JP2012046604A - Curable silicone-based composition containing polycyclic hydrocarbon skeleton component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable silicone-based composition having a gas barrier property, causing no warpage of a substrate even when the substrate is subjected to sealing, and providing a transparent cured product having a hardness suitable for dicing.SOLUTION: This curable silicone-based composition includes: (A) a reaction product of an addition reaction between (a) a compound represented by General Formula (1): [where R is an unsubstituted or halogen atom or the like-substituted monovalent hydrocarbon group or alkoxy group] which has in the molecule thereof, two SiH bonds and (b) a polycyclic hydrocarbon having in the molecule thereof, two addition-reactable carbon-carbon double bonds, which has in the molecule thereof, two addition-reactable carbon-carbon double bonds; (B) a linear siloxane containing in the molecule thereof, three or more SiH bonds and a phenyl group; (C) a siloxane compound having an alkoxysilyl group and/or an epoxy group and an SiH bond; and (D) a hydrosilylation reaction catalyst.

Description

  The present invention relates to a curable silicone-based composition containing a polycyclic hydrocarbon skeleton-containing component that is useful as a member for optical equipment, an insulating material for electronic equipment, or a coating material.

2. Description of the Related Art In recent years, the use of silicone resin for various LED-related applications has progressed, including sealing materials for optical device members, particularly blue light-emitting diodes (LEDs) and white light-emitting diodes (LEDs) with large light energy. Under such circumstances, various durability is required for the sealing material.
Focusing on the silicone sealing material has the advantage of being excellent in light resistance and heat discoloration, but since silicone has gas permeability as a characteristic, the silver electrode discolors due to the ingress of corrosive gas from the outside. As a result, the brightness of the LED may decrease.

  On the other hand, when focusing on the LED sealing process, in addition to a method of dispensing a sealing material on a cup-shaped device by a dispensing method, a sealing resin is applied collectively to a substrate on which a large number of LED chips are mounted. A manufacturing method is also employed in which after curing, the product is separated into pieces by dicing. When a high-hardness silicone sealing material is used in such a manufacturing method, warping of the substrate may occur due to curing shrinkage, and precise dicing may not be possible.

  First, the present inventor has determined that at least three hydrogen atoms bonded to a silicon atom and a polycyclic hydrocarbon skeleton-containing compound having two addition-reactive carbon-carbon double bonds in one molecule are bonded to a silicon atom. The curable composition containing the compound which has and a hydrosilylation catalyst as an essential component was proposed (patent document 1). However, since the cured product obtained by heat-curing this composition is inferior in gas barrier properties, the silver electrode may be discolored. Further, when the resin is applied on the substrate and the resin is cured, the substrate warps, and there is a problem that precise dicing cannot be performed.

JP 2005-133073 A

  In view of the above-mentioned problems of the prior art, the present invention has a gas barrier property, and even if sealing is performed on a substrate on which a large number of LED chips are mounted, the substrate does not warp, and yet it is diced. An object of the present invention is to provide a curable silicone-based composition that gives a transparent cured product having sufficient hardness.

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.
That is, the present invention
(A) (a) The following general formula (1):

[Wherein, R is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group. ]
A compound having two hydrogen atoms bonded to a silicon atom represented by
(b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule;
An addition reaction product having two addition-reactive carbon-carbon double bonds per molecule,
(B) a linear siloxane having three or more hydrogen atoms bonded to a silicon atom in one molecule and containing a phenyl group;
(C) a siloxane compound having at least one functional group selected from the group consisting of an alkoxysilyl group and an epoxy group, and a hydrogen atom bonded to a silicon atom, and
(D) A curable silicone composition containing a hydrosilylation reaction catalyst is provided.

  The curable silicone composition of the present invention retains gas barrier properties to prevent discoloration of the electrode, and the substrate is not warped even when sealing is performed on the substrate on which a large number of LED chips are mounted. A curable silicone composition having a hardness sufficient for dicing can be provided. Therefore, it can be suitably used for protection and sealing applications of light emitting diode elements corresponding to various manufacturing processes. Further, since the cured product is excellent in transparency, it is useful as various optical materials such as lens materials, sealing materials for optical devices, display materials, insulating materials for electronic devices, and coating materials.

The present invention will be described in detail below. Me represents a methyl group and Ph represents a phenyl group.
-Curable silicone composition-
[Component (A)]
The component (A) of the composition of the present invention is:
(a) The following general formula (1):

[Wherein, R is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, or 1 to 6 carbon atoms, which is unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group, Preferred are 1-4 alkoxy groups]
A compound having two hydrogen atoms (hereinafter also referred to as “SiH”) bonded to a silicon atom represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule It is an addition reaction product having two.

<(A) component>
The component (a), which is a reaction raw material of the component (A), is a compound represented by the formula (1).

Wherein R is independently a monovalent hydrocarbon group having 1 to 12, preferably 1 to 6 carbon atoms, or 1 to 6 carbon atoms, which is independently unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group. , Preferably 1-4 alkoxy groups.
R in the general formula (1) is preferably other than an alkenyl group and an alkenylaryl group, and it is particularly preferable that all of them are methyl groups.

As the compound represented by the general formula (1), for example,
Structural formula: 1,4-bis (dimethylsilyl) benzene represented by HMe ₂ Si—p—C ₆ H ₄ —SiMe ₂ H;
Examples include silphenylene compounds such as 1,3-bis (dimethylsilyl) benzene represented by the structural formula: HMe ₂ Si-m—C ₆ H ₄ —SiMe ₂ H.
The compound represented by the general formula (1) can be used alone or in combination of two or more.

<(B) component>
In (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, which is a reaction raw material of component (A), the above-mentioned “addition reactivity” means bonding to a silicon atom. It means a property capable of undergoing an addition reaction with a known hydrogen atom by a well-known hydrosilylation reaction.

The component (b) includes (i) an addition-reactive carbon-carbon double bond formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic hydrocarbon skeleton. (Ii) a hydrogen atom bonded to a carbon atom forming a polycyclic hydrocarbon skeleton is substituted by an addition-reactive carbon-carbon double bond-containing group, or (iii) Among the carbon atoms forming the polycyclic hydrocarbon skeleton, an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and the polycyclic hydrocarbon skeleton is Any hydrogen atom bonded to the carbon atom formed may be substituted with an addition-reactive carbon-carbon double bond-containing group. Here, examples of the addition-reactive carbon-carbon double bond-containing group include alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, norbornyl group, particularly those having 2 to 12 carbon atoms. Etc.
Examples of the component (b) include the following structural formula (x):

5-vinylbicyclo [2.2.1] hept-2-ene represented by
The following structural formula (y):

6-vinylbicyclo [2.2.1] hept-2-ene represented by the above-mentioned combination of the two (hereinafter, when there is no need to distinguish between the three, they may be collectively referred to as “vinyl norbornene”) Can be mentioned.
Incidentally, the substitution position of the vinyl group of the vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type). Since there is no difference in the above, it may be a combination of the isomers in both configurations.

<Preparation of component (A)>
The component (A) of the composition of the present invention has two addition-reactive carbon-carbon double bonds in one molecule with respect to 1 mole of the component (a) having two SiH in one molecule. An addition reaction product containing no SiH is obtained by subjecting an excess of more than 1 mole to 10 moles or less, preferably more than 1 mole and less than 5 moles of the component (b) in the presence of a hydrosilylation reaction catalyst. Can be obtained as

  Any conventionally known hydrosilylation reaction catalyst can be used. For example, carbon powder carrying platinum, platinum black, secondary platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Platinum-based catalyst; platinum group metal-based catalyst such as palladium-based catalyst and rhodium-based catalyst. Moreover, about addition reaction conditions, use of a solvent, etc., it will not be specifically limited, What is necessary is just to be normal.

  As mentioned above, when preparing the component (A), the component (b) is used in an excess molar amount with respect to the component (a). Therefore, the component (A) is derived from the structure of the component (b). It has two addition-reactive carbon-carbon double bonds in one molecule. Furthermore, the residue derived from the component (a) is bound by a divalent residue of a polycyclic hydrocarbon not having an addition-reactive carbon-carbon double bond derived from the structure of the component (b). It may include a structure.

That is, as the component (A), for example, the following general formula (6):

Y-X- (Y'-X) p-Y (6)

Wherein X is a divalent residue of the compound of the component (a), Y is a monovalent residue of the polycyclic hydrocarbon of the component (b), and Y ′ is the above (b ) Component divalent residue, p is an integer of 0 to 10, preferably 0 to 5)
The compound represented by these is mentioned.

In addition, about the value of p which is the number of the repeating units represented by said (Y'-X), adjusting the excess molar amount of said (b) component made to react with respect to 1 mol of said (a) component. It is possible to set by.
As Y in the general formula (6), specifically, for example, the following structural formula:

(Hereinafter, when it is not necessary to distinguish the six members, these are collectively referred to as “NB group”, and “NB” without distinguishing the six-member structure). May be abbreviated.);

  As Y ′ in the general formula (6), specifically, for example, the following structural formula:

The bivalent residue represented by these is mentioned.
However, the asymmetrical divalent residue represented by the above structural formula is not limited in the left-right direction as described above. It also shows the structure rotated 180 degrees.

Preferred specific examples of the component (A) represented by the general formula (6) are shown below, but are not limited thereto. (The meaning of “NB” is as described above.)
NB-Me ₂ Si-p-C ₆ H ₄ -SiMe ₂ -NB
_{NB-Me 2 Si-m-} C 6 H 4 -SiMe 2 -NB

(In the formula, p is an integer of 1 to 10.)
Furthermore, the component (A) of the present invention can be used singly or in combination of two or more.

[Component (B)]
The component (B) of the present invention is a linear siloxane having 3 or more hydrogen atoms bonded to a silicon atom in one molecule and containing a phenyl group. SiH in the component (B) is added by an addition reactive carbon-carbon double bond and two hydrosilylation reactions in one molecule of the component (A) to give a cured product having a three-dimensional network structure. .

Examples of the component (B) include the following general formula (2):

R ' ₃ SiO (R' ₂ SiO) _n SiR ' ₃ (2)

[Wherein R ′ is independently a hydrogen atom, an unsubstituted or monovalent hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom, a cyano group or a glycidoxy group, provided that At least three of R ′ are hydrogen atoms, and at least one of R ′ in one molecule is a phenyl group, and n is a number from 0 to 100. ]
The linear siloxane type compound represented by these is mentioned.

When R ′ in the general formula (2) is an unsubstituted or monovalent hydrocarbon group substituted with a halogen atom, a cyano group or a glycidoxy group, for example, a methyl group, ethyl, propyl group, isopropyl group, butyl group Alkyl groups such as tert-butyl group, pentyl group, isopentyl group, hexyl group and sec-hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl such as phenyl group, o-, m- and p-tolyl An aralkyl group such as a benzyl group or a 2-phenylethyl group; an alkenylaryl group such as a p-vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups are a halogen atom or a cyano group Or an alkyl halide substituted with a glycidoxy group, for example, a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, etc. ; 2-cyanoethyl group; such as 3-glycidoxypropyl group. In addition, in order to form a transparent material that is compatible with the component (A) and from the viewpoint of the obtained gas barrier properties, at least one R ′ in one molecule is a phenyl group.
On the condition that the above conditions are satisfied, it is preferable that the remaining R ′ is a methyl group and a phenyl group because they are easily produced industrially and are easily available.

Although the preferable example of the said (B) component is shown below, it is not limited to this.
Me ₃ SiO (MeHSiO) ₃ (Ph ₂ SiO) ₂ SiMe ₃
Me ₃ SiO (MeHSiO) ₄ (Ph ₂ SiO) ₂ SiMe ₃
HMe ₂ SiO (MeHSiO) ₁ (Ph ₂ SiO) ₂ SiMe ₂ H
HMe ₂ SiO (MeHSiO) ₂ (Ph ₂ SiO) ₂ SiMe ₂ H
The component (B) of the present invention can be used singly or in combination of two or more.

[Component (C)]
Component (C) of the present invention is a siloxane compound having at least one functional group selected from the group consisting of an alkoxysilyl group and an epoxy group, and a hydrogen atom bonded to a silicon atom, It is added by an addition-reactive carbon-carbon double bond and a hydrosilylation reaction to give a cured product having a three-dimensional network structure and to provide adhesion to a substrate material.

  The above alkoxysilyl group and epoxy group are usually bonded to a silicon atom via a divalent organic group, and the divalent organic group includes carbon atoms such as an ethylene group, a trimethylene group, and a tetramethylene group. Examples thereof include 2 to 6 alkylene groups and alkylene groups in which some of a plurality of methylene groups constituting the alkylene groups are substituted with oxygen atoms.

  Examples of the component (C) include 1- (2-trimethoxysilylethyl) -1,3,5,7-tetramethylcyclotetrasiloxane, 1- (3-glycidoxypropyl) -1,3, 5,7-tetramethylcyclotetrasiloxane, 1- (2-trimethoxysilylethyl) -3- (3-glycidoxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane, etc. . These can be used singly or in combination of two or more.

[Amounts of components (A), (B) and (C)]
Generally, in terms of obtaining a cured product having a hardness that is sufficient for the above-described uses such as coating materials, the total amount of addition reactive carbon-carbon double bonds contained in the composition is 1 mol. The total amount of SiH contained in the composition is usually in the range of 0.5 to 3.0 mol, preferably in the range of 0.8 to 1.5 mol. That is, as an optional compounding component to be described later, a silicon-based compound having an addition-reactive carbon-carbon double bond other than the component (A) and / or silicon having SiH other than the component (B) and the component (C) When blending a system compound, it is necessary to consider the addition-reactive carbon-carbon double bond and SiH group in these optional blending components.

  However, in addition to the component (A), the component (B), and the component (C), when neither a silicon compound having an addition reactive carbon-carbon double bond nor a silicon compound having a SiH group is present, (A) , (B) and (C) are blended in such amounts that the total amount of SiH in component (B) and component (C) is based on the total mole of addition-reactive carbon-carbon double bonds in component (A). The amount is usually 0.5 to 3.0 mol, preferably 0.8 to 1.5 mol.

  In addition, when a silicon compound having an addition-reactive carbon-carbon double bond other than the component (A) is included, the addition-reactive carbon-carbon double bond of the compound is an addition reactivity in the entire composition. It is preferably 50 mol% or less, more preferably 0 to 30 mol% of the total amount of carbon-carbon double bonds. Further, when a silicon-based compound having SiH other than the component (B) and the component (C) is included, the SiH of the compound is preferably 50 mol% or less of the total amount of SiH in the entire composition. 0 to 30 mol% is more preferable.

[Component (D)]
The hydrosilylation reaction catalyst which is the component (D) of the present invention is the same as that described in the above “Preparation of the component (A)”.

  The blending amount of the component (D) in the composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst. Usually, it is preferable to add an amount of usually about 1 to 500 ppm, particularly about 2 to 100 ppm as a platinum group metal atom with respect to the total mass of the component (A) and the component (B). By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.

[Other ingredients]
In addition to the above components (A) to (D), it is optional to add other components exemplified below to the composition of the present invention as long as the objects and effects of the present invention are not impaired.
<Antioxidant>
In the cured product of the curable resin composition of the present invention, the addition-reactive carbon-carbon double bond in the component (A) may remain unreacted. The said coloring can be prevented beforehand by mix | blending an agent.

  As the antioxidant, all conventionally known antioxidants can be used. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2, 5-di-t-butylhydroquinone, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'- And methylenebis (4-ethyl-6-t-butylphenol). These can be used singly or in combination of two or more.

  In addition, when using this antioxidant, the blending amount thereof is not particularly limited as long as it is an effective amount as an antioxidant, but with respect to the total mass of the component (A) and the component (B). Usually, it is preferably 10 to 10,000 ppm, particularly preferably about 100 to 1,000 ppm. By setting the blending amount within the above range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent optical characteristics without coloration, white turbidity, oxidative deterioration and the like is obtained.

<Viscosity / Hardness modifier>
In order to adjust the viscosity of the composition of the present invention or the hardness of the cured product obtained from the composition of the present invention, a linear diorganopolysiloxane or reticulated organopolysiloxane having an alkenyl group or SiH bonded to a silicon atom A non-reactive (that is, having no alkenyl group and SiH bonded to a silicon atom) linear or cyclic diorganopolysiloxane, silphenylene compound and the like may be blended.

<Others>
Moreover, in order to ensure pot life, an addition reaction control agent such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be blended. Furthermore, an inorganic filler such as fumed silica may be blended in order to improve the strength within a range that does not affect transparency, and if necessary, a dye, pigment, flame retardant, etc. may be blended. Also good.

  Furthermore, it is also possible to use a light stabilizer in order to impart resistance to light degradation caused by light energy such as sunlight and fluorescent lamps. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidation degradation is suitable, and the antioxidant effect is further improved by using it together with the antioxidant. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like.

  Moreover, when using the composition of this invention as a sealing material, in order to improve adhesiveness with a base material, you may mix | blend a silane coupling agent and add a plasticizer for crack prevention. Also good.

  In addition, about the hardening conditions of the composition of this invention, it changes with the quantity, Although it does not restrict | limit in particular, Usually, it is preferable to set it as the conditions of 60-180 degreeC and 1 to 5 hours.

-Cured product-
The cured product obtained by curing the composition of the present invention described above has excellent gas barrier properties, and has an oxygen gas permeability of 300 cm ³ / m ² · day or less at 23 ° C. in terms of a sheet having a thickness of 1 mm. Yes, preferably 0 to 200 cm ³ / m ² · day. Therefore, when used as a sealing material in a semiconductor device such as a light emitting diode, it is possible to prevent the corrosive gas from permeating from the outside, and to prevent discoloration of the silver electrode and thus reduction in luminance of the LED.

  The cured product generally has a hardness (Shore D) of 50 or more, preferably 60 or more, and usually 60 to 70. Despite the high hardness of the cured product, since the substrate hardly deforms when applied and cured on the substrate, the composition is applied to the substrate on which many LED chips are mounted and cured. After being made, it can be used in a manufacturing method for separating into pieces by dicing.

  Since the above cured product is colorless and transparent, lens materials, LED, sealing materials for optical devices such as light receiving elements, various optical materials such as display materials, insulating materials for electronic devices such as prepregs, and coating materials It is suitable as.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[Synthesis Example 1] Preparation of Component (A) Into a 5 L four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo) [2.2.1] isomer mixture of approximately equimolar amounts of hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene) 1785 g (14.88 mol) and 455 g of toluene were added, and oil was added. Heated to 85 ° C. using a bath. To this, 3.6 g of carbon powder carrying 5 mass% platinum was added, and 1698 g (8.75 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 180 minutes while stirring. After completion of dropping, the mixture was further heated and stirred at 110 ° C. for 24 hours, and then cooled to room temperature. Thereafter, the platinum-supporting carbon was removed by filtration, and toluene and excess vinylnorbornene were distilled off under reduced pressure to obtain 3362 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 12820 mPa · s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) Compound having two p-phenylene groups (an example of a typical structural formula shown below): about 41 mol%,

(2) Compound having three p-phenylene groups (an example of a typical structural formula shown below): about 32 mol%

(3) and a compound having 4 or more p-phenylene groups: about 27 mol%
It was found to be a mixture of Moreover, the content rate of the addition reactive carbon-carbon double bond as the whole mixture was 0.36 mol / 100 g.

[Example 1]
(A) Reaction product obtained in Synthesis Example 1: 40 parts by mass
(B) Me ₃ SiO (MeHSiO) ₃ (Ph ₂ SiO) ₂ SiMe ₃ : 52 parts by mass,
(C) 1- (2-trimethoxysilylethyl) -3- (3-glycidoxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane: 8 parts by mass (in the above composition (The SiH / carbon-carbon double bond molar ratio is 1.03.)
(D) platinum-vinylsiloxane complex: an amount of 20 ppm with respect to the total mass of the composition as a platinum atom, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition.

[Example 2]
(A) Reaction product obtained in Synthesis Example 1: 56 parts by mass
(B) Me ₃ SiO (MeHSiO) ₄ (Ph ₂ SiO) ₂ SiMe ₃ : 36 parts by mass,
(C) 1- (2-trimethoxysilylethyl) -3- (3-glycidoxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane: 8 parts by mass (in the above composition (The SiH / carbon-carbon double bond molar ratio is 1.04.)
(D) platinum-vinylsiloxane complex: an amount of 20 ppm with respect to the total mass of the composition as a platinum atom, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition.

[Example 3]
(A) Reaction product obtained in Synthesis Example 1: 56 parts by mass
(B) HMe ₂ SiO (MeHSiO) ₁ (Ph ₂ SiO) ₂ SiMe ₂ H: 36 parts by mass,
(C) 1- (2-trimethoxysilylethyl) -3- (3-glycidoxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane: 8 parts by mass (in the above composition (The SiH / carbon-carbon double bond molar ratio is 1.05.)
(D) platinum-vinylsiloxane complex: an amount of 20 ppm with respect to the total mass of the composition as a platinum atom, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition.

[Example 4]
(A) Reaction product obtained in Synthesis Example 1: 59 parts by mass
(B) HMe ₂ SiO (MeHSiO) ₂ (Ph ₂ SiO) ₂ SiMe ₂ H: 33 parts by mass,
(C) 1- (2-trimethoxysilylethyl) -3- (3-glycidoxypropyl) -1,3,5,7-tetramethylcyclotetrasiloxane: 8 parts by mass (in the above composition (The SiH / carbon-carbon double bond molar ratio is 1.09.)
(D) platinum-vinylsiloxane complex: an amount of 20 ppm with respect to the total mass of the composition as a platinum atom, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition.

[Comparative Example 1]
Using 77 parts by mass of component (A) described in Example 1 above, and as component (B),
A composition was obtained in the same manner as in Example 1, except that 15 parts by mass of (MeHSIO) ₄ was used. (SiH / carbon-carbon double bond (molar ratio) = 1.01)

[Comparative Example 2]
As in Example 1, except that 33 parts by mass of the following reaction product of 1,3,5,7-tetramethylcycloterolasiloxane and vinylnorbornene was used as the component (B) described in Example 1 above. To obtain a composition. (SiH / carbon-carbon double bond (molar ratio) = 1.11)

(In the formula, n is an integer of 1 to 11.)

<Performance evaluation method>
About the composition obtained by each Example and the comparative example, about the following characteristic, the hardened | cured material was created according to the method of description, respectively, and performance evaluation was implemented. The curing was performed by heating at 100 ° C. for 1 hour and further by heating at 150 ° C. for 5 hours. The results are shown in Tables 1 and 2.

(1) Appearance A 2 mm thick spacer was interposed between two glass plates, the composition was placed in a space of 15 mm × 40 mm × 2 mm, and heat curing was performed under the above conditions. The appearance of the obtained cured product was visually evaluated.
(2) Hardness Hardness (Shore D) was measured using a cured product having a thickness of 6 mm prepared by the same method as in (1).
(3) Evaluation of gas barrier property A cured product having an outer diameter of 100 mmφ and a thickness of 1 mm was prepared and measured at 23 ° C. using an oxygen gas permeability measuring device (8001 type) manufactured by Illinois Instruments.

(4) Evaluation of substrate shape retention The occurrence of warpage of the substrate when the composition was cured on the substrate to produce a cured product was evaluated.
The composition was applied to an aluminum substrate (50 mm × 150 mm × 0.3 mm) and cured under the above conditions to produce a 1 mm thick cured product on the substrate. After standing at room temperature, the warpage of the aluminum substrate was measured.
(5) Dicing test The composition was applied to a multilayer substrate for printed wiring boards (manufactured by Mitsubishi Gas Chemical Co., Ltd., HL820, 50 mm x 150 mm x 0.2 mm) and cured under the above conditions to produce a 1 mm thick cured product on the substrate. . After leaving at room temperature, the adhesive film was attached to the substrate, and then cut into a size of 5 mm × 5 mm using a disco dicing machine (DAD341 type).

(6) Light transmittance The light transmittance of the cured product prepared in (1) was measured using a spectrophotometer at three measurement wavelengths: 800 nm, 600 nm, and 400 nm.

(Note) * In the dicing test of Comparative Examples 1 and 2, when the substrate was attached to the adhesive film, a phenomenon that the flat state could not be maintained occurred.

[Evaluation]
All of the cured products of the examples are excellent in transparency and gas barrier properties and have high hardness, but even when the cured product is prepared on the substrate, the substrate does not warp. Therefore, it is suitable for dicing. On the other hand, the composition of the comparative example was inferior in gas barrier properties, and when a cured product was prepared on the substrate, it was impossible to perform dicing due to large warpage.

  The composition of the present invention is useful for protection and sealing in the production process of various light-emitting diode elements. It is also useful as various optical materials such as lens materials, sealing materials for optical devices, display materials, insulating materials for electronic devices, and coating materials.

Claims (9)

(A) (a) The following general formula (1):

[Wherein, R is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group. ]
A compound having two hydrogen atoms bonded to a silicon atom represented by
(b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule;
An addition reaction product having two addition-reactive carbon-carbon double bonds per molecule,
(B) a linear siloxane having three or more hydrogen atoms bonded to a silicon atom in one molecule and containing a phenyl group;
(C) a siloxane compound having at least one functional group selected from the group consisting of an alkoxysilyl group and an epoxy group, and a hydrogen atom bonded to a silicon atom, and
(D) A curable silicone composition containing a hydrosilylation reaction catalyst.   The composition according to claim 1, wherein the polycyclic hydrocarbon of (b) is 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2. -A curable silicone composition which is an ene or a combination of both. The curable silicone composition according to claim 1 or 2, wherein the component (B) is a linear siloxane represented by the following general formula (2).

R ' ₃ SiO (R' ₂ SiO) _n SiR ' ₃ (2)

[Wherein R ′ is independently a hydrogen atom, an unsubstituted or monovalent hydrocarbon group having 1 to 12 carbon atoms substituted with a halogen atom, a cyano group or a glycidoxy group, provided that At least three of R ′ are hydrogen atoms, and at least one of R ′ in one molecule is a phenyl group, and n is a number from 0 to 100. ]   The component (A) is an addition reaction between the component (a) and the component (b) in an excess molar amount relative to the component (a) in the presence of platinum-supported carbon, and then the platinum-supported carbon. The curable silicone composition according to any one of claims 1 to 3, wherein the curable silicone composition is an addition-reactive organism obtained by a method comprising removing the odor by filtration.   The curable silicone composition according to any one of claims 1 to 4, wherein the cured product has gas barrier properties. 6. The curable silicone composition according to claim 5, wherein when the composition is molded and cured into a 1 mm thick sheet, the oxygen gas permeability at 23 ° C. of the sheet is 300 cm ³ / m ² · day or less.   The composition according to any one of claims 1 to 4, wherein the substrate is deformed when the composition is cured after being applied on the substrate, and the hardness of the obtained cured product. The curable silicone-based composition capable of dicing with (Shore D) of 50 or more.   The curable silicone composition according to any one of claims 1 to 7, which is used as a material for an optical device or an optical component. A cured product obtained by curing the composition according to any one of claims 1 to 4, and having an oxygen gas permeability of 300 cm ³ / m ² · day or less at 23 ° C. in terms of a thickness of 1 mm.