KR102260641B1 - Curable composition and semiconductor device - Google Patents

Abstract

The present invention has been made in view of the above circumstances, and provides a curable organopolysiloxane composition that provides a flexible cured product having high elongation and high strength, high gas barrier properties, and excellent light transmittance.
(A) (a) a compound represented by the formula (1) having two hydrogen atoms bonded to a silicon atom in one molecule, and (b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule and (c) an addition reaction product with a compound having two hydrogen atoms bonded to a silicon atom in one molecule, represented by the formula (2), (B) three or more addition reactive carbon-carbon double bonds in one molecule A curable composition comprising a compound having, (C) a hydrosilylation catalyst containing a platinum group metal.

Description

Curable composition and semiconductor device {CURABLE COMPOSITION AND SEMICONDUCTOR DEVICE}

The present invention relates to a curable composition useful as a material for an optical device or optical component, an insulating material for an electronic device or electronic component, or a coating material, and a semiconductor device in which a semiconductor element is coated with a cured product of the composition.

The curable organopolysiloxane composition comprises an organopolysiloxane containing an addition reactive carbon-carbon double bond and an organohydrogenpolysiloxane, and is cured by a hydrosilylation reaction to give a cured product. The hardened|cured material obtained in this way is excellent in heat resistance, cold resistance, and electrical insulation, and since it is transparent, it is used for various optical uses, such as an LED sealing material (patent document 1, patent document 2, patent document 3).

However, since the sealing material for optical elements containing the said composition has low gas-barrier property as a characteristic of organopolysiloxane, there exists a fault in which a silver electrode discolors by penetration of a corrosive gas from the outside. As a result, for example, there exists a problem that the brightness|luminance of LED will fall.

Accordingly, a sealing material for an optical element using a curable polyorganosiloxane composition containing a polycyclic hydrocarbon skeleton-containing component has been proposed. Since the sealing material obtained from such a composition has high gas-barrier property, it is possible to prevent the penetration|invasion of corrosive gas from the outside, and to suppress discoloration of a silver electrode (patent document 4). However, since the sealing material obtained from such a composition has drawbacks such as being high in hardness and prone to cracking in a temperature cycle test, development of a material having flexible rubber elasticity and high gas barrier properties has been desired.

Japanese Patent Application Laid-Open No. 2004-186168 Japanese Patent Application Laid-Open No. 2004-143361 Japanese Patent Application Laid-Open No. 2008-069210 Japanese Patent Application Laid-Open No. 2012-046604

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable organopolysiloxane composition which provides a flexible cured product having high elongation and high strength, high gas barrier properties, and excellent light transmittance.

In order to solve the above problems, in the present invention,

(A) (a) a compound represented by the following formula (1) having two hydrogen atoms bonded to a silicon atom in one molecule;

(Wherein, R ¹ 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. to be.)

(b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule;

(c) an addition reaction product with a compound having two hydrogen atoms bonded to a silicon atom in one molecule, which is represented by the following formula (2);

(In the formula, R ² is an unsubstituted or substituted monovalent hydrocarbon group or alkoxy group that is the same or different from each other other than an addition reactive carbon-carbon double bond, and n is a positive number satisfying 1≤n<4.)

(B) a compound having three or more addition reactive carbon-carbon double bonds in one molecule,

(C) a hydrosilylation catalyst comprising a platinum group metal

It provides a curable composition comprising a.

If it is such a curable composition, it becomes a flexible curable composition which is high elongation and high intensity|strength, has high gas-barrier property, and is excellent in light transmittance.

In the component (A), the compound (a) and the polycyclic hydrocarbon (b) are subjected to an addition reaction such that the polycyclic hydrocarbon (b) is disposed at both terminals, and the compound (c) is preferably further reacted with the compound (c). Do.

If it is such a component (A), it becomes a curable composition with higher weather resistance and heat resistance.

It is preferable that the said polycyclic hydrocarbon (b) is vinylnorbornene.

If it is such a component (b), it will be higher hardness and will become a flexible curable composition excellent in heat discoloration resistance and light transmittance.

Preferably, the polycyclic hydrocarbon (b) is any one of 5-vinylbicyclo[2.2.1]hepto-2-ene and 6-vinylbicyclo[2.2.1]hepto-2-ene, or a combination thereof. Do.

If it is such a component (b), it will be high hardness, and it will become a flexible curable composition excellent in heat discoloration resistance and light transmittance.

It is preferable that the compound having three or more addition reactive carbon-carbon double bonds in one molecule of the component (B) is an organopolysiloxane represented by the following average compositional formula (3).

R ³ _a SiO _{(4-a)/ 2} (3)

(Wherein, R ³ is an unsubstituted or substituted monovalent hydrocarbon group identical to or different from each other, ^{three or more of R 3} are addition reactive carbon-carbon double bonds, and a is a positive number satisfying 1≤a≤3 to be.)

When such component (B) is contained, it becomes a curable composition which has more moderate hardness and intensity|strength.

It is preferable that the compound which has 3 or more addition reactive carbon-carbon double bonds in 1 molecule of the said (B) component is a compound which has an isocyanuric ring.

When such component (B) is contained, it becomes a curable composition which has more moderate hardness and intensity|strength.

Moreover, at this time, it is preferable that the refractive index (25 degreeC) in visible light (589 nm) of the hardened|cured material of the said curable composition is 1.45 or more.

Moreover, at this time, it is preferable that the light transmittance (25 degreeC) in wavelength 400nm of the hardened|cured material of the said curable composition is 80 % or more.

In this case, the cured product of the curable composition preferably has a cut elongation of 100 or more and a tensile strength of 3 or more as measured according to JIS-K6249.

Moreover, at this time, it is preferable that the 1 mm-thick oxygen gas transmittance|permeability of the hardened|cured material of the said curable composition is 500 cc/m<2>*day or less in 23 degreeC.

When the hardened|cured material of the said curable composition has such a characteristic, it will become more suitable as a sealing material for optical elements.

Moreover, this invention provides the semiconductor device by which the optical-semiconductor element was coat|covered with the hardened|cured material of the said curable composition.

If it is a semiconductor device covered with such a cured product, a semiconductor device having excellent reliability can be obtained.

The curable composition of the present invention has high elongation and high strength, is flexible, has high crack resistance, and has high gas barrier properties, so that the silver electrode has high protection against corrosive gas from the outside, and has excellent light transmittance, that is, transparency. Since a cargo can be provided, it can be suitably used for protection, sealing or adhesion of a light emitting diode element, wavelength change or adjustment, or uses, such as a lens. It is also useful as a lens material, a sealing material for an optical device or optical component, various optical materials such as a display material, an insulating material for an electronic device or electronic component, and a coating material.

As mentioned above, in order to use it for various optical uses, such as an LED sealing material, development of the material which has flexible rubber elasticity and high gas-barrier property was calculated|required.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest examination about the said subject, the present inventors discovered that the said subject can be achieved by using for the optical device material the curable composition which siloxane-modified the compound containing a polycyclic hydrocarbon backbone containing component, and this invention has completed

That is, the present invention is

(A) (a) a compound represented by the following formula (1) having two hydrogen atoms bonded to a silicon atom in one molecule;

(Wherein, R ¹ 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. to be.)

(b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule;

(c) an addition reaction product with a compound having two hydrogen atoms bonded to a silicon atom in one molecule, which is represented by the following formula (2);

(In the formula, R ² is an unsubstituted or substituted monovalent hydrocarbon group or alkoxy group that is the same or different from each other other than an addition reactive carbon-carbon double bond, and n is a positive number satisfying 1≤n<4.)

(B) a compound having three or more addition reactive carbon-carbon double bonds in one molecule,

(C) a hydrosilylation catalyst comprising a platinum group metal

It is a curable composition comprising.

Hereinafter, although this invention is demonstrated in detail, this invention is not limited to these.

In the present invention, "addition reactivity" means a property capable of addition reaction with a hydrogen atom bonded to a silicon atom (hereinafter sometimes referred to as "SiH") by a known hydrosilylation reaction.

In addition, in this invention, "Me" shall represent a methyl group.

[(A) component]

(A) component of the curable composition of the present invention,

(a) a compound having two hydrogen atoms bonded to a silicon atom in one molecule represented by the following formula (1);

(Wherein, R ¹ 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. to be.)

(b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule;

(c) an addition reaction product with a compound represented by the following formula (2) and having two hydrogen atoms bonded to a silicon atom in one molecule.

(In the formula, R ² is an unsubstituted or substituted monovalent hydrocarbon group or alkoxy group that is the same or different from each other other than an addition reactive carbon-carbon double bond, and n is a positive number satisfying 1≤n<4.)

<(a) component>

The component (a), which is a raw material for the reaction of the component (A), is a compound represented by the following formula (1) and has two SiH in one molecule.

(Wherein, R ¹ 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. to be.)

^{As R<1>} in the said Formula (1), it is preferable that it is a monovalent hydrocarbon group other than an addition reactive carbon-carbon double bond, and it is especially preferable that the whole is a methyl group.

As the compound represented by such general formula (1), for example,

Structural formula: 1,4-bis(dimethylsilyl)benzene represented by _{HMe 2} Si-pC ₆ H ₄ -SiMe _{2 H;}

and silphenylene compounds such as 1,3-bis(dimethylsilyl)benzene represented by the structural formula: HMe ₂ Si-mC ₆ H ₄ -SiMe _{2 H.}

In addition, (a) component can also be used individually by 1 type or in combination of 2 or more type.

<(b) component>

Component (b), which is another reaction raw material for component (A), is a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule.

In addition, (b) component, (i) one in which an addition reactive carbon-carbon double bond is formed between two adjacent carbon atoms among carbon atoms forming the skeleton of the polycyclic hydrocarbon, (ii) a polycyclic hydrocarbon A hydrogen atom bonded to a carbon atom forming a skeleton is substituted with an addition reactive carbon-carbon double bond-containing group, or (iii) between two adjacent carbon atoms among carbon atoms forming a skeleton of a polycyclic hydrocarbon. Any of those in which an addition-reactive carbon-carbon double bond is formed and a hydrogen atom bonded to a carbon atom forming the backbone of the polycyclic hydrocarbon is substituted with an addition-reactive carbon-carbon double bond-containing group may be used.

(b) The component is preferably vinylnorbornene, specifically 5-vinylbicyclo[2.2.1]hepto-2-ene represented by the following structural formula (x), and 6- represented by the following structural formula (y) Any one of vinylbicyclo[2.2.1]hepto-2-ene or a combination thereof is preferable. (Hereinafter, when it is not necessary to distinguish these three, in the case of generically referred to as "vinylnorbornene") there is).

In addition, the substitution position of the vinyl group of vinylnorbornene may be either cis configuration (exo type) or trans configuration (endo type), and there is no particular difference in the reactivity of the component (b) due to the difference in configuration. , may be a combination of isomers of both configurations.

<(c) component>

Component (c), which is another reaction raw material for component (A), is a compound having two hydrogen atoms bonded to silicon atoms in one molecule, which is represented by the following average compositional formula (2).

(In the formula, R ² is an unsubstituted or substituted monovalent hydrocarbon group or alkoxy group that is the same or different from each other other than an addition reactive carbon-carbon double bond, and n is a positive number satisfying 1≤n<4.)

^{R 2} in the general formula (2) is preferably a monovalent hydrocarbon group other than an addition reactive carbon-carbon double bond, and includes an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms, particularly Preferably, it is a methyl group or a phenyl group.

As the compound represented by such general formula (2), for example,

Structural formula: 1,1,3,3-tetramethyldisiloxane represented by _{HMe 2} SiOSiMe _{2 H;}

and compounds such as 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane represented by Structural Formula: HMe ₂ SiOSi(C ₆ H ₅ ) ₂ OSiMe _{2 H.}

In addition, (c) component can also be used individually by 1 type or in combination of 2 or more type.

In addition, n in general formula (2) is a positive number which satisfy|fills 1<=n<4. When n is less than 1, it becomes difficult to provide flexibility to hardened|cured material, and it becomes inferior to crack resistance. Conversely, when n is 4 or more, the cured product tends to be brittle, and elongation and strength are poor.

<(A) Preparation of component>

The component (A) is an addition reaction of the component (a), the component (b), and the component (c), and the component (a) and the component (b) are subjected to an addition reaction such that the component (b) is disposed at both ends ( c) It is preferable that the component was further reacted. For example, with respect to 1 mole of component (a) having two SiH in one molecule, more than 1 mole to 10 moles or less of component (b) having two addition reactive carbon-carbon double bonds in one molecule, preferably By carrying out the addition reaction in the presence of a hydrosilylation reaction catalyst in an excess amount of preferably more than 1 mole to 5 moles or less, an addition reaction product having no SiH can be obtained. In addition, the hydrosilylation reaction catalyst in an excess amount of more than 1 mol and 10 mol or less, preferably more than 1 mol to 5 mol or less of component (c) having two SiH in one molecule with respect to 1 mol of this addition reaction product By carrying out an addition reaction in the presence of SiH, it can be obtained as an addition reaction product having two SiHs in one molecule.

As a hydrosilylation reaction catalyst, a conventionally well-known thing can be used.

For example, platinum-based catalysts such as carbon powder carrying platinum metal, platinum black, platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and monohydric alcohol, a complex of chloroplatinic acid and olefins, platinum bisacetoacetate; Platinum group metal-type catalysts, such as a palladium-type catalyst and a rhodium-type catalyst, are mentioned. In addition, about addition reaction conditions, use of a solvent, etc. are not specifically limited, What is necessary is just to carry out normally.

As described above, in the production of component (A), by using an excess molar amount of component (c) with respect to the addition reaction product of component (a) and component (b), component (A) has the structure of component (c) It can be set as having two SiH derived from 1 molecule in 1 molecule.

Suitable specific examples of the addition reaction product of component (a) and component (b) are shown in the following formula, but are not limited thereto.

(In the formula, p is preferably a positive number satisfying 0≤p≤10.)

(A) Although the suitable specific example of a component is shown to the following formula, it is not limited to this.

(In the formula, p is the same as above, and q is preferably a positive number satisfying 0≤q≤3.)

In addition, (A) component can also be used individually by 1 type or in combination of 2 or more type.

[(B) component]

Component (B) is a compound having three or more addition reactive carbon-carbon double bonds in one molecule, and the organopolysiloxane represented by the following average compositional formula (3) is preferable.

R ³ _a SiO _(4-a)/2

(Wherein, R ³ is an unsubstituted or substituted monovalent hydrocarbon group identical to or different from each other, ^{three or more of R 3} are addition reactive carbon-carbon double bonds, and a is a positive number satisfying 1≤a≤3 to be.)

^{As R 3 in} component (B), as an unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom other than an addition reactive carbon-carbon double bond, for example, an alkyl group having 1 to 6 carbon atoms and 6 carbon atoms -10 aryl groups are mentioned, Especially preferably, they are a methyl group or a phenyl group.

In addition, in the average compositional formula (3), a is a positive number satisfying 1≤a≤3. In addition, any of linear, branched, and cyclic|annular form may be sufficient as the molecular structure of this component.

When the component (B) is linear and cyclic, the viscosity measured by a rotational viscometer is preferably 100 to 20,000 mPa·s at 25° C., and particularly about 500 to 10,000 mPa·s from the viewpoint of workability. range is preferred. With such a viscosity, there is no fear of forming burrs caused by the viscosity being too low and easy to flow, and there is a fear that air bubbles mixed in the mixing of the necessary components due to the viscosity being too high are difficult to escape. there is no Moreover, when it is branched, it becomes liquid or solid, and when it is a liquid, it is preferable that the viscosity in 25 degreeC is the range of about 1,000-5,000 mPa*s. When using a solid state thing, it is preferable to use this together with soluble linear organopolysiloxane, and to make the viscosity in 25 degreeC become 100-20,000 mPa*s.

Further, the compound having three addition reactive carbon-carbon double bonds in one molecule of component (B) may be a compound having an isocyanuric ring.

As such a compound, triallyl isocyanurate is mentioned, for example. Moreover, trivinylcyclohexane etc. are mentioned as another example.

As component (B), the organopolysiloxane represented by the formula (3), the compound having an isocyanuric ring, and the trivinylcyclohexane may be used alone, or may be used in combination.

[Amount of components (A) and (B)]

In addition, the blending amount of the components (A) and (B) is such that the total amount of SiH groups in each component is 0.8 to 1.5 moles per mole of the total of addition reactive carbon-carbon double bonds in each component. it's good By setting it as such a compounding quantity, the hardened|cured material which has sufficient hardness can be obtained.

[(C) component]

The hydrosilylation reaction catalyst which is component (C) of this invention is the same as that described in the said "production of component (A)".

The amount of component (C) to be blended into the composition of the present invention may be an effective amount as a catalyst, and is not particularly limited, but is usually 1 to 500 ppm, particularly 2 to, as platinum group metal atoms with respect to the total mass of the component (A) and component (B). It is preferable to mix|blend the quantity used as about 100 ppm. By setting it as such a compounding quantity, the time required for hardening reaction becomes a suitable thing, and a problem, such as coloring hardened|cured material, does not arise.

[Other Ingredients]

In addition to the said (A)-(C) component, you may mix|blend other components with the composition of this invention according to the objective.

In addition, these other components may be used individually by 1 type, and may be used in combination of 2 or more type.

ㆍ Compounds containing aliphatic unsaturated groups other than component (B)

You may mix|blend the aliphatic unsaturated group containing compound which addition-reacts with (A) component with the composition of this invention for the purpose of improving the adhesiveness with the base material of a sealing material other than (B) component.

As such an aliphatic unsaturated group-containing compound other than the component (B), it is preferable to participate in the formation of the cured product, and organopolysiloxanes other than the component (B) having at least one aliphatic unsaturated group per molecule are exemplified. The molecular structure may be, for example, linear, cyclic, branched, or three-dimensional network. Specific examples include N-allyl-N',N"-bis(3-trimethoxysilylpropyl)isocyanurate, N-allyl-N',N"-bis(3-triethoxysilylpropyl)isocyanurate rate etc. are mentioned.

Moreover, it is possible to mix|blend the aliphatic unsaturated group containing organic compound other than the said organopolysiloxane.

Specific examples of the aliphatic unsaturated group-containing compound include monomers such as butadiene and diacrylate derived from polyfunctional alcohol; polyolefins such as polyethylene, polypropylene, or copolymers of styrene and other ethylenically unsaturated compounds (eg, acrylonitrile or butadiene); oligomers or polymers derived from functionally substituted organic compounds such as esters of acrylic acid, methacrylic acid or maleic acid.

In addition, the aliphatic unsaturated group containing compound other than (B) component may be liquid or solid at room temperature may be sufficient as it.

(B) It is preferable that content of the aliphatic unsaturated group containing compound other than component is the range of 0.1-10 mass parts with respect to a total of 100 mass parts of (A) and (B) component, More preferably, it is the range of 0.5-5 mass parts. to be. If it is 0.1 mass part or more, the effect with respect to an adhesive improvement is acquired, and if it is 10 mass parts or less, there is no possibility that problems, such as a heat resistance fall of hardened|cured material, will arise.

ㆍ Addition reaction control agent

To ensure pot life, an addition reaction controlling agent may be incorporated into the composition of the present invention. The addition reaction control agent will not be specifically limited if it is a compound which has a hardening inhibitory effect with respect to the hydrosilylation catalyst of (C)component, A conventionally well-known thing can be used.

Specific examples thereof include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; sulfur-containing compounds; acetylene-based compounds such as acetylene alcohols (eg, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-dodecin-3-ol); compounds containing two or more alkenyl groups; hydroperoxy compounds; maleic acid derivatives; and the like.

The degree of the curing inhibitory effect of the addition reaction controlling agent depends on the chemical structure of the addition reaction controlling agent. Therefore, with respect to each addition reaction controlling agent to be used, although it is preferable to adjust the addition amount to the optimal amount, it is usually about 0.0001-5 mass parts with respect to a total of 100 mass parts of components (A) and (B). By adding the optimum amount of the addition reaction controlling agent, the composition becomes excellent in long-term storage stability at room temperature and heat curing properties.

In addition to the above components, for example, in order to suppress the occurrence of coloration, cloudiness, oxidative deterioration of the cured product, a conventionally known antioxidant such as 2,6-di-t-butyl-4-methylphenol is added to the composition of the present invention. can be combined. In addition, in order to impart resistance to light degradation, a light stabilizer such as a hindered amine stabilizer may be blended into the composition of the present invention. In addition, in order to improve the strength of the cured product obtained from the composition of the present invention, an inorganic filler such as fumed silica may be blended into the composition of the present invention, or if necessary, a dye, a pigment, a flame retardant, etc. may be blended with the composition of the present invention.

If it is such a curable composition, it will be high elongation and high intensity|strength, and it will be a curable composition excellent in gas barrier property and crack resistance.

[Cured material]

The curable organopolysiloxane composition of the present invention can be cured by a known curing method under known curing conditions.

Specifically, the composition can be cured by heating at usually 80 to 200°C, preferably at 100 to 160°C. The heating time may be about 0.5 minutes to 5 hours, particularly about 1 minute to 3 hours. However, when reliability such as for LED sealing is required, it is preferable to lengthen the curing time. The form in particular of the hardened|cured material obtained is not restrict|limited, For example, any of a gel hardened|cured material, elastomer hardened|cured material, and resin hardened|cured material may be sufficient.

Moreover, when it is set as hardened|cured material, it is preferable that the curable composition obtained above has the following various characteristics. The refractive index (25°C) in visible light (589 nm) is 1.45 or more. The light transmittance (25°C) at a wavelength of 400 nm is 80% or more. The elongation at cut measured according to JIS-K6249 is 100 or more, and the tensile strength is 3 or more. The oxygen gas permeability of a thickness of 1 mm is 500 cc/m 2 ·day or less at 23°C.

Such a hardened|cured material becomes a thing which suppresses penetration of corrosive gas from the outside, and has high heat-resistant discoloration, and becomes a hardened|cured material which can be used more suitably as sealing material for optical elements.

[Sealing material for optical element/optical element]

The cured product of the composition of the present invention is excellent in gas barrier properties and heat discoloration resistance as described above, and is excellent in heat resistance, cold resistance, and electrical insulation properties like a cured product of a conventional curable organopolysiloxane composition. As an optical element sealed with the sealing material containing the composition of this invention, LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, CCD, etc. are mentioned, for example. Such an optical element can be sealed by applying a sealing material containing the composition of the present invention to the optical element, and curing the applied sealing material by a known curing method under known curing conditions, specifically, curing as described above. have. If it is a semiconductor device covered with such a cured product, a semiconductor device having excellent reliability can be obtained.

[Example]

Hereinafter, the present invention will be specifically described using Preparation Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

In addition, in the following example, a viscosity is the value measured at 23 degreeC using the rotational viscometer. The content ratio of the addition reactive carbon-carbon double bond was measured by the method according to the iodine number measurement method described in JISK0070. The number of hydrogen atoms bonded to silicon atoms was calculated from the amount of hydrogen gas generated when an aqueous sodium hydroxide solution was added dropwise to the sample.

In addition, in the following example, the symbol which shows the average composition of organopolysiloxane shows the following units.

^{_{M H: (CH 3) 2}} HSiO 1/2

D:(CH ₃ ) ₂ SiO _{2 /2}

D ^Vi :(CH ₂ ═CH)(CH ₃ )SiO _{2 /2}

^{_{M Vi: (CH 3) 2}} (CH 2 = CH) SiO 1/2

D ^2φ :(C ₆ H ₅ ) ₂ SiO _{2 /2}

[Preparation Example 1] Preparation of an addition reaction product of component (a) and component (b)

Vinylnorbornene (trade name: V0062, manufactured by Tokyo Chemical Corporation; 5-vinylbicyclo[2.2.1]hepto-2-ene and 1785 g (14.88 mol) and 455 g of toluene (a mixture of approximately equimolar isomers of 6-vinylbicyclo[2.2.1]hepto-2-ene) were added and heated to 85° C. using an oil bath. To this, 3.6 g of carbon powder carrying 5 mass % of platinum metal was added, and 1698 g (8.75 mol) of 1,4-bis(dimethylsilyl)benzene was added dropwise over 180 minutes while stirring. After completion|finish of dripping, after heating and stirring at 110 degreeC for 24 hours, it cooled to room temperature. Thereafter, the platinum metal-supported 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: 12.8 Pa·s).

The reaction product was analyzed by FT-IR, NMR, GPC and the content ratio of the addition reactive carbon-carbon double bond (0.36 mol/100 g) by iodine value measurement. As a result, the reaction product was a compound represented by the following structural formula it turned out that

[Preparation Example 2] Preparation of (A-1) component

1,1,3,3-tetramethyldisiloxane 258 g (1.92 mol), 60 g (0.12 mol) of the addition reaction product of Production Example 1 in a 2 L four-necked flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer , 200 g of toluene was added, and heated to 90 to 95°C using an oil bath. 0.2 g of CAT-PL-50T (manufactured by Shin-Etsu Chemical) was added thereto, and 240 g (0.47 mol) of the addition reaction product of Production Example 1 diluted with 100 g of toluene was added dropwise. After completion|finish of dripping, it stirred between 90-95 degreeC for 2 hours. After the stirring was completed, the temperature was returned to room temperature, 2.2 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, filtration and concentration were performed to obtain 383 g (yield 93%) of a colorless and transparent oily reaction product (A-1) component (viscosity: 1.9 Pa·s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC and the amount of hydrogen gas generated (55.6 mL/g), it was found that the reaction product was a compound represented by the following structural formula (r=0).

[Preparation Example 3] (A-2) Preparation of component

1,1,3,3-tetramethyldisiloxane 120.9 g (0.9 mol), 68 g (0.13 mol) of the addition reaction product of Production Example 1 to a 2 L four-necked flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer ), 200 g of toluene were added, and the mixture was heated to 90 to 95°C using an oil bath. To this, 0.6 g of CAT-PL-50T (manufactured by Shin-Etsu Chemical) was added, and 274.6 g (0.54 mol) of the addition reaction product of Production Example 1 diluted with 80 g of toluene was added dropwise. After completion|finish of dripping, it stirred between 90-95 degreeC for 2 hours. After completion of stirring, the mixture was returned to room temperature, 2.3 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated to obtain 413.9 g (yield: 89.3%) of a colorless and transparent oily reaction product (A-2) component (viscosity: 58.8 Pa·s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC and the amount of hydrogen gas generated (41.0 mL/g), it was found that this reaction product was a compound represented by r=0.48 in the structural formula shown in Production Example 2.

[Preparation Example 4] (A-3) Preparation of component

119.5 g (0.89 mol) of 1,1,3,3-tetramethyldisiloxane, 72.1 g (0.14) of the addition reaction product of Preparation Example 1 to a 2 L four-necked flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer mol), 200 g of toluene were added, and the mixture was heated to 90 to 95°C using an oil bath. 0.2 g of CAT-PL-50T (manufactured by Shin-Etsu Chemical) was added thereto, and 274.6 g (0.57 mol) of the addition reaction product of Production Example 1 diluted with 80 g of toluene was added dropwise. After completion|finish of dripping, it stirred between 90-95 degreeC for 2 hours. After the stirring was completed, the temperature was returned to room temperature, 2.4 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated to obtain 426.1 g (yield: 88.8%) of a colorless and transparent oily reaction product (A-3) component (viscosity: 514 Pa·s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC and the amount of hydrogen gas generated (29.6 mL/g), it was found that this reaction product was a compound represented by r=1.1 in the structural formula shown in Production Example 2.

[Preparation Example 5] Preparation of (A-4) component

In a 2 L four-neck flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer, ^{300 g (0.84 mol) of organopolysiloxane of M H} ₂ D ₃ , 28 g (0.055 mol) of the addition reaction product of Preparation Example 1 , 140 g of toluene was added, and heated to 90 to 95°C using an oil bath. 0.2 g of CAT-PL-50T (manufactured by Shin-Etsu Chemical) was added thereto, and 114.1 g (0.22 mol) of the addition reaction product of Production Example 1 diluted with 60 g of toluene was added dropwise. After completion|finish of dripping, it stirred between 90-95 degreeC for 2 hours. After completion of stirring, the mixture was returned to room temperature, 2.2 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated to obtain 277.4 g (yield: 81.1%) of a colorless and transparent oily reaction product (A-4) component (viscosity: 0.55 Pa·s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC and the amount of hydrogen gas generated (30.4 mL/g), it was found that the reaction product was a compound represented by the following structural formula.

[Example 1]

To 100 parts of component (A-1) prepared in Production Example 2, ^{21.4 parts of organopolysiloxane of the average composition formula: D Vi} ₄ and 0.12 parts of 1-ethynylcyclohexanol as a reaction control agent were added, platinum catalyst After adding 10 ppm as platinum atoms, the mixture was uniformly mixed to obtain a composition. The composition was heated at 150° C. for 2 hours and cured to measure the physical properties of the obtained elastomer. Each measurement result is shown in Table 1.

[Example 2]

To 100 parts of component (A-2) prepared in Production Example 3, ^{14.4 parts of organopolysiloxane having an average composition formula: D Vi} ₄ and 0.11 parts of 1-ethynylcyclohexanol as a reaction control agent were added, platinum catalyst After adding 10 ppm as platinum atoms, the mixture was uniformly mixed to obtain a composition. The composition was heated at 150° C. for 2 hours and cured to measure the physical properties of the obtained elastomer. Each measurement result is shown in Table 1.

[Example 3]

To 100 parts of component (A-3) prepared in Production Example 4, ^{10.4 parts of organopolysiloxane having an average composition formula: D Vi} ₄ and 0.11 parts of 1-ethynylcyclohexanol as a reaction control agent were added, platinum After adding 10 ppm of the catalyst as platinum atoms, it was uniformly mixed to obtain a composition. The composition was heated at 150° C. for 2 hours and cured to measure the physical properties of the obtained elastomer. Each measurement result is shown in Table 1.

[Example 4]

To 100 parts of component (A-3) prepared in Production Example 4, 9.9 parts of triallyl isocyanurate and 0.11 part of 1-ethynylcyclohexanol as a reaction control agent were added to the platinum catalyst as a platinum atom. After adding 10 ppm as , uniformly mixed to obtain a composition. The composition was heated at 150° C. for 2 hours and cured to measure physical properties of the obtained elastomer. Each measurement result is shown in Table 1.

[Comparative Example 1]

To 100 parts of component (A-4) prepared in Production Example 5, ^{11.7 parts of organopolysiloxane having an average composition formula: D Vi} ₄ and 0.11 parts of 1-ethynylcyclohexanol as a reaction control agent were added, platinum After adding 10 ppm of the catalyst as platinum atoms, it was uniformly mixed to obtain a composition. The composition was heated at 150° C. for 2 hours and cured to measure the physical properties of the obtained elastomer. Each measurement result is shown in Table 2.

[Comparative Example 2]

To 100 parts of the organopolysiloxane of the average composition formula: M ^H ₂ D ₁₀₀ ^{, 2.7 parts of the organopolysiloxane of the average composition formula: D Vi} ₄ and 0.10 parts of 1-ethynylcyclohexanol as a reaction control agent were added, platinum After adding 10 ppm of the catalyst as platinum atoms, it was uniformly mixed to obtain a composition. The composition was heated at 150° C. for 2 hours and cured to measure the physical properties of the obtained elastomer. Each measurement result is shown in Table 2.

[Comparative Example 3]

With respect to 100 parts of component (A-1) prepared in Production Example 2, 450 parts of organopolysiloxane having an ^{average composition formula: M Vi} ₂ D ^2φ ₉ D _{19 and 0.53 parts of 1-ethynylcyclohexanol as a reaction control agent} After adding 10 ppm of a platinum catalyst as a platinum atom to what was added, it mixed uniformly and obtained the composition. When this composition was heated at 150 degreeC for 2 hours, hardened|cured material was not obtained and it became a high-viscosity oily substance.

<Evaluation method>

About the composition obtained in each Example and the comparative example, the hardened|cured material was created according to the following method, and performance evaluation was performed. As hardening conditions, heat hardening was performed at 150 degreeC for 2 hours.

(1) transmittance

A spacer having a thickness of 2 mm was mounted between two glass plates, the composition was accommodated in a space of 15 mm × 40 mm × 2 mm, and the above-described heat curing was performed to obtain a cured product having a thickness of 2 mm. The light transmittance of the obtained hardened|cured material was measured at 25 degreeC with respect to measurement wavelength 400nm (ultraviolet-ray area|region) using the spectrophotometer. The measurement results are shown in Tables 1 and 2.

(2) Hardness, elongation at cut, tensile strength

Tables 1 and 2 show the measurement results measured according to JIS-K6249.

(3) Evaluation of gas barrier properties

A cured product having an outer diameter of 100 mm (phi) and a thickness of 1 mm was prepared and measured at 23°C using an oxygen gas transmittance measuring device (type 8001) manufactured by Illinois Instruments. The measurement results are shown in Tables 1 and 2.

(4) refractive index

The refractive index was measured at a refractive index of 589 nm at 25°C using a digital refractometer RX-5000 manufactured by ATAGO. The measurement results are shown in Tables 1 and 2.

As shown in Table 1, the cured products of Examples 1 to 5 all have a high refractive index, have excellent light transmittance and gas barrier properties, and are cured products having high elongation and tensile strength when cut, so members for optical materials , it is useful as an insulating material or coating for electronic materials.

On the other hand, as shown in Table 2, instead of component (c), the cured product of Comparative Example 1 in which a compound having n=4 in the structural formula shown in formula (2) was used for the reaction, and instead of component (A), SiH In the cured product of Comparative Example 2 in which a straight-chain organopolysiloxane having two groups per molecule was used for the reaction, the cured product was inferior in gas barrier properties and tensile strength, so it is considered unsuitable for the above applications.

In addition, this invention is not limited to the said embodiment. The above-mentioned embodiment is an illustration, and any thing which has substantially the same structure as the technical idea described in the claim of this invention, and exhibits the same effect is included in the technical scope of this invention.

Claims (11)

(A) (a) a compound represented by the following formula (1) having two hydrogen atoms bonded to a silicon atom in one molecule;

(Wherein, R ¹ 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. to be.)
(b) a polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule;
(c) an addition reaction product with a compound having two hydrogen atoms bonded to a silicon atom in one molecule represented by the following formula (2), an addition reaction product having two hydrogen atoms bonded to a silicon atom in one molecule;

(In the formula, R ² is an unsubstituted or substituted monovalent hydrocarbon group of the same or different types other than an addition reactive carbon-carbon double bond, and n is a positive number satisfying 1≤n<4.)
(B) a compound having three or more addition reactive carbon-carbon double bonds in one molecule,
(C) a hydrosilylation catalyst comprising a platinum group metal
including,
The compound having three or more addition reactive carbon-carbon double bonds in one molecule of component (B) is triallyl isocyanurate, trivinylcyclohexane, or organopolysiloxane represented by the following average compositional formula (3) Characterized in the curable composition.
R ³ _a SiO _(4-a)/2 (3)
(Wherein, R ³ is an unsubstituted or substituted monovalent hydrocarbon group identical to or different from each other, ^{three or more of the total R 3} bonds are addition reactive carbon-carbon double bonds, and a is 1≤a≤3 is a positive number that satisfies The compound (a) according to claim 1, wherein the component (A) is an addition reaction product of the compound (a) and the polycyclic hydrocarbon (b) so that the polycyclic hydrocarbon (b) is disposed at both ends. ) and the polycyclic hydrocarbon (b), the curable composition, characterized in that the addition reaction of the compound (c) further. The curable composition according to claim 1 or 2, wherein the polycyclic hydrocarbon (b) is vinylnorbornene. 3. The polycyclic hydrocarbon (b) according to claim 1 or 2, wherein said polycyclic hydrocarbon (b) is selected from among 5-vinylbicyclo[2.2.1]hepto-2-ene and 6-vinylbicyclo[2.2.1]hepto-2-ene. Any one, or a combination thereof, characterized in that the curable composition. delete delete The curable composition according to claim 1 or 2, wherein the cured product of the curable composition has a refractive index (25°C) in visible light (589 nm) of 1.45 or more. The light transmittance (25 degreeC) in wavelength 400nm of the hardened|cured material of the said curable composition is 80 % or more, The curable composition of Claim 1 or 2 characterized by the above-mentioned. The curable composition according to claim 1 or 2, wherein the cured product of the curable composition has a cut elongation of 100 or more and a tensile strength of 3 or more measured according to JIS-K6249. The curable composition according to claim 1 or 2, wherein the 1 mm-thick oxygen gas permeability of the cured product of the curable composition is 500 cc/m 2 ·day or less at 23°C. The optical semiconductor element is coat|covered with the hardened|cured material of the curable composition of Claim 1 or 2, The semiconductor device characterized by the above-mentioned.