemental sulfur, and amine compounds such as triethylamine. The addition amount of the cocatalyst is not particularly limited, but the lower limit of the addition amount with respect to 1 mol of the hydrosilylation catalyst is 10 ^-2 mol, more preferably 10 ^-1 mol,
The preferable upper limit of the addition amount is 10 ² mol, and more preferably 1
It is 0 mol. (Mixing) The mixing ratio of the component (A) and the component (B) as described above is not particularly limited as long as the necessary strength is not lost, but the ratio (A) of the number (Y) of the SiH groups in the component (B) is not limited. ) In the ratio to the number of carbon-carbon double bonds (X) in the component,
The lower limit of the preferable range is Y / X ≧ 0.3, more preferably Y / X ≧ 0.5, still more preferably Y / X ≧ 0.7, and the upper limit of the preferable range is 3 ≧ Y / X, more preferably Is 2 ≧ Y / X, and more preferably 1.5 ≧ Y / X.
If it deviates from the preferable range, sufficient strength may not be obtained, or heat deterioration may easily occur.

Various methods can be used for mixing the components (A), (B) and (C).
A method of mixing the component (A) with the component (C) and the component (B) with each other is preferable. When the method of mixing the component (C) with the mixture of the components (A) and (B) 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) is reactive with moisture in the environment in the presence of the component (C). It may deteriorate during storage. (Additive) (Curing Retardant) A curing retarder is used in the curable composition of the present invention for the purpose of improving the storage stability of the curable composition or adjusting the reactivity of the hydrosilylation reaction in the production process. be able to. Examples of the curing retarder include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds and organic peroxides, and these may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleic acid esters and the like. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphines, triorganophosphites and the like. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of the tin-based compound include stannous halide dihydrate and stannous carboxylate. Examples of organic peroxides include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide,
Examples are t-butyl perbenzoate and the like.

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

The addition amount of the curing retarder can be variously set,
The lower limit of the addition amount with respect to 1 mol of the hydrosilylation catalyst used is 10 ^-1 mol, more preferably 1 mol, and the upper limit of the addition amount is preferably 10 ³ mol, more preferably 50 mol.

These curing retarders may be used alone or in combination of two or more. (Adhesiveness improver) An adhesiveness improver can be added to the curable composition of the present invention. As the adhesion improver, in addition to the commonly used adhesives, for example, various coupling agents, epoxy compounds, phenol resins, coumarone-
Examples thereof include indene resin, rosin ester resin, terpene-phenol resin, α-methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene and aromatic polyisocyanate.

Examples of the coupling agent include silane coupling agents. 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 at least one hydrolyzable silicon group in the molecule. As a group reactive with an organic group,
At least one functional group selected from an epoxy group, a methacrylic group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group is preferable from the viewpoint of handleability, and an epoxy group, from the viewpoint of curability and adhesiveness, A methacrylic group and an acrylic group are particularly preferable. The hydrolyzable silicon group is preferably an alkoxysilyl group from the viewpoint of handleability, a methoxysilyl group from the viewpoint of reactivity,
Ethoxysilyl groups are particularly preferred.

Preferred silane coupling agents are:
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and other alkoxysilanes having an epoxy functional group: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, 3
-Alkoxysilanes having a methacrylic group or an acryl group such as acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane can be exemplified. .

The addition amount of the silane coupling agent can be variously set, but the lower limit of the addition amount is preferably 0.1 parts by weight, relative to 100 parts by weight of [(A) component + (B) component].
It is more preferably 0.5 part by weight, and the preferable upper limit of the added amount is 50 parts by weight, and more preferably 25 parts by weight.
If the added amount is small, the effect of improving the adhesiveness will not be exhibited, and if the added amount is large, the physical properties of the cured product may be adversely affected.

Examples of the epoxy compound include novolac phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2'-bis (4-glycidyl). Oxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexenedioxide,
2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-
Dioxane, bis (3,4-epoxycyclohexyl)
Examples thereof include adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate and the like.

The addition amount of the epoxy compound can be variously set, but the lower limit of the addition amount is preferably 1 part by weight, more preferably 3 parts by weight, based on 100 parts by weight of [(A) component + (B) component]. Therefore, the upper limit of the preferable addition amount is 50 parts by weight, and more preferably 25 parts by weight. If the added amount is small, the effect of improving the adhesiveness will not be exhibited, and if the added amount is large, the physical properties of the cured product may be adversely affected.

These coupling agents, silane coupling agents, epoxy compounds and the like may be used alone or in combination of two or more.

Further, in the present invention, a silanol condensation catalyst can be further used in order to enhance the effects of the coupling agent and the epoxy compound, thereby improving the adhesiveness and / or
Alternatively, stabilization is possible. The silanol condensation catalyst is not particularly limited, but an aluminum compound and / or a titanium compound is preferable. As an aluminum compound that serves as a silanol condensation catalyst,
Aluminum triisopropoxide, sec-butoxyaluminum diisofuropoxide, aluminum tris
Aluminum alkoxides such as ec-butoxide:
Ethyl acetoacetate aluminum diisopropoxide, aluminum tris (ethyl acetoacetate),
Aluminum chelate M (Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide),
Aluminum chelates such as aluminum tris (acetylacetonate) and aluminum monoacetylacetonate bis (ethylacetoacetate) can be exemplified.
From the viewpoint of handleability, aluminum chelates are more preferable. Titanium compounds that serve as silanol condensation catalysts include tetraalkoxytitaniums such as tetraisopropoxytitanium and tetrabutoxytitanium: titanium chelates such as titanium tetraacetylacetonate: general compounds having a residue such as oxyacetic acid and ethylene glycol. Examples of such titanate coupling agents include:

The amount of the silanol condensation catalyst used can be variously set, but the lower limit of the amount of the coupling agent and / or the epoxy compound added to 100 parts by weight of the epoxy compound is preferably 0.1 part by weight, and more preferably 0.1 part by weight. 1 part by weight, and the preferable upper limit of the added amount is 50 parts by weight,
It is more preferably 30 parts by weight. If the added amount is small, the effect of improving the adhesiveness will not be exhibited, and if the added amount is large, the physical properties of the cured product may be adversely affected.

These silanol condensation catalysts may be used alone or in combination of two or more kinds.

Further, in the present invention, in order to further enhance the effect of improving the adhesiveness, a silanol source compound can be further used, and the adhesiveness can be improved and / or stabilized. Examples of such silanol sources include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane and methyltrimethoxysilane.

The amount of the silanol source compound used may be variously set, but the lower limit of the amount of the coupling agent and / or the epoxy compound added to the epoxy compound is preferably 0.1 part by weight, more preferably 0.1 part by weight. 1 part by weight, and the preferable upper limit of the added amount is 50 parts by weight,
It is more preferably 30 parts by weight. If the added amount is small, the effect of improving the adhesiveness will not be exhibited, and if the added amount is large, the physical properties of the cured product may be adversely affected.

These silanol source compounds may be used alone or in combination of two or more.

In the present invention, carboxylic acids and / or acid anhydrides can be used in order to enhance the effects of the coupling agent and the epoxy compound, and the adhesiveness can be improved and / or stabilized. Such carboxylic acids and acid anhydrides are not particularly limited,

[0074]

[Chemical 12] 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylhymic acid, norbornenedicarboxylic acid, hydrogenated methylnadic acid, maleic acid, acetylenedicarboxylic acid, Lactic acid, malic acid, citric acid, tartaric acid,
Examples thereof include benzoic acid, hydroxybenzoic acid, cinnamic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenecarboxylic acid, naphthalenedicarboxylic acid, and single or complex acid anhydrides thereof.

Of these carboxylic acids and / or acid anhydrides, SiH is used because it has a hydrosilylation reactivity and there is little possibility of leaching from the cured product, and it is difficult to impair the physical properties of the resulting cured product. Those containing a carbon-carbon double bond reactive with a group are preferred. Preferred carboxylic acids and / or acid anhydrides include, for example:

[0076]

[Chemical 13] Examples thereof include tetrahydrophthalic acid, methyltetrahydrophthalic acid, and their individual or complex acid anhydrides.

The amount of carboxylic acid or / and acid anhydride used can be variously set, but the coupling agent or / and the epoxy compound / epoxy compound 1
The lower limit of the amount of addition is preferably 0.1 part by weight, more preferably 1 part by weight, and the upper limit of the amount of addition is preferably 50 parts by weight, more preferably 10 parts by weight. If the added amount is small, the effect of improving the adhesiveness will not be exhibited, and if the added amount is large, the physical properties of the cured product may be adversely affected.

These carboxylic acids and / or acid anhydrides may be used alone or in combination of two or more. (Inorganic Filler) An inorganic filler may be added to the curable composition of the present invention, if necessary. The addition of the inorganic filler is effective in preventing the fluidity of the composition, increasing the strength of the material, and reducing the linear expansion. As the inorganic filler, quartz, fume silica, precipitated silica, silicic acid anhydride, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, silica such as spherical silica, silicon nitride, silver powder,
Alumina, aluminum hydroxide, titanium oxide, glass fiber, carbon fiber, mica, carbon black, graphite, diatomaceous earth, clay, talc, calcium carbonate, magnesium carbonate, barium sulfate, inorganic balloons and the like can be mentioned. Of these, silicas are preferred from the viewpoint of being less likely to inhibit the curing reaction and having a large effect of reducing the linear expansion coefficient, and spherical silica is more preferred from the viewpoint of decreasing the viscosity when added.

These inorganic fillers may be appropriately surface-treated. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment and silicone treatment.

As a method of adding other fillers, for example, hydrolyzable silane monomers or oligomers such as alkoxysilane, acyloxysilane and halogenated silane, and alkoxides, acyloxides and halides of metals such as titanium and aluminum are used. A method of adding the composition to the composition of the present invention and reacting it in the composition or in a partial reaction product of the composition to form an inorganic filler in the composition can also be mentioned.

It is preferable that these inorganic fillers have a low radiation property.

The addition amount of the inorganic filler is not particularly limited, but the lower limit of the preferable addition amount is 20% by weight, more preferably 30% by weight of the whole curable composition, and the upper limit of the preferable addition amount is in the curable composition. Of 80% by weight, more preferably 50% by weight. If the amount added is small, the desired effect is difficult to obtain, and if the amount added is large, the material tends to become brittle.

These inorganic fillers may be used alone or in combination of two or more. (Thermosetting Resin) Various thermosetting resins may be added for the purpose of modifying the properties of the curable composition of the present invention. Examples of the thermosetting resin include epoxy resin, cyanate resin, phenol resin, polyimide resin, urethane resin and the like, but are not limited thereto. Of these, epoxy resins are preferable from the viewpoint of excellent practical properties such as adhesiveness.

Examples of the epoxy resin include novolac phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether and 2,2'-bis (4-glycidyl). Oxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexenedioxide, 2
-(3,4-Epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid Bisglycidyl ester, triglycidyl isocyanurate,
Epoxy resins such as monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate, and the like are used as aliphatic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and hydrogenated methylnadic acid anhydride. The thing hardened with a thing is mentioned. These epoxy resins or curing agents may be used alone or in combination.

The amount of the thermosetting resin added is not particularly limited, but the lower limit of the preferable amount used is 5 based on the total amount of the curable composition.
%, More preferably 10% by weight, and the preferable upper limit of the amount used is 50% by weight in the curable composition, more preferably 30% by weight. If the amount of addition is small, the desired effects such as adhesiveness are difficult to obtain, and if the amount of addition is large, it becomes brittle.

Even if these thermosetting resins are used alone,
You may combine several things.

The thermosetting resin may be obtained by dissolving the resin raw material or / and the cured resin in the component (A) and / or the component (B) and mixing them in a uniform state, or by pulverizing and mixing in a particle state. Alternatively, they may be dissolved in a solvent and mixed to form a dispersed state. From the viewpoint that the obtained cured product is likely to be more transparent, it is preferable to dissolve it in the component (A) and / or the component (B) and mix them in a uniform state. Also in this case, the thermosetting resin may be directly dissolved in the component (A) and / or the component (B), or may be uniformly mixed using a solvent or the like,
After that, the solvent may be removed to obtain a uniformly dispersed state and / or a mixed state.

When the thermosetting 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 1.
It is 0 μm. The particle system may have a distribution, and may have a single dispersion or a plurality of peak particle sizes, but the particle size may be reduced from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. It is preferable that the coefficient of variation is 10% or less. (Thermoplastic Resin) Various thermoplastic resins may be added for the purpose of modifying the properties of the curable composition of the present invention. As the thermoplastic resin, various ones can be used, for example, polymethylmethacrylate resin such as homopolymer of methylmethacrylate or random, block or graft polymer of methylmethacrylate and other monomers (for example, Hitachi Chemical Opttrets, etc.), homopolymer of butyl acrylate or random, block of butyl acrylate and other monomers,
Alternatively, a polycarbonate resin such as an acrylic resin represented by a polybutyl acrylate resin such as a graft polymer or a polycarbonate resin containing bisphenol A, 3,3,5-trimethylcyclohexylidene bisphenol or the like as a monomer structure (for example, Teijin APEC, etc.), norbornene derivatives, resins obtained by homopolymerizing or copolymerizing vinyl monomers, etc., resins obtained by ring-opening metathesis polymerization of norbornene derivatives, or cycloolefin resins such as hydrogenated products thereof (for example, manufactured by Mitsui Chemicals, Inc. APEL, ZEONOR, ZEONE manufactured by Nippon Zeon Co., Ltd.
X, JSR's ARTON, etc.), ethylene-maleimide copolymers and other olefin-maleimide resins (eg Tosoh's TI-PAS, etc.), bisphenol A, bis (4- (2-hydroxyethoxy) phenyl) fluorene. Polyester resins such as polyesters obtained by polycondensing bisphenols such as diols such as diethylene glycol and phthalic acids such as terephthalic acid and isophthalic acid, and aliphatic dicarboxylic acids (for example, O-PET manufactured by Kanebo Co., Ltd.
Etc.), polyether sulfone resin, polyarylate resin, polyvinyl acetal resin, polyethylene resin, polypropylene resin, polystyrene resin, polyamide resin, silicone resin, fluororesin, etc., as well as natural rubber, E
A rubber-like resin such as PDM is exemplified, but the present invention is not limited to this.

The thermoplastic resin may have a carbon-carbon double bond or / and a SiH group reactive with the SiH group in the molecule. From the viewpoint that the resulting cured product is likely to be tougher, it has at least one carbon-carbon double bond or / and SiH group reactive in the molecule with SiH group in one molecule. It is preferable.

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

The molecular weight of the thermoplastic resin is not particularly limited, but the number average molecular weight is 100 in that compatibility with the components (A) and (B) tends to be good.
It is preferably 00 or less, and more preferably 5000 or less. On the contrary, in that the obtained cured product is likely to be tough, the number average molecular weight is 10,000.
It is preferably not less than 100,000, more preferably not less than 100,000. Although the molecular weight distribution is not particularly limited, the molecular weight distribution is preferably 3 or less, more preferably 2 or less, and more preferably 1.5 or less, from the viewpoint that the viscosity of the mixture is low and the moldability is likely to be good.
The following is more preferable.

The blending amount of the thermoplastic resin is not particularly limited, but the preferred lower limit of the amount used is 5 based on the total amount of the curable composition.
%, More preferably 10% by weight, and the preferable upper limit of the amount used is 50% by weight in the curable composition, more preferably 30% by weight. If the added amount is small, the obtained cured product tends to be brittle, and if the added amount is large, heat resistance (elastic modulus at high temperature) tends to be low.

A single thermoplastic resin may be used, or a plurality of thermoplastic resins may be used in combination.

The thermoplastic resin may be dissolved in the component (A) or / and the component (B) and mixed in a uniform state, may be pulverized and mixed in a particle state, or may be dissolved in a solvent and mixed. For example, it may be in a dispersed state. In that the resulting cured product tends to be more transparent,
It is preferable to dissolve it in the component (A) or / and the component (B) and mix them in a uniform state. Also in this case, the thermoplastic resin may be directly dissolved in the component (A) and / or the component (B), or may be uniformly mixed by using a solvent or the like, and thereafter the solvent may be removed to obtain a uniform dispersion. It may be in a state or / and a mixed state.

When the thermoplastic resin is dispersed and used,
The average particle diameter can be variously set, but the lower limit of the preferable average particle diameter is 10 nm, and the upper limit of the preferable average particle diameter is 1.
It is 0 μm. The particle system may have a distribution, and may have a single dispersion or a plurality of peak particle sizes, but the particle size may be reduced from the viewpoint that the viscosity of the curable composition is low and the moldability tends to be good. It is preferable that the coefficient of variation is 10% or less. (Additive for Light-Emitting Diode Encapsulant) Various additives for improving light-emitting diode characteristics may be added to the curable composition of the present invention. Examples of these additives include phosphors such as yttrium-aluminum-garnet-based phosphors activated by cerium, which absorb light from a light-emitting element and emit fluorescence having a longer wavelength, and absorb specific wavelengths. Colorants such as bluing agents, titanium oxide for diffusing light, aluminum oxide, silica, silicon oxide such as quartz glass, talc, calcium carbonate, melamine resin, CTU
Examples thereof include various inorganic or organic diffusion materials such as guanamine resin and benzoguanamine resin, glass, metal oxides such as aluminosilicate, and heat conductive fillers such as metal nitrides such as aluminum nitride and boron nitride.

Further, these light emitting diode sealing agent additives may be used alone or in combination of two or more kinds.

The additive for improving the characteristics of the light emitting diode may be contained uniformly or may be contained with a graded content. Such a filler-containing resin portion can be formed as a molding member on the rear side of the light emitting surface by pouring the resin for the molding member on the front surface of the light emitting surface into the mold, and subsequently, flowing the resin containing the filler. In addition, after forming the mold member, cover the lead terminals by attaching tape from both the front and back sides, and in this state, immerse the lower half of the mold member of the light emitting diode in the tank containing the resin containing the filler, and then pull it up. It may be dried to form the filler-containing resin portion. (Anti-aging agent) An anti-aging agent may be added to the curable composition of the present invention. Examples of the antiaging agent include commonly used antiaging agents, such as citric acid, phosphoric acid, and sulfur antiaging agents. Sulfur-based antioxidants include mercaptans, mercaptan salts, sulfide carboxylic acid esters and sulfides including hindered phenol sulfides, polysulfides, dithiocarboxylic acid salts, thioureas, thiophosphates, sulfonium Examples thereof include compounds, thioaldehydes, thioketones, mercaptars, mercaptors, monothio acids, polythio acids, thioamides, sulfoxides and the like.

These anti-quantification agents may be used alone or in combination of two or more kinds. (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) and 2,2′-methylene-bis (4-methyl-).
6-t-butylphenol), tetrakis (methylene-
3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane and other phenolic radical inhibitors, 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.

Further, these radical inhibitors may be used alone or in combination of two or more kinds. (Ultraviolet absorber) An ultraviolet absorber may be added to the curable composition of the present invention. As the ultraviolet absorber, for example, 2
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like can be mentioned.

These UV absorbers may be used alone or in combination of two or more kinds. (Other additives) In addition to the curable composition of the present invention,
Flame retardant, surfactant, storage stability improver, ozone deterioration inhibitor, light stabilizer, thickener, plasticizer, antioxidant, heat stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent, nucleus Agent,
Phosphorus peroxide decomposer, lubricant, pigment, metal deactivator,
A heat conductivity imparting agent, a physical property adjusting agent and the like can be added within a range that does not impair the objects and effects of the present invention. (Solvent) The curable composition of the present invention may be dissolved in a solvent and used. The solvent that can be used is not particularly limited, and specific examples thereof include hydrocarbon solvents such as benzene, toluene, hexane and heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diethyl ether and the like. The ether type solvent, the ketone type solvent such as acetone and methyl ethyl ketone, and the halogen type solvent such as chloroform, methylene chloride and 1,2-dichloroethane can be preferably used.

As the solvent, toluene, tetrahydrofuran, 1,3-dioxolane and chloroform are preferable.

The amount of the solvent used can be set appropriately, but the lower limit of the amount used is preferably 0.1 mL, and the upper limit of the amount used is preferably 10 mL, per 1 g of the curable composition used. If the amount used is small, it is difficult to obtain the effect of using a solvent such as viscosity reduction, and if the amount used is large, the solvent remains in the material and problems such as thermal cracking easily occur, and also in terms of cost. It becomes disadvantageous and the industrial utility value decreases.

These solvents may be used alone,
It can also be used as a mixed solvent of two or more kinds. (Curing) The curable composition of the present invention is preliminarily mixed and cured by reacting a carbon-carbon double bond reactive with the SiH group in the curable composition with a part or all of the SiH group. And can be used as a material for a semiconductor device.

When the composition is reacted and cured, the necessary amounts of the components (A), (B) and (C) may be mixed and reacted at one time, but a part of them may be mixed and reacted. After mixing, the remaining amount is mixed and further reacted, or after mixing, only a part of the functional groups in the composition is reacted by controlling the reaction conditions and utilizing the difference in reactivity of the substituents (B stage conversion) It is also possible to adopt a method in which after the treatment, a treatment such as molding is performed to further cure. According to these methods, the viscosity adjustment during molding becomes easy.

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

The curing temperature can be variously set, but the lower limit of the preferable temperature is 30 ° C., more preferably 100 ° C., and the upper limit of the preferable temperature is 300 ° C., more preferably 2 ° C.
It is 00 ° C. If the reaction temperature is low, the reaction time for sufficiently reacting becomes long, and if the reaction temperature is high, the molding process tends to be difficult.

The curing may be carried out at a constant temperature, but the temperature may be changed in multiple stages or continuously if necessary. It is preferable to carry out the reaction while raising the temperature in multiple stages or continuously rather than to carry out the reaction at a constant temperature, because it is easy to obtain a uniform cured product without distortion.

Although the curing time can be set variously, it is preferable to react at a relatively low temperature for a long time rather than at a high temperature for a shorter time because a uniform cured product without distortion can be easily obtained.

The pressure during the reaction can be variously set as necessary,
The reaction can be carried out under normal pressure, high pressure, or reduced pressure. It is preferable to cure in a reduced pressure state in terms of easy removal of volatile components generated in some cases and good fillability into the details. (Molding method) The composition for optical materials of the present invention is preliminarily mixed and cured by reacting a carbon-carbon double bond reactive with the SiH group in the composition with a part or all of the SiH group. Then, it can be used as an optical material.

There are no particular restrictions on the shape of the material obtained by curing, depending on the application, and there is no particular limitation. For example, it may be in the shape of a film, sheet, tube, rod, coating, bulk or the like. You can

As the molding method, various methods can be adopted including the method used for molding thermosetting resins such as conventional epoxy resins. For example, a molding method such as a potting method, a cast method, a pressing method, a casting method, a transfer molding method, a coating method, or a RIM method can be applied. Molds are glass, metals such as stainless steel, polycarbonate, polyethylene terephthalate, polymethylmethacrylate, polymethylpentene,
Polybutylene terephthalate, polyphthalamide, etc. can be applied. Further, in order to improve the releasability from the molding die, it is possible to apply polyethylene terephthalate film, polycarbonate film, polyvinyl chloride film, polyethylene film, polytetrafluoroethylene film, polypropylene film, polyimide film, various release agents, etc. it can. If necessary, various treatments can be performed during molding. For example, a treatment of defoaming the composition or a partially reacted composition by centrifugation, reduced pressure, or the like, a treatment of temporarily releasing the pressure during pressing, or the like can be applied in order to suppress voids generated during molding. (Properties) As the curable composition of the present invention, various combinations can be used as described above, but in terms of easy moldability and good filling of details, the curable composition is The viscosity of is 10 at 23 ° C.
It is preferably 0 Pa · s or less, more preferably 10 Pa · s or less, even more preferably 1.0 Pa · s or less, and particularly preferably 0.1 or less. For the same reason, 10P at 100 ° C
It is preferably a · s or less, more preferably 1.0 Pa · s or less, and further preferably 0.1 Pa · s or less.

From the viewpoint of good heat resistance, a cured product obtained by curing the composition preferably has a Tg of 0 ° C. or higher, more preferably 50 ° C. or higher. On the contrary, in terms of low stress and high reliability of the semiconductor device, the cured product obtained by curing the composition preferably has a Tg of 100 ° C. or less, and 70 ° C.
The following are more preferable, and those below 50 ° C. are particularly preferable.

In addition, in terms of low stress and high reliability of the semiconductor device, the elastic modulus of the cured product obtained by curing the composition is 2 GPa at 23 ° C.
It is preferably not more than 1.5 GPa, more preferably not more than 1.5 GPa, even more preferably 1.0 GPa, and particularly preferably not more than 0.5 GPa. (Optical Material) The term “optical material” as used in the present invention refers to a general material used for the purpose of passing light such as visible light, infrared rays, ultraviolet rays, X-rays, and lasers through the material.

More specifically, a liquid crystal display such as a substrate material in the field of liquid crystal displays, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, a film for liquid crystal such as a polarizer protective film, and the like. It is a material around the device. In addition, encapsulant for color PDP (plasma display) expected as next-generation flat panel display, antireflection film, optical correction film, housing material, front glass protective film, front glass substitute material,
Adhesives, light emitting element molding materials used in light emitting diode display devices, light emitting diode sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays , Light guide plate, prism sheet, polarizing plate, retardation plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, Further, they are various film substrates for field emission displays (FED), protective films for front glass, front glass substitute materials, and adhesives.

In the optical recording field, 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, sealant, adhesive and the like.

In the field of optical equipment, materials for steel camera lenses, finder prisms, target prisms,
It is a finder cover and a light receiving sensor. It is also a shooting lens and viewfinder for video cameras. Further, it is a projection lens of a projection television, a protective film, a sealing agent, an adhesive agent and the like. Materials for lenses of optical sensing devices, sealants, adhesives, films and the like.

In the field of optical components, there are fiber materials, lenses, waveguides, element sealants and adhesives around optical switches in optical communication systems. Examples include optical fiber materials around optical connectors, ferrules, sealants, and adhesives. In the case of optical passive components and optical circuit components, they are lenses, waveguides, sealing agents for light emitting elements, adhesives, and the like. Substrate materials around the optoelectronic integrated circuit (OEIC), fiber materials, element sealants, adhesives, and the like. In the field of optical fibers, it is an optical fiber for illumination and light guides for decorative displays, sensors for industrial applications, displays and signs, and for communication infrastructure and for connecting digital devices in the home.

A peripheral material for semiconductor integrated circuits 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, switch parts, headlamps, engine internal parts, electrical parts, various internal and external parts, drive engines, brake oil tanks, Anti-corrosion steel plate for automobiles, interior panel,
Interior materials, protection and binding wireness, fuel hoses, automobile lamps, glass substitutes. In addition, it is a double glazing for railway vehicles. Also, a toughening agent for aircraft structural materials,
Engine peripherals, protection / bundling wireness, corrosion-resistant coating.

In the field of construction, materials for interior and processing, electric covers, sheets, glass intermediate films, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house coating film. Organic E is the next-generation optical / electronic functional organic material.
L element peripheral material, organic photorefractive element, light-
Examples include a light amplification element which is a light conversion device, an optical operation element, a substrate material around an organic solar cell, a fiber material, a sealing agent for an element, and an adhesive.

The optical material also includes a light emitting diode sealing material.

Further, various transparent films can be used. Examples of the use of the transparent film include the following various types. Display device field: Membrane switch, liquid crystal display device (retardation film, polarizing film, plastic liquid crystal cell), electroluminescence, electrochromic, electrophoretic display, plasma display panel, field emission display, diffusion film for backlight, color filter , Recording field: Electrostatic recording substrate, OHP, 2nd original drawing, slide film, micro film, X-ray film, optical / magnetic memory field: Thermo plastic recording, ferroelectric memory, magnetic tape, ID card, bar code , Antistatic field: Meter windows, TV cathode ray tubes, clean room windows, semiconductor packaging materials, VTR tapes, dust mask films for photomasks, Electromagnetic wave shielding field: Measuring instruments, medical equipment, radiation detectors, I
C component, CRT, liquid crystal display device, photoelectric conversion element field: solar cell window, optical amplifier, optical sensor, heat ray reflection field: window (architecture, automobile, etc.), incandescent light bulb, cooking oven window, furnace viewing window, Selective permeable membrane, planar heating element field: defroster, aircraft, automobile, freezer, incubator, goggles, medical equipment, liquid crystal display device, electronic component / circuit material field: capacitor, resistor, thin film composite circuit, leadless LSI chip Carrier mounting, Electrode field: Paper battery electrode, Light transmission filter field: UV cut filter, UV transmission filter, UV transmission visible light absorption filter,
Color separation filter, color temperature conversion filter, neutral density filter, contrast filter, wavelength calibration filter, interference filter, infrared transmission filter, infrared cut filter, heat ray absorption filter,
Heat ray reflective filter, gas selective permeable membrane field: oxygen / nitrogen separation membrane, carbon dioxide separation membrane, hydrogen separation membrane, electrical insulation field: insulating adhesive tape,
Motor slot liner, transformer interphase insulation, polymer sensor field: optical sensor, infrared sensor, sound wave sensor, pressure sensor, surface protection field: liquid crystal display, CRT, furniture, system kitchen, automobile interior and exterior, other fields: Electric heat transfer, printer ribbon, wire cable shield, water leakage prevention film.

It is also possible to use a transparent conductive film. The transparent conductive film is a film in which a transparent conductive layer is provided on at least one surface of the transparent film, and the thickness, appearance and shape are not particularly limited.

The transparent conductive layer can be produced by coating at least one surface of the transparent film with a transparent conductive film such as a metal thin film, a semiconductor thin film, or a multilayer thin film, and the entire surface, one surface, etc. It is not limited.

As the metal thin film, nickel, titanium, chromium, silver, zinc, aluminum, copper, gold, palladium, etc. are added. As the semiconductor thin film, tin, tellurium, cadmium, molybdenum, tungsten, fluorine, etc. are added as impurities. Examples thereof include metal oxide films such as indium oxide, cadmium oxide, tin oxide, zinc oxide added with aluminum as an impurity, and titanium oxide. In particular,
Indium oxide containing 2 to 15% by weight of tin oxide (I
The semiconductor thin film of (TO) is excellent in transparency and conductivity and is preferably used. Examples of the multilayer thin film composed of dielectric / metal / dielectric include titanium oxide / gold / titanium oxide.

The thickness of the transparent conductive layer is 5 to 200 nm.
However, if it is less than 5 nm, it may be difficult to form a uniform film, and if it exceeds 200 nm, the transparency may be lowered or the bending resistance may be deteriorated.

Examples of the method for forming these transparent conductive films include a vacuum vapor deposition method, a sputtering method, an ion plating method and an ion beam sputtering method.

As the method for producing the transparent film which is the base material of the transparent conductive film, various methods including the conventional method for molding a thermosetting resin can be used.

As the material of the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethylmethacrylate plate or the like can be applied. Further, in order to improve the releasability from the molding die, 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 applied.

The transparent conductive film has a gas barrier property,
A thin film may be applied for the purpose of imparting functions such as scratch resistance and chemical resistance. That is, various thermoplastic resins, thermosetting resins having an amino group, an imino group, an epoxy group, a silyl group, etc., a radiation curable resin having an acryloyl group, a methacryloyl group, a vinyl group, etc., or a mixture of these resins is polymerized. Inhibitors, waxes,
Gravure roll coating method, Meyer bar coating method, reverse roll coating method, dip coating method, air knife coating method, calender, with addition of dispersant, pigment, solvent, dye, plasticizer, UV absorber, inorganic filler, etc. The coating can be performed by a coating method, a squeeze coating method, a kiss coating method, a fan-ten coating method, a spray coating method, a spin coating method, or the like. Further, after coating, if necessary, curing by irradiation of radiation or heat curing by heating can be performed to form a cured thin film layer. Further, when printing is performed, methods such as a gravure method, an offset method, a flexo method, and a silk screen method can be used. Further, for the purpose of imparting gas sealability and the like, aluminum, silicon, magnesium,
A metal oxide layer containing zinc or the like as a main component may be included, and the metal oxide layer is formed by a vacuum evaporation method, a sputtering method, an ion plating method, or a plasma CVD method.

It is also possible to laminate it with another film. As a method for laminating, any publicly known method may be used, for example, a heat sealing method,
Impulse sealing method, ultrasonic bonding method, heat bonding method such as high frequency bonding method, extrusion laminating method, hot melt laminating method, dry laminating method, wet laminating method, solventless adhesive laminating method, thermal laminating method, co-extrusion method, etc. A laminating method and the like can be mentioned. As the film to be laminated, for example, polyester resin film, polyvinyl alcohol resin film, cellulose resin film, polyvinyl fluoride resin film, polyvinylidene chloride resin film, polyacrylonitrile resin film, nylon resin film, polyethylene resin film, polypropylene resin film , Acetate resin film, polyimide resin film, polycarbonate film, polyacrylate film and the like. (Liquid crystal display device) A liquid crystal display device can be manufactured using the composition for optical materials of the present invention.

In this case, the composition for optical materials is a substrate material,
Liquid crystal film such as light guide plate, prism sheet, polarizing plate, retardation film, viewing angle correction film, adhesive, polarizer protective film, color filter protection / flattening film (coating), TFT protection / flattening The liquid crystal display device may be manufactured by a usual method by using it as a coating agent such as a film (coating). (Light Emitting Diode) A light emitting diode can be manufactured using the optical material of the present invention. In this case, the light emitting diode can be manufactured by coating the light emitting element with the composition for optical material as described above. More specifically, the composition for optical materials is used as, for example, a sealing agent, a die bonding agent, a coating agent for a chip, a molding agent for a light emitting diode module, a lens material, a window material for a can seal, etc. Can be manufactured.

In this case, the light emitting element is not particularly limited, and a light emitting element used in a conventionally known light emitting diode can be used. As such a light emitting element, for example, M
Examples include those prepared by laminating a semiconductor material on a substrate provided with a buffer layer such as GaN or AlN, if necessary, by various methods such as an OCVD method, an HDVPE method, and a liquid phase growth method. As the substrate in this case, various materials can be used, for example, sapphire, spinel,
Examples thereof include SiC, Si, ZnO, and GaN single crystal.
Of these, sapphire is preferably used from the viewpoint that GaN having good crystallinity can be easily formed and has high industrial utility value.

As the semiconductor material to be laminated, GaA is used.
s, GaP, GaAlAs, GaAsP, AlGaIn
P, GaN, InN, AlN, InGaN, InGaA
1N, SiC, etc. are mentioned. Of these, from the viewpoint of obtaining high brightness, a nitride-based compound semiconductor (I
nx GayAlz N) is preferred. Such a material may contain an activator or the like.

The structure of the light emitting element is MIS junction, p
Examples include an n-junction, a homojunction having a PIN junction, a heterojunction, and a double hetero structure. Also, a single or multiple quantum well structure can be adopted.

The light emitting element may or may not be provided with a passivation layer.

Electrodes can be formed on the light emitting element by a conventionally known method.

The electrodes on the light emitting element can be electrically connected to lead terminals and the like by various methods. The electrical connection member preferably has good ohmic mechanical connectivity with the electrodes of the light emitting element, and examples thereof include bonding wires using gold, silver, copper, platinum, aluminum or alloys thereof. . A conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can also be used. Among these, it is preferable to use an aluminum wire or a gold wire from the viewpoint of good workability.

A light emitting device is obtained as described above.
In the light emitting diode of the present invention, any luminous intensity of the light emitting element can be used as long as the luminous intensity in the vertical direction is 1 cd or more. However, depending on the case where the luminous intensity in the vertical direction is 2 cd or more, the present invention can be used. The effect of the present invention is remarkable, and the effect of the present invention is more remarkable when a light emitting device of 3 cd or more is used.

The light output of the light emitting element is not particularly limited and any one can be used, but the effect of the present invention is remarkable when a light emitting element of 1 mW or more at 20 mA is used, and a light emission of 4 mW or more at 20 mA. The effect of the present invention is more remarkable when an element is used, and the effect of the present invention is more remarkable when a light emitting element of 5 mW or more at 20 mA is used.

Various light emission wavelengths of the light emitting element can be used from the ultraviolet region to the infrared region, and the effect of the present invention is particularly remarkable when the main light emission peak wavelength is 550 nm or less. One type of light emitting element may be used for single color emission, or a plurality of light emitting elements may be used for single color or multicolor emission.

The lead terminal used in the light emitting diode of the present invention is preferably one that has good adhesion to an electrical connecting member such as a bonding wire and good electrical conductivity,
The electric resistance of the lead terminal is preferably 300 μΩ-cm or less, more preferably 3 μΩ-cm or less.
Examples of these lead terminal materials include iron, copper, iron-containing copper, tin-containing copper, and those obtained by plating these with silver, nickel, or the like. The glossiness of these lead terminals may be adjusted appropriately in order to obtain good light spread.
The light emitting diode of the present invention can be manufactured by coating the light emitting element with the curable composition as described above, but in this case, the coating is not limited to one that directly seals the light emitting element, but indirectly. Including the case of coating. Specifically, the light emitting device may be sealed with the curable composition of the present invention directly by various methods conventionally used, or conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin, etc. After encapsulating the light emitting element with the encapsulating resin or glass, the top or the periphery thereof may be coated with the curable composition of the present invention. Further, the light emitting element may be sealed with the curable composition of the present invention and then molded with a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin or the like. It is possible to provide various effects such as a lens effect by the difference in refractive index and specific gravity by the above method. Various methods can be applied as a sealing method. For example, a liquid curable composition may be injected into a cup, a cavity, a package recess or the like having a light emitting element arranged at the bottom by a dispenser or other method and cured by heating, or a solid or high viscosity liquid. The curable composition may be heated to make it flow, and similarly, it may be injected into the concave portion of the package and further heated to be cured. The package in this case can be made using various materials, and examples thereof include polycarbonate resin, polyphenylene sulfide resin, epoxy resin, acrylic resin, silicone resin, ABS resin, polybutylene terephthalate resin, polyphthalamide resin, and the like. be able to. Alternatively, a method of injecting a curable composition into a mold form in advance, immersing a lead frame or the like having a light emitting element fixed therein and then curing the composition may be applied. Injection with a dispenser, transfer molding,
The sealing layer of the curable composition may be molded and cured by injection molding or the like. Further, a curable composition which is simply in a liquid or fluid state may be dropped or coated on the light emitting element to be cured. Alternatively, the curable resin can be molded and cured by stencil printing, screen printing, or application through a mask on the light emitting element. In addition, a method of fixing a curable composition which is partially cured or cured in advance into a plate shape or a lens shape on the light emitting element may be used. Further, it can be used as a die bonding agent for fixing the light emitting element to a lead terminal or a package, or can be used as a passivation film on the light emitting element. It can also be used as a package substrate.

The shape of the covered portion is not particularly limited and can be various shapes. Examples thereof include a lens shape, a plate shape, a thin film shape, and the shape described in JP-A-6-244458. These shapes may be formed by molding and curing the curable composition, or may be formed by post-processing after curing the curable composition. The light emitting diode of the present invention can be of various types, for example, any type such as a lamp type, an SMD type and a chip type. Various types of SMD type and chip type package substrates are used, and examples thereof include epoxy resin, BT resin, and ceramics.

In addition, various conventionally known methods can be applied to the light emitting diode of the present invention. For example, a method in which a layer for reflecting or condensing light is provided on the back surface of the light emitting element, a method in which a complementary color coloring portion is formed on the bottom in response to yellowing of the sealing resin,
A method in which a thin film that absorbs light of a wavelength shorter than the main emission peak is provided on the light emitting element, a method in which the light emitting element is sealed with a soft or liquid encapsulating material and then the surroundings are molded with a hard material, and light from the light emitting element is A method in which a light emitting element is sealed with a material containing a phosphor that absorbs and emits fluorescence of a longer wavelength, and then the periphery is molded, a method in which a material containing the phosphor is molded in advance and then molded with the light emitting element. -244458, a molding material having a special shape to improve light emission efficiency, a method in which a package is formed into a two-step recess for reducing uneven brightness, a method in which a light emitting diode is inserted and fixed in a through hole, and light emission is performed. By a method of forming a thin film that absorbs light of a wavelength shorter than the main emission wavelength on the element surface, flip-chip connection of the light emitting element using solder bumps, etc. Method in which light is taken out from the substrate direction by connecting the lead member or the like Te, and the like.

The light emitting diode of the present invention can be used in various conventionally known applications. Specifically, examples thereof include a backlight, an illumination, a sensor light source, a vehicle instrument light source, a signal light, an indicator light, a display device, a light source of a planar light emitter, a display, a decoration, and various lights.

[0146]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited thereto. (Synthesis Example 1) A magnetic stir bar, a dropping funnel and a cooling tube were set in a 1 L four-necked flask. Toluene 2 in this flask
200 g of 00 g, 1,3,5,7-tetramethylcyclotetrasiloxane was added, and the mixture was heated to 50 ° C. and stirred in an oil bath under a nitrogen atmosphere. Allyl glycidyl ether 9
5.0 g, xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum) 31.5 μL, toluene 5
0 g of the mixture was added dropwise from the dropping funnel over 30 minutes.
After heating at the same temperature for 1 hour, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ¹ H-NMR shows that this is 1, 3,
SiH of 5,7-tetramethylcyclotetrasiloxane
It was found that some of the groups were hydrosilylated with allyl glycidyl ether (referred to as reactant A). Moreover, when the content of SiH groups was determined by ¹ H-NMR using 1,2-dibromomethane as an internal standard, it was found to contain 6.63 mmol / g of SiH groups. The product is a mixture, but contains the following as the component (B) of the present invention as a main component. Further, it contains a platinum vinyl siloxane complex which is the component (C) of the present invention.

[0147]

[Chemical 14] (Synthesis Example 2) A magnetic stir bar, a dropping funnel and a cooling tube were set in a 2 L four-necked flask. Toluene 6 in this flask
00g, 1,3,5,7-tetramethylcyclotetrasiloxane 600g was put, and it heated and stirred at 50 degreeC in the oil bath in nitrogen atmosphere. 295 g of α-methylstyrene,
A mixture of 94.5 μL of a platinum vinyl siloxane complex xylene solution (containing 3 wt% as platinum) and 150 g of toluene was added dropwise from a dropping funnel over 40 minutes. After heating to 100 ° C. and heating for 4 hours, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ¹ H-NMR shows that this is 1, 3,
SiH of 5,7-tetramethylcyclotetrasiloxane
It was found that some of the groups were hydrosilylated with α-methylstyrene (referred to as reactant B). In addition, 1,2-dibromomethane was used as an internal standard for ¹ H-
When the SiH group content was determined by NMR, it was 6.4.
It was found to contain 3 mmol / g SiH groups. The product is a mixture, but contains the following as the component (B) of the present invention as a main component. Further, it contains a platinum vinyl siloxane complex which is the component (C) of the present invention.

[0148]

[Chemical 15] (Synthesis Example 3) A 5 L two-necked flask was equipped with a stirrer, a dropping funnel and a cooling tube. Toluene 18 in this flask
00g, 1,3,5,7-tetramethylcyclotetrasiloxane 1440g were put, and it heated and stirred in a 120 degreeC oil bath. Triallyl isocyanurate 200
g, toluene 200 g, and xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum) 1.44 ml
The mixed solution of was added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours, and then the unreacted 1, 3, 5, 7
-Tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure. ¹ H-NMR shows that this
SiH of 5,7-tetramethylcyclotetrasiloxane
It was found that some of the groups were reacted with triallyl isocyanurate (referred to as Reactant C). Also,
¹ H-NM with 1,2-dibromomethane as internal standard
When the SiH group content was calculated by R, it was 8.08 m.
It was found to contain mol / g SiH groups.
The product is a mixture, but contains the following as the component (B) of the present invention as a main component. Further, it contains a platinum vinyl siloxane complex which is the component (C) of the present invention.

[0149]

[Chemical 16] (Examples 1 to 4 and Comparative Examples 1 to 3) As the component (A), diallyl ether of bisphenol A or triallyl isocyanurate is used, and as the component (B), synthesis examples 1 to 3 are used.
A curable composition was prepared by using the reactants A to C synthesized in 1. and using the platinum vinyl siloxane complex as the component (C) in the formulation shown in the table. The curable composition was mixed and poured into a cell formed by sandwiching a silicone rubber sheet having a thickness of 3 mm between two glass plates as a spacer, and then poured at 60 ° C / 6 hours, 70 ° C / 1 hour, 80 ° C / 1 hour, Stepwise heating was performed under the conditions of 120 ° C./1 hour and 150 ° C./10 hours to obtain a plate-shaped cured product. Using this cured product, thermal discoloration resistance and thermal shock resistance were examined. (The heat discoloration resistance was obtained by subjecting the obtained 3 mm thick test piece to 1 in a hot air oven in an air atmosphere at 120 ° C.
The sample was stored for 00 hours, and the color was visually observed. The sample showing no coloration was marked with ◯, and the sample showing yellowing was marked with x. Thermal shock resistance was measured using a prismatic test piece of 3 mm x 5 mm x 30 mm,
Immersion in a solder bath heated to 250 ° C. for 10 seconds and then immediately in a water bath at 20 ° C. for 3 seconds to visually observe the condition of the test piece. . )

[0150]

【table 1】

[0151]

EFFECTS OF THE INVENTION By using the curable composition of the present invention, a thermosetting resin using a hydrosilylation reaction as a curing reaction has high resistance to heat coloring and suppresses the occurrence of cracks in a thermal shock test. Therefore, it is possible to manufacture a highly reliable liquid crystal display device and light emitting diode using this.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02F 1/1335 510 G02F 1/1335 510 1/13357 1/13357 H01L 33/00 H01L 33/00 NF term (Reference) 2H090 HB07X HB13X JB03 JD13 JD17 LA06 LA09 LA11 2H091 FA08X FA08Z FA11X FA11Z FC10 FC22 FC25 LA02 LA04 LA30 4J035 CA02U CA07M CA22M FB01 FB02 LB17 LB20 5F041 AA31 CA34 CA76 DA77 DAFF DA46 DA77 DAFF

Claims (8)

[Claims] 1. An organic compound containing at least two (A) allyloxy groups and / or metalyloxy groups in one molecule, (B) allyl glycidyl ether or / and methallyl glycidyl ether (α), and one molecule. A compound obtainable by a hydrosilylation reaction of a chain and / or cyclic polyorganosiloxane (β) having at least 3 SiH groups therein, and
A compound containing at least two SiH groups in the molecule,
A composition for optical materials, which comprises (C) a hydrosilylation catalyst as an essential component. 2. The composition for optical materials according to claim 1, wherein the component (A) is an allylated phenolic compound and / or a methallylated phenolic compound. 3. The component (β) has the following general formula (I): (In the formula, R ¹ represents an organic group having 1 to 6 carbon atoms, and n is 3 to
Represents the number 10. 3. The composition for optical materials according to claim 1 or 2, which is a cyclic polyorganosiloxane having at least 3 SiH groups in one molecule represented by the formula (1). 4. An optical material using the composition for optical materials according to claim 1. 5. A liquid crystal display device using the optical material according to claim 4. 6. A light emitting diode using the optical material according to claim 4. 7. A method of manufacturing a liquid crystal display device using the optical material according to claim 4. 8. A method of manufacturing a light emitting diode using the optical material according to claim 4.