JP2014181287A - Curable composition for optical materials and cured product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of improving the heat resistance and light resistance of a cured product without adversely affecting the hydrosilylating reactivity thereof.SOLUTION: The problem-solving curable composition for optical materials comprises (A) a compound possessing two or more intramolecular SiH groups, (B) a compound possessing two or more intramolecular alkenyl groups, and, at a ratio of 0.005-0.4 pt.wt. with respect to 100 pts.wt. of the sum of components (A) and (B), (C) a specified hindered amine antioxidant such as a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, etc.

Description

The present invention is a curable composition for optical materials having high heat resistance and light resistance, excellent gas barrier properties and cold shock resistance, and good handling properties when sealing an optical semiconductor element, and curing thereof. Related to things.

  Polysiloxane-based curable compositions and cured products have heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical properties, flame resistance, water resistance, transparency, non-tackiness, and non-corrosion. It is excellent and used in various industries. Among them, a curable composition composed of polysiloxane having a polyhedral structure may exhibit good heat resistance, light resistance, excellent chemical stability, low dielectric constant, etc. from its specific chemical structure. Are known. However, there remains room for further improvement in heat resistance and light resistance (Patent Document 1).

Addition of an antioxidant is effective for improving heat resistance and light resistance, but in a curable composition utilizing a hydrosilylation reaction such as a polysiloxane curable composition, the antioxidant is coated with a catalyst. May poison. In that case, curing failure occurs and a cured product exhibiting sufficient physical properties cannot be obtained.
Development of a composition capable of improving the heat resistance and light resistance of a cured product without impairing hydrosilylation reactivity is desired (Patent Documents 2 and 3).

WO08 / 066116 2010-132726 2011-111585

  To provide a composition capable of improving the heat resistance and light resistance of a cured product without impairing hydrosilylation reactivity.

As a result of intensive studies to solve the above problems, the present inventors have
The inventors have found that the above-mentioned problems can be solved by adding 0.005 to 0.4 parts by weight of a specific hindered amine-based antioxidant to the main agent, and have reached the present invention.
That is, the present invention has the following configuration.

1). (A) a compound having two or more SiH groups in one molecule;
(B) a compound having two or more alkenyl groups in one molecule;
(C) 0.005 to 0.4 parts by weight of a specific hindered amine antioxidant having the structure represented by the following general formula (1) with respect to 100 parts by weight of the total of the components (A) and (B) What is claimed is: 1. A curable composition for optical materials. (In the formula, X is represented by -H, -R, -R'-, and it is hydrogen or carbon that is directly bonded to the nitrogen atom, and R and R 'are monovalent or carbon, hydrogen, and oxygen. Represents a divalent substituent.)

  2). The curable composition for optical materials according to 1), wherein X in the general formula (1) of the component (C) is carbon directly bonded to nitrogen.

  3). The compound (A) having two or more SiH groups in one molecule comprises a polyhedral polysiloxane compound (a) having an alkenyl group, a compound (b) having a hydrosilyl group, and an alkenyl group in one molecule. The curable composition for optical materials according to any one of 1) and 2), which is obtained by subjecting one compound (c) to a hydrosilylation reaction.

4). The polyhedral polysiloxane compound (a) having an alkenyl group has the formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
3) The curable composition for optical materials according to 3), which is a polyhedral polysiloxane compound having an alkenyl group composed of a siloxane unit represented by formula (1).

  5). 3. The curable composition for optical materials according to any one of 3) to 4), wherein the compound (b) having a hydrosilyl group is a cyclic polysiloxane or a linear polysiloxane having a hydrosilyl group. object.

  6). The optical material according to any one of 3) to 5), wherein the organosilicon compound (c) having one alkenyl group in one molecule is an organosilicon compound having one or more aryl groups. Curable composition.

7). The component (A) has the formula: [XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[{A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, an aryl Group or a group linked to other polyhedral skeleton polysiloxane, X has a structure of either of the following general formula (2) or general formula (3), and when there are a plurality of X, the general formula ( The structure of 2) or general formula (3) may be different, and the structure of general formula (2) or general formula (3) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Which may be the same or different. Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain, which may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has a structure of the following general formula (4).

(1 is an integer greater than or equal to 2; R ⁵ is a group derived from an organosilicon compound); R is an alkyl group or an aryl group}] A curable composition for optical materials.

8). The curable composition for optical materials according to 7), wherein R ⁵ contains one or more aryl groups.

9). 8. The curable composition for optical materials according to 8), wherein the aryl group of R ⁵ is directly bonded to a silicon atom.

  10). The compound (B) having two or more alkenyl groups in one molecule is an organopolysiloxane (B-1) having two or more alkenyl groups in one molecule. The curable composition for optical materials according to any one of the above.

  11). Compound (B) having two or more alkenyl groups in one molecule is an organic compound (B-2) represented by the following general formula (5),

In the formula, R ¹ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ¹ may be different or the same, and any one of 1) to 9) The curable composition for optical materials according to item 1.

  12). The compound (B) having two or more alkenyl groups in one molecule includes (B-1) and (B-2), and is described in any one of 1) to 11) above A curable composition for optical materials.

  13). The curable composition for optical materials according to any one of 1) to 12), wherein a curing retarder is added.

  14). The curable composition for optical materials according to any one of 1) to 13), wherein a hydrosilylation catalyst is added.

  15). Hardened | cured material formed by hardening | curing the curable composition for optical materials of 1) -14).

  16). An optical device obtained by curing the curable composition for optical materials according to 1) to 14).

  17). The semiconductor light-emitting device formed by hardening | curing the curable composition for optical materials of 1) -14).

  By using a specific hindered amine-based antioxidant, a cured product having heat resistance and light resistance can be obtained without inhibiting hydrosilylation reactivity.

Hereinafter, the present invention will be described in detail.
The present invention is a curable composition for optical materials and a cured product comprising the following components (A) to (C).
(A) a compound having two or more SiH groups in one molecule;
(B) a compound having two or more alkenyl groups in one molecule;
(C) A specific hindered amine-based antioxidant having a structure represented by the following general formula (1) in an amount of 0.005 to 0.4 parts by weight based on the main agent,
(In the formula, X is represented by -H, -R, -R'-, and it is hydrogen or carbon that is directly bonded to the nitrogen atom, and R and R 'are monovalent or carbon, hydrogen, and oxygen. Represents a divalent substituent.)

<Compound (A) having two or more SiH groups in one molecule>
The compound (A) having two or more SiH groups in one molecule of the present invention is not particularly limited as long as it is a compound having two or more SiH groups in one molecule, but in the presence of a hydrosilylation catalyst described later. A reaction product obtained by hydrosilylating a polyhedral polysiloxane compound (a) having an alkenyl group and a compound (c) having one alkenyl group in one molecule with a compound (b) having a hydrosilyl group However, it is preferable in terms of a good balance of handling properties of the curable composition, heat resistance of the cured product, light resistance, gas barrier properties, and thermal shock resistance.

<Polyhedral polysiloxane compound (a) having an alkenyl group>
The polyhedral polysiloxane compound (a) having an alkenyl group in the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and having a polyhedral skeleton. Specifically, for example, the following formula [R ⁶ SiO _3/2 ] _x [R ⁷ SiO _3/2 ] _y
(X + y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ⁶ is an alkenyl group or a group having an alkenyl group; R ⁷ is any organic group, or Groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by the formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of siloxane units represented by the formula:

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

R ¹ is an alkyl group or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ¹ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.
R ² is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ² in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

  a is not particularly limited as long as it is an integer of 1 or more, but is preferably 2 or more, and more preferably 3 or more, from the handleability of the compound and the physical properties of the resulting cured product. Further, b is not particularly limited as long as it is 0 or an integer of 1 or more.

The sum of a and b (= a + b) is an integer from 6 to 24, but from the viewpoint of the stability of the compound and the stability of the resulting cured product, it should be 6 to 12, and more preferably 6 to 10. preferable.
The method for synthesizing the component (a) is not particularly limited, and the component can be synthesized using a known method. As a synthesis method, for example, a silane of R ⁸ SiX ^a ₃ (wherein R ⁸ represents R ⁶ or R ⁷ described above, and X ^a represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by the hydrolysis condensation reaction of the compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolytic condensation reaction of R ⁸ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds, and polyhedral Methods for synthesizing structural polysiloxanes are also known.

  In addition, for example, there is a method of hydrolytic condensation of tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide. In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polyhedral polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded through a siloxane bond. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

<Compound (b) having hydrosilyl group>
The compound (b) having a hydrosilyl group used in the present invention is not particularly limited as long as it has one or more hydrosilyl groups in the molecule, but the obtained polyhedral polysiloxane modified product has transparency, heat resistance, From the viewpoint of light resistance, it is preferably a siloxane compound having a hydrosilyl group, and more preferably a cyclic siloxane having a hydrosilyl group or a linear polysiloxane. In particular, from the viewpoint of gas barrier properties, a cyclic siloxane is preferable.

  The linear polysiloxane having a hydrosilyl group includes a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit. Copolymers, copolymers of methylphenylsiloxane units and methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked at the end with dimethylhydrogensilyl groups, polyblocked at the ends with dimethylhydrogensilyl groups Examples thereof include diphenylsiloxane and polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group.

  In particular, as a linear polysiloxane having a hydrosilyl group, a polysiloxane having a molecular end blocked with a dimethylhydrogensilyl group from the viewpoints of reactivity during modification, heat resistance of the resulting cured product, light resistance, etc. Furthermore, polydimethylsiloxane having a molecular end blocked with a dimethylhydrogensilyl group can be suitably used. Specific examples thereof include tetramethyldisiloxane and hexamethyltrisiloxane.

Examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1. , 3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen -1,3,5-trimethylcyclotrisiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7, Examples include 9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclohexasiloxane. Specific examples of the cyclic siloxane in the present invention include, for example, 1,3,5,7-tetrahydro, from the viewpoints of industrial availability and reactivity, or heat resistance, light resistance, strength, and the like of the resulting cured product. Gen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.
These compounds (b), which have a hydrosilyl group, may be used alone or in combination of two or more.

<Compound (c) having one alkenyl group in one molecule>
In the present invention, the compound (c) having one alkenyl group in one molecule reacts with the hydrosilyl group of the compound (b) having a hydrosilyl group. By using the component (c), the elastic modulus of the obtained cured product can be reduced, and the thermal shock resistance can be improved.
Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.
The component (c) in the present invention is not particularly limited as long as it is a compound having one alkenyl group in one molecule, but that it contains at least one aryl group in one molecule, From the viewpoint of refractive index, it is more preferable that the aryl group is directly bonded to a silicon atom from the viewpoint of heat resistance and light resistance.

  The component (c) in the present invention is preferably silane or polysiloxane from the viewpoints of heat resistance and light resistance. When the component (c) is a silane having one alkenyl group in one molecule, specifically, for example, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, triphenylvinylsilane, triethylvinylsilane, diethylphenylvinylsilane And ethyldiphenylvinylsilane, allyltrimethylsilane, allyldimethylphenylsilane, allylmethyldiphenylsilane, allyltriphenylsilane, allyltriethylsilane, allyldiethylphenylsilane, allylethyldiphenylsilane, and the like. Among these, trimethylvinylsilane, dimethylphenylvinylsilane, methyldiphenylvinylsilane, and triphenylvinylsilane are preferable examples from the viewpoint of heat resistance and light resistance, and dimethylphenylvinylsilane and methyldiphenylvinylsilane are also preferable from the viewpoint of gas barrier properties and refractive index. Triphenylvinylsilane is a preferred example.

  In addition, when the component (c) is a polysiloxane, examples include a linear polysiloxane having one alkenyl group, a polysiloxane having one alkenyl group at the molecular end, and a cyclic siloxane having one alkenyl group. .

  When the component (c) is a linear polysiloxane having one alkenyl group, specifically, for example, polydimethylsiloxane, dimethylvinyl each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Polymethylphenylsiloxane blocked with a silyl group and a trimethylsilyl group each at one end, polydiphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group respectively, and terminated with a dimethylvinylsilyl group and a trimethylsilyl group A copolymer of a dimethylsiloxane unit and a methylphenylsiloxane unit, each of which is blocked one by one, a dimethylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Copolymers, copolymers of terminal and methylphenylsiloxane units and diphenylsiloxane units are blocked one by one, respectively dimethylvinylsilyl group and trimethylsilyl group and the like.

In the case of a polysiloxane having one alkenyl group at the molecular end, specifically, for example, polysiloxane having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group as exemplified above, SiO ₂ unit, SiO _{3 /} Examples include at least one siloxane unit selected from the group consisting of ₂ units, SiO units, and SiO _1/2 units, and polysiloxane composed of one dimethylvinylsiloxane unit.

  When the component (c) is a cyclic siloxane having one alkenyl group, specifically, for example, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl -3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1 -Vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane and the like are exemplified.

  The component (c) of the present invention may be a cyclic olefin compound having one carbon-carbon double bond in one molecule. By having a cyclic olefin compound, the gas barrier property of the obtained cured product is greatly improved.

  The carbon-carbon double bond of the cyclic olefin compound having one carbon-carbon double bond in one molecule may be any of a vinylene group, a vinylidene group, and an alkenyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

  In addition, the component (c) in the present invention preferably has an average molecular weight of 1000 or less from the viewpoint of reactivity with the component (b). Examples of such cyclic olefin compounds include aliphatic cyclic olefin compounds and substituted aliphatic cyclic olefin compounds.

  Specific examples of the aliphatic cyclic olefin compound include cyclohexene, cycloheptene, cyclooctene, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, allylcyclohexane, allylcycloheptane, allylcyclooctane, and methylenecyclohexane. It is done.

  Specific examples of the substituted aliphatic cyclic olefin compound include norbornene, 1-methylnorbornene, 2-methylnorbornene, 7-methylnorbornene, 2-vinylnorbornane, 7-vinylnorbornane, 2-allylnorbornane, 7-allylnorbornane, 2-methylene norbornane, 7-methylene norbornane, camphene, vinyl norcamphene, 6-methyl-5-vinyl-bicyclo [2,2,1] -heptane, 3-methyl-2-methylene-bicyclo [2,2,1 ] -Heptane, α-pinene, β-pinene, 6,6-dimethyl-bicyclo [3,1,1] -2-heptaene, 2-vinyladamantane, 2-methyleneadamantane and the like.

  Among these, cyclohexene, vinylcyclohexane, norbornene, camphene, and pinene are preferable examples from the viewpoint of availability.

  These compounds (c), which are compounds having one alkenyl group in one molecule, may be used alone or in combination of two or more.

  Component (c) is added such that the number of alkenyl groups in component (c) is 0.01 to 0.5 per hydrosilyl group in compound (b) having the hydrosilyl group described above. It is preferable. When the addition amount is small, the thermal shock resistance of the resulting cured product may be lowered, and when the addition amount is large, a curing failure may occur in the resulting cured product.

  The method for obtaining the compound (A) having two or more SiH groups in one molecule of the present invention is not particularly limited and can be variously set, but after reacting the component (a) and the component (b) in advance, The component (c) may be reacted, the component (c) and the component (b) are reacted in advance, the component (a) may be reacted, or the component (a) and the component (c) You may make it coexist and make it react with (b) component. After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of a compound containing only the component (c) and the component (b) and not including the component (a), the component (a) and the component (b) are reacted, and the unreacted (b) A method in which the component (c) is reacted after the component is distilled off is preferred.

  In the compound (A) having two or more SiH groups in one molecule thus obtained, a part of the alkenyl group of the component (a) used for the reaction may remain.

Although there is no restriction | limiting in particular as the addition amount of the hydrosilylation catalyst used at the time of the synthesis | combination of the compound (A) which has 2 or more SiH groups in 1 molecule, The alkenyl group 1 of (a) component and (c) component used for reaction It is good to use in the range of 10 ^{< -1} > ^-10-10 mol with respect to mol. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. When there are many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. There is also a risk of foaming. Moreover, when there are few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  The compound (A) having two or more SiH groups in one molecule thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and a hydrosilyl group is introduced into the molecule. Therefore, it can be reacted with a compound having various alkenyl groups. Specifically, a cured product can be obtained by reacting with an organopolysiloxane having two or more alkenyl groups in one molecule described later.

In addition, the compound (A) having two or more SiH groups in one molecule in the present invention can be liquefied at a temperature of 20 ° C. Since the compound (A) having two or more SiH groups in one molecule is liquid, it is preferable because of excellent handling properties.
In the present invention, the compound (A) having two or more SiH groups in one molecule has the formula
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure represented by the following general formula (2) or general formula (3), and when there are a plurality of X, the general formula (2 ) Or the structure of the general formula (3) may be different, or the structure of the general formula (2) or the general formula (3) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Which may be the same or different. Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain, which may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has a structure of the following general formula (4).

(L is an integer of 0 or more; R ⁵ is a group containing a cyclic olefin compound); R is an alkyl group or an aryl group}]
It is a polyhedral polysiloxane compound composed of siloxane units represented by the formula:

  The compound (A) having two or more SiH groups in one molecule thus obtained should control the amount of addition of components (a) to (c), reaction sequence, reaction time, reaction temperature, etc. Thus, it is possible to control the viscosity of the modified polyhedral polysiloxane. It is also possible to adjust the viscosity of the polysiloxane composition described later by controlling the viscosity of the compound (A) having two or more SiH groups in one molecule. The viscosity of the compound (A) having two or more SiH groups in one molecule is not particularly limited, but the compound (A) having two or more SiH groups in one molecule is liquid at a temperature of 20 ° C. In this case, the viscosity at 20 ° C. is preferably 0.01 Pa · s to 300 Pa · s, more preferably 1 Pa · s to 100 Pa · s. If the viscosity of the compound (A) having two or more SiH groups in one molecule is too low, the viscosity of the polysiloxane composition described later will be low, and additives such as phosphors may settle without dispersing. is there. If the viscosity is too high, the handling property may be deteriorated.

  In addition, the compound (A) having two or more SiH groups in one molecule contains at least three hydrosilyl groups in the molecule from the viewpoint of the strength and hardness of the obtained cured product, and further, heat resistance and light resistance. It preferably has a group.

<(B) Compound having two or more alkenyl groups in one molecule>
The curing agent (B) in the present invention is a material for curing with the compound (A) having two or more SiH groups in one molecule of the present invention and is not particularly limited. Organopolysiloxanes (B-1) and (B-2) each having two or more alkenyl groups are preferable from the viewpoints of gas barrier properties and thermal shock resistance of the obtained cured product.

<(B-1) Organopolysiloxane having two or more alkenyl groups in one molecule>
The number of siloxane units of the organopolysiloxane having two or more alkenyl groups in one molecule in the present invention is not particularly limited, but is preferably 2 or more, and more preferably 2 to 10. When the number of siloxane units in one molecule is small, the composition tends to volatilize, and desired physical properties may not be obtained after curing. Moreover, when there are many siloxane units, the gas barrier property of the obtained hardened | cured material may fall.

  The organopolysiloxane having two or more alkenyl groups in one molecule in the present invention preferably has an aryl group from the viewpoint of gas barrier properties. In addition, in the organopolysiloxane having two or more alkenyl groups in one molecule having an aryl group, the aryl group is preferably bonded directly to the Si atom from the viewpoint of heat resistance and light resistance. In addition, the aryl group may be present at either the side chain or the end of the molecule, and the molecular structure of such an aryl group-containing polysiloxane is not limited. For example, the aryl group-containing polysiloxane has a straight chain, branched chain, or partially branched chain. In addition to the chain shape, it may have a cyclic structure.

  Examples of such aryl groups include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, and 4-ethylphenyl. Group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, biphenyl group, 2,3,4-trimethyl Examples include phenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxyphenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group and the like. . Among these, a phenyl group is a preferred example from the viewpoint of heat resistance and light resistance. These may be used alone or in combination of two or more.

  The organopolysiloxane having two or more alkenyl groups in one molecule in the present invention is a linear polysiloxane having two or more alkenyl groups from the viewpoint of heat resistance and light resistance, and 2 alkenyl groups at the molecular ends. Preferred examples include polysiloxane having at least one group and cyclic siloxane having at least two alkenyl groups.

  Specific examples of the linear polysiloxane having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer, methylphenylsiloxane unit, copolymer of methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane blocked with dimethylvinylsilyl group, endblocked with dimethylvinylsilyl group Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular terminals include polysiloxanes whose ends are blocked with the dimethylvinylsilyl group exemplified above, two or more dimethylvinylsiloxane units and SiO ₂ units, SiO _{3 /} Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

  Examples of the cyclic siloxane compound having two or more alkenyl groups include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-vinyl-1-phenyl. -3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -Diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-tri Nyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11 -Hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane and the like are exemplified.

  These organopolysiloxanes having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

  The addition amount of the organopolysiloxane having two or more alkenyl groups in one molecule can be set variously, but the Si atoms contained in the polyhedral polysiloxane-based modified product, which is a modified polyhedral polysiloxane, per alkenyl group It is desirable that the hydrogen atoms directly connected to be added at a rate of 0.3 to 5, preferably 0.5 to 3. When the proportion of alkenyl groups is small, appearance defects due to foaming or the like are likely to occur, and when the proportion of alkenyl groups is large, physical properties after curing may be adversely affected.

  Curing is achieved by hydrosilylating the hydrosilyl group of the compound (A) having two or more SiH groups in one molecule of the present invention and the alkenyl group of an organopolysiloxane having two or more alkenyl groups in one molecule. Can be made with things. In the hydrosilylation reaction, it is preferable to use a hydrosilylation catalyst. As the hydrosilylation catalyst that can be used in this reaction, those described below can be used. In the hydrosilylation reaction between the polyhedral polysiloxane modified and the organopolysiloxane having two or more alkenyl groups in one molecule, the hydrosilylation catalyst used in the synthesis of the polyhedral polysiloxane modified is the polyhedral structure. Since it is brought together with the modified polysiloxane, it is not necessary to use a separate hydrosilylation catalyst.

<(B-2) Organic compound>
The component (B-2) in the present invention specifically serves as, for example, a crosslinking agent for the component (A), and can provide a cured product having heat resistance, light resistance, and gas barrier properties.
The organic compound (B-2) in the present invention is not particularly limited as long as it is an organic compound represented by the following general formula (5).

(Wherein R ¹ represents a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom, and each R ¹ may be different or the same.)

  The component (B-2) in the present invention may contain an average of two or more alkenyl groups in one molecule from the viewpoint of the strength, gas barrier properties, heat resistance, light resistance, and the like of the resulting cured product. Preferably, more preferably 2 are contained. Further, from the viewpoint of gas barrier properties, the number average molecular weight is preferably less than 900.

Specific examples of the component (B-2) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraary. Roxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl dimethyl isocyanurate, 1,2,4-trivinylcyclohexane , Diallylmonomethyl isocyanurate and the like are exemplified, and these may be used alone or in combination of two or more.
Among the above specific examples, for example, it is preferable to use an isocyanuric acid derivative from the viewpoint of adhesion to the base material when the composition is cured with the base material. Further, from the viewpoint of a balance between heat resistance and light resistance, It is more preferable to use allyl isocyanurate, diallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoglycidyl isocyanurate, for example, diallyl monomethyl isocyanurate is more preferable from the viewpoint of thermal shock resistance.
Moreover, although you may have functional groups other than an alkenyl group in the skeleton of (B-2) component, from a viewpoint of compatibility with (A) component, a methyl group, an ethyl group, a propyl group, etc. A functional group having a low polarity such as an aliphatic hydrocarbon group on a straight chain is preferred, and a methyl group is particularly preferred from the viewpoint of heat resistance and light resistance.
Although the addition amount of (B-2) component can be set variously, it is contained in the compound (A) which has two or more SiH groups in the above-mentioned 1 molecule per alkenyl group contained in (B-2) component. It is desirable that the added hydrosilyl group is 0.3 to 5, preferably 0.5 to 3. If the ratio of the alkenyl group is too small, appearance defects due to foaming and the like are likely to occur, and if too large, the physical properties of the cured product may be adversely affected.

<(C) Specific hindered amine antioxidant>
By adding the specific hindered amine antioxidant which is (C) component of this invention, the heat resistance and light resistance of hardened | cured material are improved. The specific hindered amine antioxidant of the present invention is excellent in compatibility with the components (A) and (B) of the present invention, has no inhibition of curing, and is particularly excellent with respect to other antioxidants.
(C) As a compounding quantity of a component, 0.005-0.4 weight part is preferable with respect to a total of 100 weight part of (A) component and (B) component from a long-term heat resistant viewpoint, More preferably, it is 0. 0.01 to 0.3 parts by weight. When the blending amount is less than 0.005 parts by weight, the effect of improving the heat aging resistance may not be sufficient, and when it exceeds 0.5 parts by weight, the heat resistance of the cured product obtained from the curable composition is deteriorated. May become significant.
The specific hindered amine antioxidant is at least one general formula (1) shown below per molecule.

(In the formula, X is represented by -H, -R, -R'-, and it is hydrogen or carbon that is directly bonded to the nitrogen atom, and R and R 'are monovalent or carbon, hydrogen, and oxygen. The divalent substituent is typically a methyl group, an ethyl group, an alkyl group containing an alicyclic structure having 3 to 20 carbon atoms, an acetyl group, a propionyl group or the like having 2 to 20 carbon atoms. Although an acyl group etc. can be illustrated, Although not limited to these, From an influence on sclerosis | hardening property, Preferably it is an alkyl group, More preferably, it is a methyl group.

Specific examples of carbon in which the general formula (1) is directly bonded to a nitrogen atom include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6. A mixture of pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) 2-n-butyl-2- (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) 4-methoxybenzylidene malonate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate 1,2,2,6,6-pentamethyl-4-piperidyl, and tridecyl-1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2 2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Mixed esterified product, propanedioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester, 1,5,8,12-tetrakis [4 6-bis (n-dibutyl-n-1,2,2,6,6-pentamethyltetraazadodecane, dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidi N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4 Examples include -yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine.
Specific examples of hydrogen in which the general formula (1) is directly bonded to a nitrogen atom include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2,2,6,6-tetramethyl. -4-piperidylbenzoate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-oxa-3,8-diaza-2-undecamemethyleno-4-oxo-7,7,9,9-tetramethyl Spiro [4.5] decane, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid , 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol esterified product, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl Mixed esterified product of -4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, and dimethyl succinate Polymer with 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N ″ -bis (2,2,6,6-tetramethyl-4-piperidyl) ) Polymer of hexamethylenediamine and 1,2-dibromoethane, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1 , 3,5- Triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2,4,6-trichloro 1,3,5-triazine and N A reaction product of butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine and N, N′-bis (2,2,6,6-tetramethyl-4- A mixture with a polymer of piperidinyl) -1,6-hexanediamine can be exemplified.
Among these specific hindered amine-based antioxidants, X in the general formula (1) is an alkyl group directly bonded to a nitrogen atom from the viewpoint of excellent storage stability of the curable composition and weatherability of the resulting cured product. A mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- n-Butyl-2- (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 4-methoxybenzylidene Ronate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidyl, and Tridecyl-1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis ( 2-Hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, propanedioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester, 1,5,8,12-tetrakis [4,6-bis (n-dibutyl-n-1,2,2,6) , 6-pentamethyltetraazadodecane, etc. Among them, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4 are more preferable. A mixture of piperidyl sebacate is particularly preferred.
Furthermore, it is preferable that X of the said General formula (1) is a methyl group couple | bonded directly with the nitrogen atom from the point which is excellent in compatibility with a curable composition and the heat resistance of the hardened | cured material obtained.
These specific hindered amine antioxidants may be used alone or in combination of two or more.

<Hydrosilylation catalyst>
In the present invention, a hydrosilylation catalyst is used in synthesizing a polyhedral polysiloxane modified product and curing the composition containing the modified product.

  As the hydrosilylation catalyst used in the present invention, a known hydrosilylation catalyst can be used, and there is no particular limitation.

Specifically, a platinum-olefin complex, chloroplatinic acid, platinum alone, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum, a platinum-vinylsiloxane complex, such as Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, such as Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer) , Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Patent Platinum is described in the 3220972 Pat Arcola - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

<Curing retarder>
The curing retarder is a component for improving the storage stability of the polyhedral polysiloxane composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process. In the present invention, as the retarder, known compounds used in addition-type curable compositions with hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organophosphorus compounds , Organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like. These may be used alone or in combination of two or more.

  Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1- Examples thereof include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like.

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, and N, N-dibutyl. -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

The addition amount of the curing retarder is not particularly limited, but is preferably used in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, per 1 mol of the hydrosilylation catalyst. preferable. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

<Curable composition for optical material>
In the curable composition for optical materials of the present invention, an organopolysiloxane having two or more alkenyl groups in one molecule, a hydrosilylation catalyst, and a curing retarder are added to the modified polyhedral polysiloxane as necessary. Can be obtained. The polyhedral polysiloxane composition of the present invention can be handled as a liquid resin composition. By using a liquid resin composition, it is possible to easily obtain a molded body according to the application by injecting or applying to a mold, package, substrate or the like and curing.

When adding temperature when making it harden | cure, Preferably it is 30-400 degreeC, More preferably, it is 50-250 degreeC. If the curing temperature is too high, the resulting cured product tends to have poor appearance, and if it is too low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.
The curing time can be appropriately selected depending on the curing temperature, the amount of the hydrosilylation catalyst to be used and the amount of the reactive group, and other combinations of the composition of the present application. Preferably, a cured product can be obtained by performing the treatment for 10 minutes to 8 hours.

<Adhesive agent>
An adhesiveness imparting agent can be added to the curable composition for optical materials of the present invention as necessary.

  The adhesion-imparting agent is used for the purpose of improving the adhesion between the curable composition for optical materials and the substrate in the present invention, and is not particularly limited as long as it has such an effect. A ring agent can be exemplified as a preferred example.

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

Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysila Alkoxysilanes having a methacrylic group or an acrylic group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.
The addition amount of the silane coupling agent is 0.05 to 30 parts by weight with respect to 100 parts by weight of the mixture of the modified polyhedral polysiloxane and the organopolysiloxane having two or more alkenyl groups in one molecule. It is preferably 0.1 to 10 parts by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  In the present invention, a known adhesion promoter can be used to enhance the effect of the adhesion promoter. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic ester compounds, organoaluminum compounds, and organotitanium compounds.

<Inorganic filler>
An inorganic filler can be added to the polysiloxane composition of the present invention as necessary.
By using an inorganic filler as the composition of the polysiloxane composition of the present invention, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance of the molded product obtained Various physical properties such as flame retardancy, fire resistance, and gas barrier properties can be improved.
The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, etc. Silica-based inorganic filler, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, Examples thereof include ferrite, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, and silver powder. These may be used alone or in combination of two or more.

  The inorganic filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a silane coupling agent, and the like, but are not particularly limited.

As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape can be used. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but from the viewpoint of gas barrier properties, the average particle size is preferably 0.005 to 50 μm, more preferably 0.01 to 20 μm. More preferably. Similarly, the BET specific surface area, although not particularly limited, from the viewpoint of gas barrier properties, it is preferably ^70m 2 / g or more, more preferably 100 m ² / g or more, further 200 meters ² / It is especially preferable that it is g or more.

  The addition amount of the inorganic filler is not particularly limited, but it is 1 to 1000 parts by weight, more preferably 1 to 1000 parts by weight with respect to 100 parts by weight of the mixture of the polyhedral polysiloxane modified and organopolysiloxane having two or more alkenyl groups in one molecule. Preferably, it is 3-500 weight part, More preferably, it is 5-300 weight part. When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.

  The order of mixing the inorganic filler is not particularly limited. However, in terms of easy storage stability, after mixing with an organopolysiloxane having two or more alkenyl groups in one molecule, polyhedral structure poly A method of mixing the modified siloxane is desirable. In addition, the modified polyhedral polysiloxane, which is a reaction component, is modified with polyhedral polysiloxane in that an organopolysiloxane having two or more alkenyl groups in one molecule is well mixed and a stable molded product is easily obtained. It is preferable to mix an inorganic filler with a mixture of an organopolysiloxane having two or more alkenyl groups in one molecule.

The means for mixing these inorganic fillers is not particularly limited, but specifically, for example, a stirrer such as a two-roll or three-roll, a planetary stirring deaerator, a homogenizer, a dissolver, a planetary mixer, etc. And melt kneaders such as a plast mill. The mixing of the inorganic filler may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.
The curable composition for optical materials of the present invention may optionally contain various additives such as phosphors and colorants, reaction control agents, mold release agents, and dispersants for fillers as necessary. Can do. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  In the curable composition for an optical material of the present invention, the above-described components are uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and heat-treated as necessary. Or may be given.

  The hardened | cured material of the curable composition for optical materials of this invention can be used as a molded object. As a molding method, any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding can be used.

For the optical material of the present invention, general materials used for the purpose of passing light such as visible light, infrared light, ultraviolet light, X-rays, and laser through the material.
Specific uses of the molded product obtained in the present invention include, for example, substrate materials in the field of liquid crystal displays, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, color filters, polarizers. Examples of the peripheral material of the liquid crystal display device such as a protective film and a film for liquid crystal such as a passivation film are exemplified. It is also used in PDP (plasma display) sealants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, color filters, passivation films, and LED display devices. LED element mold material, front glass protective film, front glass substitute material, adhesive, color filter, passivation film, substrate material for plasma addressed liquid crystal display, light guide plate, prism sheet, deflector plate, retardation plate, field of view Corner correction film, adhesive, color filter, polarizer protective film, passivation film, front glass protective film, front glass substitute material, color filter, adhesive, passivation film, and field emission in organic EL displays Various film substrate in Isupurei (FED), front glass protective films, front glass substitute material, adhesive, a color filter, a passivation film is exemplified.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives. More specifically, optical pickup members such as next-generation DVDs, such as pickup lenses, collimator lenses, objective lenses, sensor lenses, protective films, element sealants, sensor sealants, gratings, adhesives, prisms And a wave plate, a correction plate, a splitter, a hologram, a mirror, and the like.

  In the field of optical equipment, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

  In the field of optical components, fiber materials, lenses, waveguides, element sealants, adhesives and the like around optical switches in optical communication systems are exemplified. Examples include optical fiber materials, ferrules, sealants, adhesives and the like around the optical connector. Examples of optical passive components and optical circuit components include lenses, waveguides, LED element sealants, adhesives, and the like. Examples include substrate materials, fiber materials, element sealants, adhesives, and the like around an optoelectronic integrated circuit (OEIC).

  In the field of optical fibers, examples include sensors for industrial use such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in the home.

  Examples of the semiconductor integrated circuit peripheral material include an interlayer insulating film, a passivation film, an LSI, and a resist material for microlithography for an LSI material.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Examples include rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, and glass substitutes. Moreover, the multilayer glass for rail vehicles is illustrated. Further, examples thereof include a toughness imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating.

  In the construction field, interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials are exemplified. In agriculture, a house covering film is exemplified.

  Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.

  Next, although the curable composition for optical materials of this invention is demonstrated in detail based on an Example, this invention is not limited only to these Examples.

(viscosity)
An E-type viscometer manufactured by Tokyo Keiki was used. Measurement was performed at a measurement temperature of 23.0 ° C. and an EHD type 48φ1 times cone.

(SiH value)
Bruker 400 MHz NMR was used. The SiH value of the modified polyhedral polysiloxane is obtained by calculating the following formula (1) by making a mixture of the modified polyhedral polysiloxane and dibromoethane and measuring the NMR.
SiH value (mol / kg) = [integral value of peak attributed to SiH group of polyhedral polysiloxane modified product] / [integral value of peak attributed to methyl group of dibromoethane] × 4 × [in the mixture Dibromoethane weight] / [Molecular weight of dibromoethane] / [Modified polyhedral polysiloxane weight in mixture] (1)
Calculated using

(Preparation of samples for heat resistance test and light resistance test)
The mold was filled with the curable composition and thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 180 ° C. × 1 hour to prepare a sample having a thickness of 2 mm.

(Heat resistance test)
The sample prepared as described above was stored in a convection oven (in air) set at 180 ° C. for 24 hours. The sample after this heat test was placed on a white paper and visually observed, and there was no color change or slight color change, ◯ for yellow color, Δ for yellow color, and x for brown color.

(Light resistance test)
Using a metering weather meter (model M6T) manufactured by Suga Test Instruments Co., Ltd., a sample prepared as described above was used with a black panel temperature of 120 ° C., an irradiance of 0.53 kW / m ² and an integrated irradiance of 50 MJ / m. Irradiated to ² . The sample after this heat test was placed on a white paper and visually observed, and there was no color change or slight color change, ◯ for yellow color, Δ for yellow color, and x for brown color.

(Snap-up time (SUT))
A small amount of the blended composition was placed on an aluminum plate heated on a hot plate set at 150 ° C., and the time required to reach a cured state was measured visually while mixing at the tip of the toothpick.

(LED evaluation)
A chip-mounted LED before sealing was prepared by dicing dicing a reflector with a lead frame (MAP (Mold Array Package)) manufactured by Kaneka Co., Ltd. mounted with a blue LED chip manufactured by Cree (product number: TR5270). 10g, 0.96g phosphor manufactured by Denki Kagaku Kogyo Co., Ltd. (product number: GR240) and 0.24g phosphor manufactured by Mitsubishi Chemical (product number: BR102C) were stirred and defoamed with a planetary stirring deaerator made by Shinky. The curable composition in which the phosphor is uniformly dispersed is prepared, and within 15 minutes, the dispenser 1500 series manufactured by Sanei Tech Co., Ltd., the 3cc barrel-piston set (Product No .: SH09CP-B) manufactured by Sanei Tech Co., Ltd. It is injected into the above chip-mounted LED using a manufactured chip (product number: SH23-B), and after injection 3 Within minutes, 80 ° C. 2 hours in a convection oven, 100 ° C. 1 hour, and cured under conditions of 180 ° C. 1 hour.

The obtained LED was mounted on an aluminum substrate and emitted light at 85 ° C. and 200 mA to conduct an energization test.
The LED evaluation after the above energization test was conducted using an Otsuka Electronics total luminous flux measurement (φ300 mm) system (Part No .: HM-0930) and energized under conditions of a temperature of 25 ° C., a current of 200 mA, and a standby time of 10 seconds. The total luminous flux (lm) of the luminescent color was measured. Six measurement samples were used, and the average value was used as the measurement value. Table 2 shows the total luminous flux maintenance factor at 85 ° C., 200 mA, 1000 hours.

(Production Example 1)
To 1262 g of a 48% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), 1083 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1000 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  While stirring a solution of 716 g of dimethylvinylchlorosilane, 516 g of trimethylsilyl chloride and 1942 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the produced solid is washed by stirring vigorously in methanol and filtered to obtain tetrakis (polysiloxane compound containing alkenyl groups having 16 Si atoms and 4 vinyl groups). 601 g of vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane (Fw = 1178.2) was obtained as a white solid.

(Production Example 2)
30 g of tetrakis (vinyldimethylsiloxy) tetrakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, and 30.1 g of vinyldiphenylmethylsilane (1,3 used) , 5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane in an amount of 0.27 alkenyl groups for 1 hydrosilyl group in toluene 120 g. 5.72 μL of a xylene solution of a complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added. The solution thus obtained was added to 23.0 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (tetrakis (vinyldimethylsiloxy) tetrakis (trimethyl) used). Siloxy) An alkenyl group of octasilsesquioxane was added dropwise slowly to a solution of 3.8 hydrosilyl groups) and 23.0 g of toluene, and reacted at 105 ° C. for 2 hours. After completion of the reaction, 10.93 μl of ethynylcyclohexanol and 2.54 μl of dimethyl maleate were added, and toluene was distilled off to obtain 80.5 g of a modified polyhedral polysiloxane structure (SiH value 1.71 mol / kg). It was.

(Examples 1-5, Comparative Examples 1-4)
The compounding liquid was produced with the compounding quantity of Table 1 and 2. In the blending procedure, diallyl monomethyl isocyanurate, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane and hindered amine antioxidant were weighed in this order to obtain a uniform solution. Further, a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) and dimethyl maleate were weighed in this order to obtain a uniform solution. Further, the reactant I synthesized in Production Example 2 and 1-ethynylcyclohexanol were added, and the mixture was stirred and defoamed with a planetary stirring deaerator. Various evaluations described above were performed using the obtained curable composition, and the results are shown in Tables 1 and 2.

(Evaluation results)
As shown in Table 1, Examples 1 and 2 in which specific hindered amine antioxidants according to the claims were added to Comparative Example 2 gave good results in the heat and light resistance test. In particular, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, which is a hindered amine antioxidant having a direct alkyl group on the nitrogen atom, and methyl 1,2,2,6,6-pentamethyl- Example 1 to which a mixture of 4-piperidyl sebacate was added showed even better results in the heat resistance test.

  On the other hand, the comparative example 1 which added the hindered amine antioxidant which does not have a specific structure brought a result inferior to the comparative example 2 in the heat test.

  Based on the above results, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, which is a hindered amine-based antioxidant having an alkyl group directly on the nitrogen atom, and methyl 1,2,2,6, The amount of addition was examined using a mixture of 6-pentamethyl-4-piperidyl sebacate, and the results are shown in Table 2 (all studies shown in Table 2 set the catalyst amount to 0.7 times that in Table 1). Have been).

  The addition amount of a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate is 0.005-0. Heat resistance and light resistance were improved as compared with Comparative Example 3 which was not added in Example 3, Example 4 and Example 5 within the range of 3 parts by weight. Moreover, as a result of LED evaluation of Example 3 and Comparative Example 3, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4- It was found that the addition of the piperidyl sebacate mixture suppressed the decrease in brightness. On the other hand, in Comparative Example 4 in which the addition amount was 0.5 parts by weight, the same results as in Comparative Example 3 without addition were obtained.

Claims (17)

(A) a compound having two or more SiH groups in one molecule;
(B) a compound having two or more alkenyl groups in one molecule;
(C) 0.005 to 0.4 parts by weight of a specific hindered amine antioxidant having the structure represented by the following general formula (1) with respect to 100 parts by weight of the total of the components (A) and (B) What is claimed is: 1. A curable composition for optical materials. (In the formula, X is represented by -H, -R, -R'-, and it is hydrogen or carbon that is directly bonded to the nitrogen atom, and R and R 'are monovalent or carbon, hydrogen, and oxygen. Represents a divalent substituent.)

The curable composition for optical materials according to claim 1, wherein X in the general formula (1) of the component (C) is carbon directly bonded to nitrogen. The compound (A) having two or more SiH groups in one molecule comprises a polyhedral polysiloxane compound (a) having an alkenyl group, a compound (b) having a hydrosilyl group, and an alkenyl group in one molecule. The curable composition for optical materials according to any one of claims 1 to 2, which is obtained by subjecting one compound (c) to a hydrosilylation reaction. The polyhedral polysiloxane compound (a) having an alkenyl group has the formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
The curable composition for optical materials according to claim 3, which is a polyhedral polysiloxane compound having an alkenyl group composed of a siloxane unit represented by the formula: The curable composition for optical materials according to any one of claims 3 to 4, wherein the compound (b) having a hydrosilyl group is a cyclic polysiloxane or a linear polysiloxane having a hydrosilyl group. object. 6. The optical material according to claim 3, wherein the organosilicon compound (c) having one alkenyl group in one molecule is an organosilicon compound having one or more aryl groups. Curable composition. The component (A) has the formula: [XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
[{A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, an aryl Group or a group linked to other polyhedral skeleton polysiloxane, X has a structure of either of the following general formula (2) or general formula (3), and when there are a plurality of X, the general formula ( The structure of 2) or general formula (3) may be different, and the structure of general formula (2) or general formula (3) may be mixed.

{L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Which may be the same or different. Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain, which may be the same or different. However, at least one of Y or Z is a hydrogen atom, and at least one has a structure of the following general formula (4).

(L is an integer of 2 or more; R ⁵ is a group derived from the organic silicon compound); R is characterized by being constituted from an alkyl group or a siloxane unit expressed by an aryl group}], according to claim 1 A curable composition for optical materials. The curable composition for optical materials according to claim 7, wherein R ⁵ contains one or more aryl groups. The curable composition for optical materials according to claim 8, wherein the aryl group of R ⁵ is directly bonded to a silicon atom. The compound (B) having two or more alkenyl groups in one molecule is an organopolysiloxane (B-1) having two or more alkenyl groups in one molecule. The curable composition for optical materials according to any one of the above. Compound (B) having two or more alkenyl groups in one molecule is an organic compound (B-2) represented by the following general formula (5),

In the formula, R ¹ represents a monovalent organic group or hydrogen atom having 1 to 50 carbon atoms, and each R ¹ may be different or the same. The curable composition for optical materials according to item 1. The compound (B) having two or more alkenyl groups in one molecule includes (B-1) and (B-2). A curable composition for optical materials. A curable composition for optical materials according to any one of claims 1 to 12, wherein a curing retarder is added.   The curable composition for optical materials according to any one of claims 1 to 13, wherein a hydrosilylation catalyst is added. Hardened | cured material formed by hardening | curing the curable composition for optical materials of Claims 1-14. An optical device obtained by curing the curable composition for optical materials according to claim 1. The semiconductor light-emitting device formed by hardening | curing the curable composition for optical materials of Claims 1-14.