JPWO2018062513A1 - LED encapsulant composition - Google Patents

Abstract

To provide a sealing material composition for an LED, a cured product obtained by curing the composition, and an LED device in which an LED element is sealed by the cured product. (A) A linear organopolysiloxane having three structural units represented by the following formula (1) and having at least two alkenyl groups bonded to a silicon atom in one molecule; R1R2R3SiO1 / 2) a (R4R5SiO2 / 2) b (R62SiO2 / 2) c (1) (B) has one of three structural units represented by the following formula (2) and one hydrogen atom bonded to a silicon atom (R7R8R9SiO1 / 2) d (R10R11SiO2 / 2) e (R122SiO2 / 2) f (2) and (C) hydrosilylation reaction catalyst, containing at least two linear organopolysiloxanes therein, and the above-mentioned formula (1) The sealing material composition for LED which at least one of R4 in (4) and R10 in said Formula (2) represents a biphenylyl group. 【Selection chart】 None

Description

  The present invention relates to a sealing material composition for an LED, a cured product obtained by curing the composition, and an LED device in which an LED element is sealed by the cured product.

  Since a silicone composition forms a cured product excellent in rubbery properties such as weather resistance, heat resistance, hardness, and elongation, it is used for the purpose of protecting LED elements, electrodes, substrates and the like in LED devices. In addition, silver or a silver-containing alloy having good conductivity is used as an electrode in the LED device, and the substrate may be plated with silver to improve the luminance.

  Generally, cured products made of silicone compositions have high gas permeability, and when used in high brightness LEDs with high light intensity and large heat generation, discoloration of the encapsulant due to corrosive gas in the environment, There is a problem that a decrease in luminance occurs due to the corrosion of silver plated on an electrode or a substrate.

In Patent Document 1, (A) diorganopolysiloxane containing at least two alkenyl groups bonded to silicon atoms, (B) SiO _4/2 units, Vi (R ² ) ₂ SiO _1/2 units, and R ² Organopolysiloxane of resin structure consisting of ₃ SiO _1/2 units, (C) organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule, and (D) platinum group metal catalyst An addition-curable silicone composition has been proposed which comprises

  However, such an addition-curable silicone composition is very easy to transmit the corrosive gas in the environment, and the silver plated on the electrode or substrate is easily corroded.

  Patent document 2 discloses (A) an organopolysiloxane represented by an average unit formula, a linear chain having at least two alkenyl groups in one molecule and having no silicon-bonded hydrogen atom in an optional (B) molecule. A curable silicone composition is proposed which comprises at least an organopolysiloxane, (C) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and (D) a catalyst for hydrosilylation reaction.

  The curable silicone composition described in Patent Document 2 has high hydrosilylation reactivity, an organopolysiloxane that forms a cured product with low gas permeability, has high reactivity, and low gas permeability. A curable silicone composition that forms a cured product is said to provide a cured product with low gas permeability.

  However, even if the electrode or the substrate is sealed with a silver-plated LED substrate with the curable silicone composition described in Patent Document 2, for example, silver plating is corroded in an environment of 80 ° C. in a sulfur atmosphere. There is a problem that the brightness of the light emitted by the LED decreases.

JP 2000-198930 A JP, 2014-84417, A

  The object of the present invention has been made in view of the above circumstances, and is excellent in heat-resistant transparency, adhesion to an LED substrate, and sealing for an LED in which silver plating is not corroded even under a severe environment of 80 ° C. under sulfur atmosphere. It is providing a material composition, a cured product obtained by curing the composition, and an LED device in which the LED element is sealed by the cured product.

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, as an LED encapsulant composition, (A) an alkenyl group having three structural units and bonded to a silicon atom A linear organopolysiloxane having at least two in the molecule, (B) A linear organopolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule. And (C) at least one of the organopolysiloxane (A) and the organopolysiloxane (B) when forming a composition containing a hydrosilylation reaction catalyst, an organohaving a structural unit having a biphenylyl group bonded to a silicon atom. When it is made into polysiloxane, the sealing material for LEDs formed of this composition is excellent in heat-resistant transparency, adhesiveness with the LED substrate, and at 80 ° C. in a sulfur atmosphere. Cormorant found that silver plating is not corroded even in a severe environment, thereby completing the present invention.
That is, as the first aspect of the present invention,
(A) A linear organopolysiloxane having three structural units represented by the following formula (1) and having at least two alkenyl groups bonded to a silicon atom in one molecule,
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ ₂ SiO _2/2 ) _c (1)
(Wherein, R ¹ represents an alkenyl group having 2 to 12 carbon atoms, R ² represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and R ³ represents a number of carbon atoms R 6 represents an aryl group of 6 to 20 or an alkyl group having 1 to 12 carbon atoms, R ⁴ represents an aryl group having 6 to 20 carbon atoms or biphenylyl group, and R ⁵ represents an aryl group having 6 to 20 carbon atoms or 2 R 12 represents an alkyl group having 1 to 12 carbon atoms, two R ⁶ each represent an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and a, b and c each represent 0. 01 ≦ a ≦ 0.5, 0.01 ≦ b ≦ 0.7, 0.1 ≦ c ≦ 0.9, and a + b + c = 1.
(B) A linear organopolysiloxane having three structural units represented by the following formula (2) and having at least two hydrogen atoms bonded to a silicon atom in one molecule,
(R ⁷ R ⁸ R ⁹ SiO _1/2 ) _d (R ¹⁰ R ¹¹ SiO _2/2 ) _e (R ¹² ₂ SiO _2/2 ) _f (2)
(Wherein, R ⁷ represents a hydrogen atom, R ⁸ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and R ⁹ represents an aryl group having 6 to 20 carbon atoms or R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms, R ¹⁰ represents an aryl group having 6 to 20 carbon atoms, or biphenylyl group, R ¹¹ represents an aryl group having 6 to 20 carbon atoms or 1 to 12 carbon atoms And R ¹² represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and d, e and f each represent 0.01 ≦ d ≦ 0.5. , 0.01 ≦ e ≦ 0.7, 0.1 ≦ f ≦ 0.9, and d + e + f = 1.
And (C) a hydrosilylation reaction catalyst, wherein at least one of R ⁴ in the formula (1) and R ¹⁰ in the formula (2) represents a biphenylyl group.
In the present invention, the aryl group having 6 to 20 carbon atoms is defined as one that does not contain a biphenylyl group and a terphenylyl group.

As a second aspect, the invention relates to a sealing material composition for an LED according to the first aspect, wherein R ⁴ in the formula (1) represents a phenyl group or a biphenylyl group.
As a third aspect, the present invention relates to the sealing material composition for an LED as described in the first aspect or the second aspect, wherein R ¹⁰ in the formula (2) represents a phenyl group or a biphenylyl group.

  The present invention relates to the sealing material composition for an LED according to any one of the first to third aspects, which further contains (D) an adhesion-imparting agent as a fourth aspect.

The present invention relates to, as a fifth aspect, a cured product obtained from the sealing material composition for an LED according to any one of the first to fourth aspects.
The present invention relates to, as a sixth aspect, an LED device in which an LED element is sealed with the cured product described in the fifth aspect.

  The sealing material composition for LEDs of the present invention is characterized in that it forms a cured product excellent in heat resistance transparency, resistance to sulfurization and adhesion. Moreover, the LED element sealed by the cured | curing material obtained from the sealing material composition for LED which is this invention has the characteristics excellent in reliability.

The LED sealing material composition of the present invention will be described in detail.
The linear organopolysiloxane of the component (A) has three structural units represented by the following formula (1), and has at least two alkenyl groups bonded to a silicon atom in one molecule.
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ ₂ SiO _2/2 ) _c (1)

In the formula, R ¹ represents an alkenyl group having 2 to 12 carbon atoms, and as the alkenyl group, vinyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, A dodecenyl group is exemplified, preferably a vinyl group. R ² represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and when R ² represents an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group as the aryl group , Anthracenyl group, phenanthryl group, pyrenyl group, and hydrogen atoms of these aryl groups are alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, or halogen atoms such as chlorine atom and bromine atom A substituted group is exemplified, preferably a phenyl group. When R ² represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. A group is exemplified, preferably a methyl group. R ³ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and when R ³ represents an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group as the aryl group , Anthracenyl group, phenanthryl group, pyrenyl group, and hydrogen atoms of these aryl groups are alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, or halogen atoms such as chlorine atom and bromine atom A substituted group is exemplified, preferably a phenyl group. When R ³ represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. A group is exemplified, preferably a methyl group. R ⁴ represents an aryl group having 6 to 20 carbon atoms or a biphenylyl group, and as the aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, and an aryl group thereof Examples thereof are groups in which a hydrogen atom is substituted with an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a halogen atom such as a chlorine atom or a bromine atom. A biphenylyl group is preferable as R ⁴ from the viewpoint of preventing a decrease in luminance due to discoloration of the sealing material due to corrosive gas in the environment and corrosion of silver plated on the electrode or the substrate. R ⁵ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and when R ⁵ represents an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group as the aryl group , Anthracenyl group, phenanthryl group, pyrenyl group, and hydrogen atoms of these aryl groups are alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, or halogen atoms such as chlorine atom and bromine atom A substituted group is exemplified, preferably a phenyl group. When R ⁵ represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. A group is exemplified, preferably a methyl group. R ⁶ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and when R ⁶ represents an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group as the aryl group , Anthracenyl group, phenanthryl group, pyrenyl group, and hydrogen atoms of these aryl groups are alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, or halogen atoms such as chlorine atom and bromine atom A substituted group is exemplified, preferably a phenyl group. When R ⁶ represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. A group is exemplified, preferably a methyl group.

  Further, in the formula, a, b and c satisfy 0.01 ≦ a ≦ 0.5, 0.01 ≦ b ≦ 0.7, 0.1 ≦ c ≦ 0.9, and a + b + c = 1, respectively. The number is preferably a number satisfying 0.02 ≦ a ≦ 0.5, 0.1 ≦ b ≦ 0.6, 0.1 ≦ c ≦ 0.8, and a + b + c = 1, and more preferably 0.05 ≦ a ≦ 0.5, 0.2 ≦ b ≦ 0.6, 0.1 ≦ c ≦ 0.7, and a number satisfying a + b + c = 1. This is because when a is less than the lower limit of the above range, the strength of the cured product is not sufficiently obtained and the gas resistance of the cured product is reduced, while when it is greater than the upper limit of the above range, the cured product is It becomes brittle. When a is within the above range, the cured product has sufficient strength, and the gas resistance of the cured product becomes good. When b is less than the lower limit of the above range, the gas resistance of the cured product is lowered, and when it is greater than the upper limit of the above range, the cured product becomes white and hazy. When b is within the above range, the gas resistance of the cured product is good, and a transparent cured product is obtained. When c is less than the lower limit of the above range, the crack resistance of the cured product is reduced, and when it is greater than the upper limit of the above range, the gas resistance of the cured product is reduced. When c is within the above range, there is crack resistance and the gas resistance of the cured product becomes high.

In addition, the linear organopolysiloxane of (A) component may further have a siloxane unit represented by _{SiO4 / 2} in the range which does not impair the objective of the present invention. In addition, this organopolysiloxane has an alkoxy group bonded to a silicon atom such as a methoxy group, an ethoxy group or a propoxy group, or a hydroxyl group bonded to a silicon atom bond within the range not impairing the object of the present invention. It is also good.

As a method of synthesizing the organopolysiloxane of the component (A), for example,
General formula (I): R ¹ R ² R ³ SiX ¹
A silane compound represented by
General formula (II): R ⁴ R ⁵ Si (X ² ) ₂
In silane compound represented by, and the general formula _{^{(III): R 6 2 Si}} (X 3) 2
And a method of causing a hydrolysis / condensation reaction in the presence of an acid or an alkali.

General formula (I): R ¹ R ² R ³ SiX ¹
In a silane compound represented by the organopolysiloxane of the ^formula: is a raw material for introducing the siloxane units represented by _{^{R 1 R 2 R 3 SiO 1/2}} . In general formula (I), R ¹ represents an alkenyl group having 2 to 12 carbon atoms, R ² represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and R ³ represents It represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms. Moreover, in the formula, X ¹ represents an alkoxy group, an acyloxy group, a hydroxyl group or a —OSiR ¹ R ² R ³ group. When X ¹ represents an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. When X ¹ represents an acyloxy group, an acetoxy group is exemplified as the acyloxy group.

  Examples of such silane compounds include alkoxysilanes such as dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylphenylvinylmethoxysilane and methylphenylvinylethoxysilane, acetoxysilanes such as dimethylvinylacetoxysilane and methylphenylvinylacetoxysilane, and dimethyl Examples thereof include hydroxysilanes such as vinylhydroxysilane and methylphenylvinylhydroxysilane, and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

General formula (II): R ⁴ R ⁵ Si (X ² ) ₂
In a silane compound represented by the organopolysiloxane of the formula: is a raw material for introducing the siloxane units represented by R ⁴ R ⁵ SiO _2/2. In general formula (II), R ⁴ represents an aryl group having 6 to 20 carbon atoms or a biphenylyl group, and R ⁵ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms. Further, in the formula, X ² represents an alkoxy group, an acyloxy group or a hydroxyl group. When X ² represents an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. When X ² represents an acyloxy group, an acetoxy group is exemplified as the acyloxy group.

  As such a silane compound, methylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylbiphenylyldimethoxysilane, methylbiphenylyldiethoxy Silane, alkoxybisilane such as phenylbiphenylyldimethoxysilane and phenylbiphenylyldiethoxysilane, methylphenyldiacetoxysilane, ethylphenyldiacetoxysilane, diphenyldiacetoxysilane, methylbiphenylyldiacetoxysilane, phenylbiphenylyldiacetoxysilane, etc. Acetoxysilane, methylphenyl dihydroxysilane, ethylphenyl dihydroxysilane, diphenyl dihydro Shishiran, methyl biphenylyl dihydroxysilane, hydroxy silanes and phenyl biphenylyl dihydroxysilane are exemplified.

General formula (III): R ⁶ ₂ Si (X ³ ) ₂
The silane compound represented by these is a raw material for introduce | transducing the siloxane unit represented by Formula: R _< ⁶ > _{2SiO2 / 2} to organopolysiloxane. In general formula (III), R ⁶ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and X ³ represents an alkoxy group, an acyloxy group, a halogen atom or a hydroxyl group. When X ³ represents an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. When X ³ represents an acyloxy group, an acetoxy group is exemplified as the acyloxy group.

  As such silane compounds, alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, acetoxysilanes such as dimethyldiacetoxysilane and diphenyldiacetoxysilane, dimethyldihydroxysilane, diphenyldihydroxy Examples are hydroxysilanes such as silanes.

  The linear organopolysiloxanes of component (A) can be selected from silane compounds (I), silane compounds (II), silane compounds (III) and, if necessary, other silane compounds, cyclic silicone compounds or silane oligomers. It is characterized in that it is obtained by hydrolysis / condensation reaction in the presence of an acid or an alkali.

  Examples of the acid that can be used include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid, trifluoromethanesulfonic acid, and ion exchange resin. Moreover, as an alkali which can be used, inorganic alkalis, such as potassium hydroxide and sodium hydroxide, triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, triethanolamine, aqueous ammonia, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, amino Examples are organic base compounds such as alkoxysilanes having amino groups and aminopropyltrimethoxysilane.

  In the above preparation method, an organic solvent can be used. Examples of the organic solvent that can be used include ethers, ketones, alcohols, acetates, aromatic or aliphatic hydrocarbons, γ-butyrolactone, and a mixture of two or more of these. Preferred organic solvents include diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Examples are propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, γ-butyrolactone, pentane, hexane, heptane, toluene and xylene.

  In the above preparation method, it is preferable to add water or a mixed solution of water and an alcohol in order to accelerate the hydrolysis / condensation reaction of each component. As this alcohol, methanol, ethanol and isopropanol are preferable. The reaction is promoted by heating, and when an organic solvent is used, it is preferable to carry out the reaction at the reflux temperature.

The linear organopolysiloxane of the component (B) has three structural units represented by the following formula (2), and has at least two hydrogen atoms bonded to a silicon atom in one molecule.
(R ⁷ R ⁸ R ⁹ SiO _1/2 ) _d (R ¹⁰ R ¹¹ SiO _2/2 ) _e (R ¹² ₂ SiO _2/2 ) _f (2)

In the formula, R ⁷ represents a hydrogen atom. R ⁸ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and when R ⁸ represents an aryl group, as the aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group , Anthracenyl group, phenanthryl group, pyrenyl group, and hydrogen atoms of these aryl groups are alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, or halogen atoms such as chlorine atom and bromine atom A substituted group is exemplified, preferably a phenyl group. When R ⁸ represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. A group is exemplified, preferably a methyl group. R ⁹ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and when R ⁹ represents an aryl group, as the aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group , Anthracenyl group, phenanthryl group, pyrenyl group, and hydrogen atoms of these aryl groups are alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, or halogen atoms such as chlorine atom and bromine atom A substituted group is exemplified, preferably a phenyl group. When R ⁹ represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. A group is exemplified, preferably a methyl group. R ¹⁰ represents an aryl group having 6 to 20 carbon atoms or a biphenylyl group, wherein the aryl group is exemplified by phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, and aryl groups thereof Examples thereof are groups in which a hydrogen atom is substituted with an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a halogen atom such as a chlorine atom or a bromine atom. A biphenylyl group is preferable as R ¹⁰ from the viewpoint of preventing a decrease in luminance due to discoloration of the sealing material due to corrosive gas in the environment and corrosion of silver plated on the electrode or the substrate. R ¹¹ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and when R ¹¹ represents an aryl group, as the aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group , Anthracenyl group, phenanthryl group, pyrenyl group, and hydrogen atoms of these aryl groups are alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, or halogen atoms such as chlorine atom and bromine atom A substituted group is exemplified, preferably a phenyl group. When R ¹¹ represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. A group is exemplified, preferably a methyl group. R ¹² represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and when R ¹² represents an aryl group, as the aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group , Anthracenyl group, phenanthryl group, pyrenyl group, and hydrogen atoms of these aryl groups are alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group, or halogen atoms such as chlorine atom and bromine atom A substituted group is exemplified, preferably a phenyl group. When R ¹² represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. A group is exemplified, preferably a methyl group.

  Further, in the formula, d, e and f satisfy 0.01 ≦ d ≦ 0.5, 0.01 ≦ e ≦ 0.7, 0.1 ≦ f ≦ 0.9, and d + e + f = 1, respectively. A number, preferably 0.02 ≦ d ≦ 0.5, 0.1 ≦ e ≦ 0.6, 0.1 ≦ f ≦ 0.8, and d + e + f = 1, and more preferably 0.05 ≦ d ≦ 0.5, 0.2 ≦ e ≦ 0.6, 0.1 ≦ f ≦ 0.7, and d + e + f = 1. This is because when d is less than the lower limit of the above range, the strength of the cured product is not sufficiently obtained and the gas resistance of the cured product is lowered, while when it is greater than the upper limit of the above range, the cured product is It becomes brittle. When d is within the above range, the cured product has sufficient strength and the gas resistance of the cured product is good. When e is less than the lower limit value of the above range, the gas resistance of the cured product is lowered, and when it is larger than the upper limit value of the above range, the cured product becomes white and cloudy. When e is within the above range, the gas resistance of the cured product is good, and a transparent cured product is obtained. When f is less than the lower limit of the above range, the crack resistance of the cured product is reduced, and when it is greater than the upper limit of the above range, the gas resistance of the cured product is reduced. When f is within the above range, there is crack resistance, and the gas resistance of the cured product becomes high.

In addition, the organopolysiloxane of the component (B) may have a siloxane unit represented by SiO _{4/2 as long as} the object of the present invention is not impaired. The organopolysiloxane may have a silicon-bonded alkoxy group such as a methoxy group, an ethoxy group or a propoxy group, or a hydroxyl group bonded to a silicon atom, as long as the object of the present invention is not impaired.

As a method of synthesizing the organopolysiloxane of the component (B), for example,
General formula (IV): R ⁷ R ⁸ R ⁹ SiX ¹
A silane compound represented by
General formula (V): R ¹⁰ R ¹¹ Si (X ² ) ₂
Silane compounds represented by the general formula (VI): R ¹² ₂ Si (X ² ) ₂
And a method of causing a hydrolysis and condensation reaction in the presence of an acid or an alkali.

General formula (IV): R ⁷ R ⁸ R ⁹ SiX ¹
In a silane compound represented by the organopolysiloxane of the ^formula: is a raw material for introducing the siloxane units represented by _{^{R 7 R 8 R 9 SiO 1/2}} . In general formula (IV), R ⁷ represents a hydrogen atom, R ⁸ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and R ⁹ represents 6 to 20 carbon atoms An aryl group or an alkyl group having 1 to 12 carbon atoms is represented, and X ¹ represents an alkoxy group, an acyloxy group, a hydroxyl group or a —OSiR ⁷ R ⁸ R ⁹ group. When X ¹ represents an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. When X ¹ represents an acyloxy group, an acetoxy group is exemplified as the acyloxy group.

  Examples of such silane compounds include alkoxysilanes such as dimethylmethoxysilane, dimethylethoxysilane, methylphenylmethoxysilane and methylphenylethoxysilane, acetoxysilanes such as dimethylacetoxysilane and methylphenylacetoxysilane, dimethylhydroxysilane and methylphenylhydroxyl. Examples thereof include hydroxysilanes such as silane and 1,1,3,3-tetramethyldisiloxane.

General formula (V): R ¹⁰ R ¹¹ Si (X ² ) ₂
In a silane compound represented by the organopolysiloxane of the ^formula: is a raw material for introducing the siloxane units represented by ^R 10 ^{R 11} SiO _2/2. In formula (V), R ¹⁰ represents an aryl group having 6 to 20 carbon atoms or biphenylyl group, and R ¹¹ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, X ² represents an alkoxy group, an acyloxy group or a hydroxyl group. When X ² represents an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. When X ² represents an acyloxy group, an acetoxy group is exemplified as the acyloxy group.

  As such a silane compound, methylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylbiphenylyldimethoxysilane, methylbiphenylyldiethoxy Silane, alkoxybisilane such as phenylbiphenylyldimethoxysilane and phenylbiphenylyldiethoxysilane, methylphenyldiacetoxysilane, ethylphenyldiacetoxysilane, diphenyldiacetoxysilane, methylbiphenylyldiacetoxysilane, phenylbiphenylyldiacetoxysilane, etc. Acetoxysilane, methylphenyl dihydroxysilane, ethylphenyl dihydroxysilane, diphenyl dihydro Shishiran, methyl biphenylyl dihydroxysilane, hydroxy silanes and phenyl biphenylyl dihydroxysilane are exemplified.

General formula (VI): R ¹² ₂ Si (X ² ) ₂
The silane compound represented by these is a raw material for introduce | transducing the siloxane unit represented by Formula: R _< ¹² > _{2SiO2 / 2} to organopolysiloxane. In formula (VI), R ¹² represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and X ² represents an alkoxy group, an acyloxy group, or a hydroxyl group. When X ² represents an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. When X ² represents an acyloxy group, an acetoxy group is exemplified as the acyloxy group.

  As such silane compounds, alkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, acetoxysilanes such as dimethyldiacetoxysilane and diphenyldiacetoxysilane, dimethyldihydroxysilane, diphenyldihydroxy Examples are hydroxysilanes such as silanes.

  The organopolysiloxane of component (B) can be selected from silane compounds (IV), silane compounds (V), silane compounds (VI), and, if necessary, other silane compounds, cyclic silicone compounds or silane oligomers as acids. It is characterized in that it is obtained by hydrolysis / condensation reaction in the presence.

  Examples of the acid that can be used include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid, trifluoromethanesulfonic acid, and ion exchange resin.

R ^{4 of the} silane compound represented by the general formula (II) used in the synthesis of the linear organopolysiloxane of the component (A), and used in the synthesis of the linear organopolysiloxane of the component (B) At least one of R ¹⁰ of the silane compound represented by Formula (V) represents a biphenylyl group.

  In the above preparation method, an organic solvent can be used. Examples of the organic solvent that can be used include ethers, ketones, alcohols, acetates, aromatic hydrocarbons, aliphatic hydrocarbons, γ-butyrolactone, and a mixture of two or more of these. Preferred organic solvents include diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Examples are propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, γ-butyrolactone, pentane, hexane, heptane, toluene and xylene.

  In the above preparation method, it is preferable to add water or a mixed solution of water and an alcohol in order to accelerate the hydrolysis / condensation reaction of each component. As this alcohol, methanol, ethanol and isopropanol are preferable. The reaction is promoted by heating, and when an organic solvent is used, it is preferable to carry out the reaction at the reflux temperature.

  In the present composition, the content of the component (B) is such that the silicon-bonded hydrogen atoms in the component are in the range of 0.1 to 5 moles with respect to 1 mole of the alkenyl group in the component (A). Preferably, the amount is in the range of 0.5 to 2 moles. This is because if the content of the component (B) is less than the lower limit of the above range, the composition does not cure sufficiently, and if it is more than the above range, the heat resistance transparency of the cured product is adversely affected. The cured product gradually discolors in a high temperature state, and can not be used as a sealing material for LEDs. When the content is within the above range, the composition is sufficiently cured to exhibit sufficient resistance to sulfurization, and the reliability of the LED device produced using the composition of the present invention is improved.

  The component (C) is a hydrosilylation reaction catalyst for promoting the curing of the present composition, and examples thereof include a platinum-based catalyst, a rhodium-based catalyst and a palladium-based catalyst. In particular, the component (C) is preferably a platinum-based catalyst because it can significantly accelerate the curing of the present composition. Examples of the platinum-based catalyst include fine platinum powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenyl siloxane complex, platinum-olefin complex, platinum-carbonyl complex, and preferably platinum-alkenyl siloxane complex. is there.

  In the present composition, the content of the component (C) is an amount effective to accelerate the curing of the present composition. Specifically, since the content of the component (C) can sufficiently accelerate the curing reaction of the present composition, the content of the component (C) is 100 parts by mass in total of the components (A) and (B). The amount of the catalyst metal is preferably in the range of 0.000001 to 0.05 parts by mass, more preferably in the range of 0.000001 to 0.03 parts by mass, and particularly preferably 0. The amount is preferably in the range of 00000 to 0.01 parts by mass.

  In the present invention, it is preferable that the organopolysiloxane of the component (A) and the organopolysiloxane of the component (B) be both or one or two organopolysiloxanes having a biphenylyl group. When the organopolysiloxane having a biphenylyl group is included, the resistance to sulfurization of the cured product of the present composition is significantly improved.

  In the present invention, in order to improve the adhesion of the cured product to a substrate which is in the process of being cured, (D) an adhesion promoter may be contained. The component (D) is preferably an organosilicon compound having at least one alkoxy group bonded to a silicon atom in one molecule. As this alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group are exemplified, and a methoxy group is particularly preferable in terms of excellent adhesion with a substrate. Further, as a group other than an alkoxy group to be bonded to a silicon atom of this organosilicon compound, a substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogenated alkyl group, 3 -Glycidoxy alkyl group such as glycidoxypropyl group, 4-glycidoxybutyl group, epoxy such as 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group Epoxy group-containing monovalent organic group such as oxiranyl alkyl group such as cyclohexyl alkyl group, 4-oxiranyl butyl group, 8-oxiranyl octyl group, etc. Acrylic group-containing monovalent organic group such as 3-methacryloxypropyl group Groups and hydrogen atoms are exemplified. The organosilicon compound preferably has an alkenyl group bonded to a silicon atom or a hydrogen atom bonded to a silicon atom. In addition, it is preferable that the organic silicon compound has at least one epoxy group-containing monovalent organic group in one molecule, because it can impart good adhesion to various substrates. Examples of such organosilicon compounds include organosilane compounds, organosiloxane oligomers, and alkyl silicates. Examples of the molecular structure of this organosiloxane oligomer or alkyl silicate include linear, partially branched linear, branched, cyclic, and network-like, and in particular, linear, branched or network-like. Is preferred. As such organosilicon compounds, silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc., in one molecule A siloxane compound having at least one silicon-bonded alkenyl group or silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy group, a silane compound having at least one silicon-bonded alkoxy group, or a siloxane compound in one molecule Examples thereof include a mixture of a silicon atom-bonded hydroxyl group and a siloxane compound having at least one silicon atom-bonded alkenyl group, methyl polysilicate, ethyl polysilicate, and epoxy group-containing ethyl polysilicate.

  In the present composition, although the content of the component (D) is not limited, it adheres well to the substrate in contact during curing, so that the component (A), component (B), component (C) It is preferable to exist in the range of 0.01-10 mass parts with respect to a total of 100 mass parts of components.

  In the present invention, 3-butyn-2-ol, 2-methyl-3-butyn-2-ol, 1-pentyne-3-ol, 3,4-dimethyl-1-pentyne, and the like, as other optional components. -3-ol, 3-methyl-1-pentyn-3-ol, 3-ethyl-1-pentyn-3-ol, 1-heptin-3-ol, 5-methyl-1-hexyn-3-ol, 1 -Octin-3-ol, 4-ethyl-1-octin-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-ethyl-1-heptin-3-ol, 1-ethynyl-1 Alkyne compounds such as cyclohexanol, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5, 7-Tetrahexenyl cyclote Siloxane compound La siloxanes, may contain a reaction inhibitor benzotriazole. In the present composition, the content of the reaction inhibitor is not limited, but the range of 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of the components (A), (B) and (C) It is preferably inside.

In the present invention, a phosphor can be contained as another optional component. This phosphor is, for example, a yellow phosphor composed of an oxide-based phosphor, an oxynitride-based phosphor, a nitride-based phosphor, a sulfide-based phosphor, an acid sulfide-based phosphor, etc. widely used for LEDs. Red, green and blue light emitting phosphors. Oxide-based phosphors include yttrium, aluminum, garnet-based YAG green to yellow light-emitting phosphors including cerium ions, terbium including cerium ions, aluminum, TAG-based yellow light-emitting phosphors based on garnets, and cerium And silicate based green to yellow light emitting phosphors including europium ions. The oxynitride-based phosphor is exemplified by silicon including a europium ion, aluminum, oxygen, and a sialon-based red to green light-emitting phosphor based on nitrogen. Examples of the nitride-based phosphors include calcium, strontium, aluminum, silicon and europium-based, and cascading (CASN and S-CASN) red light-emitting phosphors based on nitrogen. The sulfide-based phosphor is exemplified by a ZnS-based green color-developing phosphor including copper ions and aluminum ions. The acid sulfide based phosphor is exemplified by Y ₂ O ₂ S based red light emitting phosphor including europium ion. These phosphors may be used alone or in combination of two or more. In the present composition, the content of the phosphor is not particularly limited, but is in the range of 1 to 20 parts by mass with respect to 100 parts by mass in total of the components (A), (B), and (C). Is preferred.

  The sealing material composition for LED of the present invention can contain an additive as needed in the range which does not impair the object and effect of the present invention other than the above-mentioned ingredient. As the additive, for example, an inorganic filler, an antioxidant, an ultraviolet light absorber, a heat light stabilizer, a dispersant, an antistatic agent, a polymerization inhibitor, an antifoamer, a solvent, an inorganic phosphor, a radical inhibitor, a surfactant Examples thereof include agents, conductivity imparting agents, pigments, dyes, metal deactivators, and various additives are not particularly limited.

  The organopolysiloxane of the component (A), the organopolysiloxane of the component (B), and the hydrosilylation reaction catalyst of the component (C) separately contain liquids containing one or more of these components. The LED encapsulant composition according to the present invention may be prepared by preparing a mixture of two or more liquids immediately before use. For example, the first liquid containing the organopolysiloxane of the component (A) and the second liquid containing the organopolysiloxane of the component (B) are separately prepared, and the first liquid and the first liquid are used immediately before use. The second liquid may be mixed to prepare a sealant composition for an LED according to the present invention. At least one of the first liquid and the second liquid contains the hydrosilylation reaction catalyst of the component (C). Preferably, the first solution contains a hydrosilylation reaction catalyst. Storage stability is improved by using two solutions as described above.

  The LED sealing material composition of the present invention can be cured by heating. The temperature for curing the sealing composition for an LED of the present invention is preferably about 80 ° C. to 200 ° C. The method of the heat treatment is not particularly limited, but can be exemplified by a method using a hot plate or an oven under an appropriate atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum.

  The LED sealing material composition of the present invention can be used for LED sealing. The LED element which can apply the sealing material composition for LED of this invention in particular is not restrict | limited. The method for applying the sealing material composition for an LED of the present invention to an LED element is not particularly limited. The LED sealing material composition of the present invention can be used, for example, as an optical lens other than for LED sealing.

  The properties of the cured product obtained from the sealing material composition for an LED of the present invention were measured as follows.

(Preparation of cured product)
In order to evaluate the heat-resistant transparency of the cured product obtained from the sealing material composition for LEDs, the sealing material composition for LEDs of the present invention is baked in an oven at 100 ° C. for 1 hour, then 150 ° C., 3 It baked for a time and produced the hardened | cured material of thickness 1 mm to an alkali free glass substrate. In order to evaluate the sulfidation resistance of the cured product obtained from the sealing material composition for LED, the sealing material composition for LED of the present invention is applied to an LED substrate provided with a silver-plated electrode, and 100 C. for 1 hour, and then baked at 150.degree. C. for 3 hours to fabricate an LED device.

(Heat resistance transparency test)
The UV-visible absorption spectrum of the obtained cured product was measured for transmittance of 1 mm in thickness at a wavelength of 450 nm using UV-3100PC manufactured by Shimadzu Corporation. After the measurement, the cured product was heated for 1000 hours in a convection oven (in air) set to a temperature of 150 ° C. The transmittance of the cured product after heating was measured, and when the transmittance was 90% or more, it was evaluated as having high transparency even after the heat treatment at the time of forming the cured product, and was regarded as “o”. Those having a transmittance of less than 90% and those broken in the course of the evaluation of the heat resistance transparency test were evaluated as having no heat resistance transparency and evaluated as "x".

(Sulfidation resistance test)
The manufactured LED device was placed in an oven under a sulfur atmosphere at 80 ° C., and after 24 hours, the silver-plated electrode was observed with a microscope. The case where no color change was observed on the silver-plated electrode was judged as “○”, and the case where the silver-plated electrode turned black was judged as “x”. Furthermore, when the sealing material composition for an LED is cured, if the cured product is uncured, if the cured product is cracked, or if the cured product is clouded, it is judged to be impossible to evaluate and judged as "-" did.

(Adhesion test)
After the sulfidation resistance test was performed, the cured product formed in the manufactured LED device was confirmed with a microscope. The cured product is evaluated as "剥離" as excellent in adhesion when peeling from the silver-plated electrode is not confirmed, and "X" as poor in adhesion when peeling is confirmed. When the LED encapsulant composition is evaluated, if the cured product is not cured, if the cured product is broken, or if the cured product is clouded, it is judged that evaluation is not possible, and "-" evaluated.

The following reagents were used in Preparation Examples and Examples.
Magnesium cutting piece (made by Kanto Chemical Co., Ltd.)
4-bromobiphenyl (made by Tokyo Chemical Industry Co., Ltd.)
Tetrahydrofuran (manufactured by Junsei Chemical Co., Ltd.)
Toluene (manufactured by Junsei Chemical Co., Ltd.)
Trifluoromethanesulfonic acid (made by Tokyo Chemical Industry Co., Ltd.)
Phenyltrimethoxysilane (made by Tokyo Chemical Industry Co., Ltd.)
Methyltrimethoxysilane (made by Tokyo Chemical Industry Co., Ltd.)
1,3-divinyl-1,1,3,3-tetramethyldisiloxane (made by Tokyo Chemical Industry Co., Ltd.)
Diphenyldimethoxysilane (made by Tokyo Chemical Industry Co., Ltd.)
Dimethyldimethoxysilane (made by Tokyo Chemical Industry Co., Ltd.)
1,1,3,3-Tetramethyldisiloxane (made by Tokyo Chemical Industry Co., Ltd.)
1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (manufactured by Sigma Aldrich)

  Hereinafter, the present invention will be described in more detail by way of production examples and examples. The present invention is not limited to the following production examples and examples.

<Production Example 1>
Synthesis of biphenylylphenyldimethoxysilane Into a 1 L reaction flask equipped with a condenser, 15.47 g (0.472 mol) of magnesium cuttings were charged, and air in the flask was replaced with nitrogen using a nitrogen balloon. A Grignard reagent was prepared by adding a mixture of 100.00 g (0.429 mol) of 4-bromobiphenyl and 382 g of tetrahydrofuran dropwise thereto at room temperature (approximately 23 ° C.) for 1 hour, and further stirring for 60 minutes. .
In a 2 L reaction flask, 93.57 g (0.472 mol) of phenyltrimethoxysilane and 191 g of tetrahydrofuran were charged, and air in the flask was replaced with nitrogen using a nitrogen balloon. The Grignard reagent was added dropwise thereto at room temperature for 30 minutes, and the mixture was further stirred at room temperature for 24 hours. From this reaction mixture, tetrahydrofuran was distilled off under reduced pressure using an evaporator. To the obtained residue, 500 g of hexane was added and stirred at room temperature for 60 minutes to extract solubles, and then insolubles were separated by filtration. To this insoluble matter, 500 g of hexane was again added, and the insoluble matter was similarly filtered off. The respective filtrates were mixed, and hexane was distilled off under reduced pressure using an evaporator to obtain a crude product. The crude product was distilled under reduced pressure to obtain 67.4 g (yield 49%) of the target biphenylylphenyldimethoxysilane.

<Production Example 2>
Synthesis of biphenylylmethyldimethoxysilane Into a 1 L reaction flask equipped with a condenser, 15.47 g (0.472 mol) of magnesium cuttings were charged, and the air in the flask was replaced with nitrogen using a nitrogen balloon. A Grignard reagent was prepared by adding a mixture of 100.00 g (0.429 mol) of 4-bromobiphenyl and 382 g of tetrahydrofuran dropwise thereto at room temperature (approximately 23 ° C.) for 1 hour, and further stirring for 60 minutes. .
In a 2 L reaction flask, 93.57 g (0.472 mol) of methyltrimethoxysilane and 191 g of tetrahydrofuran were charged, and air in the flask was replaced with nitrogen using a nitrogen balloon. The Grignard reagent was added dropwise thereto at room temperature for 30 minutes, and the mixture was further stirred at room temperature for 24 hours. From this reaction mixture, tetrahydrofuran was distilled off under reduced pressure using an evaporator. To the obtained residue, 500 g of hexane was added and stirred at room temperature for 60 minutes to extract solubles, and then insolubles were separated by filtration. To this insoluble matter, 500 g of hexane was again added, and the insoluble matter was similarly filtered off. The respective filtrates were mixed, and hexane was distilled off under reduced pressure using an evaporator to obtain a crude product. The crude product was distilled under reduced pressure to obtain 82.2 g (yield 76%) of the target biphenylylmethyldimethoxysilane.

Synthesis Example 1
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 103.36 g (0.40 mol) of biphenylylmethyldimethoxysilane, diphenyldimethoxysilane 122. After 19 g (0.50 mol) and 244 g of toluene were mixed, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and the low-boiling substance was removed by heating under reduced pressure from the resulting clear solution to obtain 199 g (yield: 98%) of organopolysiloxane (P-1).

Synthesis Example 2
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 103.36 g (0.40 mol) of biphenylylmethyldimethoxysilane, dimethyldimethoxysilane 60. After 11 g (0.50 mol) and 182 g of toluene were mixed, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and the low-boiling substance was removed from the resulting clear solution by heating under reduced pressure to obtain 138 g (yield: 98%) of organopolysiloxane (P-2).

Synthesis Example 3
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 128.18 g (0.40 mol) of biphenylylphenyldimethoxysilane, diphenyldimethoxysilane 122. After 19 g (0.50 mol) and 269 g of toluene were mixed, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and then the low-boiling substance was removed from the resulting clear solution by heating under reduced pressure to obtain 233 g (yield: 98%) of organopolysiloxane (P-3).

Synthesis Example 4
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 128.18 g (0.40 mol) of biphenylylphenyldimethoxysilane, and dimethyldimethoxysilane 60. After mixing 11 g (0.50 mol) and 207 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and the low-boiling substance was removed by heating under reduced pressure from the obtained clear solution to obtain 207 g (yield: 98%) of organopolysiloxane (P-4).

Synthesis Example 5
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 51.68 g (0.20 mol) of biphenylylmethyldimethoxysilane, biphenylylphenyldimethoxysilane After mixing 64.09 g (0.20 mol), 122.19 g (0.50 mol) of diphenyldimethoxysilane and 257 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. And heated to reflux for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and then the low-boiling substance was removed from the resulting clear solution by heating under reduced pressure to obtain 211 g (yield: 98%) of organopolysiloxane (P-5).

Synthesis Example 6
In a reaction vessel, 1.86 g (0.01 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 103.36 g (0.40 mol) of biphenylylmethyldimethoxysilane, diphenyldimethoxysilane 61. After mixing 09 g (0.25 mol), 30.06 g (0.25 mol) of dimethyldimethoxysilane and 226 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. It heated and refluxed for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and the low-boiling substance was removed by heating under reduced pressure from the obtained clear solution to obtain 180 g (yield: 98%) of organopolysiloxane (P-6).

Synthesis Example 7
In a reaction vessel, 55.92 g (0.30 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 77.52 g (0.30 mol) of biphenylylmethyldimethoxysilane, 61. diphenyldimethoxysilane 61. After mixing 09 g (0.25 mol), 30.06 g (0.25 mol) of dimethyldimethoxysilane and 225 g of toluene, 28.83 g (1.60 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. It heated and refluxed for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and then the low-boiling substance was removed by heating under reduced pressure from the resulting clear solution to obtain 184 g (yield: 98%) of organopolysiloxane (P-7).

Synthesis Example 8
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 25.84 g (0.10 mol) of biphenylyl methyldimethoxysilane, diphenyldimethoxysilane 97. After mixing 75 g (0.40 mol), 48.09 g (0.40 mol) of dimethyldimethoxysilane and 337 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. It heated and refluxed for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and then the low-boiling substance was removed by heating under reduced pressure from the resulting clear solution to obtain 146 g (yield: 98%) of organopolysiloxane (P-8).

Synthesis Example 9
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 180.87 g (0.70 mol) of biphenylylmethyldimethoxysilane, diphenyldimethoxysilane 36. After mixing 66 g (0.15 mol), 18.03 g (0.15 mol) of dimethyldimethoxysilane and 254 g of toluene, 36.04 g (2.00 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. It heated and refluxed for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and the low-boiling substance was removed by heating under reduced pressure from the resulting clear solution to obtain 204 g (yield: 98%) of organopolysiloxane (P-9).

Synthesis Example 10
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 32.05 g (0.10 mol) of biphenylylphenyldimethoxysilane, diphenyldimethoxysilane 97. After mixing 75 g (0.40 mol), 48.09 g (0.40 mol) of dimethyldimethoxysilane and 197 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. It heated and refluxed for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and then the low-boiling substance was removed by heating under reduced pressure from the resulting clear solution to obtain 152 g (yield: 98%) of organopolysiloxane (P-10).

Synthesis Example 11
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 224.32 g (0.70 mol) of biphenylylphenyldimethoxysilane, diphenyldimethoxysilane 36. After mixing 66 g (0.15 mol), 18.03 g (0.15 mol) of dimethyldimethoxysilane and 298 g of toluene, 36.04 g (2.00 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. It heated and refluxed for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and then the low-boiling substance was removed by heating under reduced pressure from the resulting clear solution to obtain 247 g (yield: 98%) of organopolysiloxane (P-11).

Synthesis Example 12
In a reaction vessel, 46.60 g (0.25 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 192.27 g (0.60 mol) of biphenylylphenyldimethoxysilane, diphenyldimethoxysilane 18. After mixing 33 g (0.075 mol), 9.02 g (0.075 mol) of dimethyldimethoxysilane and 229 g of toluene, 27.03 g (1.50 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. It heated and refluxed for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and then the low-boiling substance was removed from the resulting clear solution by heating under reduced pressure to obtain 191 g (yield: 98%) of organopolysiloxane (P-12).

Synthesis Example 13
In a reaction vessel, 9.32 g (0.05 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 64.09 g (0.20 mol) of biphenylylphenyldimethoxysilane, diphenyldimethoxysilane 18. After mixing 33 g (0.075 mol), 90.17 g (0.75 mol) of dimethyldimethoxysilane and 151 g of toluene, 34.24 g (1.90 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added. It heated and refluxed for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and the low-boiling substance was removed from the resulting clear solution by heating under reduced pressure to obtain 105 g (yield: 98%) of organopolysiloxane (P-13).

Synthesis Example 14
In a reaction vessel, 18.64 g (0.10 mol) of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 109.97 g (0.45 mol) of diphenyldimethoxysilane, 54.10 g of dimethyldimethoxysilane ( After mixing 0.45 mol) and 183 g of toluene, 34.24 g (1.90 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. Then, heating atmospheric pressure distillation was performed until it reached 85 ° C. Next, 0.056 g (1.0 mmol) of potassium hydroxide was added, heating under normal pressure distillation was performed until the reaction temperature reached 120 ° C., and the reaction was allowed to proceed at this temperature for 6 hours. After cooling to room temperature, 0.30 g (0.50 mmol) of acetic acid was added to carry out a neutralization reaction. The salt formed was separated by filtration, and the low-boiling substance was removed by heating under reduced pressure from the resulting clear solution to obtain 138 g (yield: 98%) of organopolysiloxane (P-14).

Synthesis Example 15
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 103.36 g (0.40 mol) of biphenylylmethyldimethoxysilane, 122.19 g (0.50 mol) of diphenyldimethoxysilane And 239 g of toluene are mixed, then 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added, and heating under atmospheric pressure distillation is performed until the reaction temperature reaches 120 ° C. Reaction for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 194 g (yield: 98%) of organopolysiloxane (P-15).

Synthesis Example 16
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 103.36 g (0.40 mol) of biphenylylmethyldimethoxysilane, 60.11 g (0.50 mol) of dimethyldimethoxysilane And, after mixing 177 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and heating and reflux were performed for 1 hour. The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 133 g (yield: 98%) of organopolysiloxane (P-16).

Synthesis Example 17
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 128.18 g (0.40 mol) of biphenylylphenyldimethoxysilane, 122.19 g (0.50 mol) of diphenyldimethoxysilane And, after mixing 264 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 218 g (yield: 98%) of organopolysiloxane (P-17).

Synthesis Example 18
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 128.18 g (0.40 mol) of biphenylylphenyldimethoxysilane, 60.11 g (0.50 mol) of dimethyldimethoxysilane After mixing 202 g of toluene and toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 157 g (yield: 98%) of organopolysiloxane (P-18).

Synthesis Example 19
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 51.68 g (0.20 mol) of biphenylylmethyldimethoxysilane, and 64.09 g (0. 20 mol), 122.19 g (0.50 mol) of diphenyldimethoxysilane and 220 g of toluene are mixed, then 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added, and the mixture is heated under reflux for 1 hour. Did. The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 175 g (yield: 98%) of organopolysiloxane (P-19).

Synthesis Example 20
In a reaction vessel, 1.34 g (0.010 mol) of 1,1,3,3-tetramethyldisiloxane, 103.36 g (0.40 mol) of biphenylylmethyldimethoxysilane, 61.09 g (0.25 mol) of diphenyldimethoxysilane After 30.06 g (0.25 mol) of dimethyldimethoxysilane and 196 g of toluene were mixed, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. The The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 151 g (yield: 98%) of organopolysiloxane (P-20).

Synthesis Example 21
In a reaction vessel, 40.03 g (0.30 mol) of 1,1,3,3-tetramethyldisiloxane, 77.52 g (0.30 mol) of biphenylylmethyldimethoxysilane, 61.09 g (0.25 mol) of diphenyldimethoxysilane After mixing 30.06 g (0.25 mol) of dimethyldimethoxysilane and 209 g of toluene, 28.83 g (1.60 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added, and the mixture is heated under reflux for 1 hour. The The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 169 g (yield: 98%) of organopolysiloxane (P-21).

Synthesis Example 22
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 25.84 g (0.10 mol) of biphenylylmethyldimethoxysilane, 97.75 g (0.40 mol) of diphenyldimethoxysilane After mixing 48.09 g (0.40 mol) of dimethyldimethoxysilane and 185 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. The The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 141 g (yield: 98%) of organopolysiloxane (P-22).

Synthesis Example 23
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 180.87 g (0.70 mol) of biphenylylmethyldimethoxysilane, 36.66 g (0.15 mol) of diphenyldimethoxysilane After mixing 18.03 g (0.15 mol) of dimethyldimethoxysilane and 249 g of toluene, 36.04 g (2.00 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added, and the mixture is heated under reflux for 1 hour. The The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 199 g (yield: 98%) of organopolysiloxane (P-23).

Synthesis Example 24
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 32.05 g (0.10 mol) of biphenylylphenyldimethoxysilane, 97.75 g (0.40 mol) of diphenyldimethoxysilane After mixing 48.09 g (0.40 mol) of dimethyldimethoxysilane and 191 g of toluene, 32.44 g (1.80 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. The The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to give 147 g (yield: 98%) of organopolysiloxane (P-24).

Synthesis Example 25
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 224.32 g (0.70 mol) of biphenylylphenyldimethoxysilane, 36.66 g (0.15 mol) of diphenyldimethoxysilane After mixing 18.03 g (0.15 mol) of dimethyldimethoxysilane and 292 g of toluene, 36.04 g (2.00 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added, and the mixture is heated under reflux for 1 hour. The The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 241 g (yield: 98%) of organopolysiloxane (P-25).

Synthesis Example 26
In a reaction vessel, 33.58 g (0.25 mol) of 1,1,3,3-tetramethyldisiloxane, 192.27 g (0.60 mol) of biphenylylphenyldimethoxysilane, 18.33 g (0.075 mol) of diphenyldimethoxysilane After mixing 9.02 g (0.075 mol) of dimethyldimethoxysilane and 216 g of toluene, 27.03 g (1.50 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added, and the mixture is heated under reflux for 1 hour. The The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 178 g (yield: 98%) of organopolysiloxane (P-26).

Synthesis Example 27
In a reaction vessel, 6.72 g (0.05 mol) of 1,1,3,3-tetramethyldisiloxane, 64.09 g (0.20 mol) of biphenylylphenyldimethoxysilane, 18.33 g (0.075 mol) of diphenyldimethoxysilane After mixing 90.17 g (0.75 mol) of dimethyldimethoxysilane and 149 g of toluene, 34.24 g (1.90 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid are added, and the mixture is heated under reflux for 1 hour. The The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 103 g (yield: 98%) of organopolysiloxane (P-27).

Synthesis Example 28
In a reaction vessel, 13.43 g (0.10 mol) of 1,1,3,3-tetramethyldisiloxane, 109.97 g (0.45 mol) of diphenyldimethoxysilane, 54.10 g (0.45 mol) of dimethyldimethoxysilane and toluene After mixing 177 g, 34.24 g (1.90 mol) of water and 0.75 g (5 mmol) of trifluoromethanesulfonic acid were added, and the mixture was heated under reflux for 1 hour. The reaction was heated under normal pressure until the reaction temperature reached 120 ° C., and the reaction was carried out at this temperature for 6 hours. It cooled to room temperature, added water and stirred. The aqueous layer was removed, and low-boiling substances were removed from the resulting clear solution by heating under reduced pressure to obtain 133 g (yield: 98%) of organopolysiloxane (P-28).

Example 1
Organopolysiloxane P-1 (10 g) which is the component (A), organopolysiloxane P-15 (10 g) which is the component (B) and 1,3-divinyl-1,1,3, which is the component (C) A 3-tetramethyldisiloxane complex (an amount such that platinum metal is contained in a weight unit of 10 ppm with respect to the entire composition) was mixed to obtain a sealing material composition for an LED.

Example 2
Organopolysiloxane P-2 (10 g) which is component (A), organopolysiloxane P-16 (10 g) which is component (B) and 1,3-divinyl-1,1,3, which is component (C) A 3-tetramethyldisiloxane complex (an amount such that platinum metal is contained in a weight unit of 10 ppm with respect to the entire composition) was mixed to obtain a sealing material composition for an LED.

Example 3
Organopolysiloxane P-3 (10 g) which is the component (A), organopolysiloxane P-17 (10 g) which is the component (B) and 1,3-divinyl-1,1,3, which is the component (C) A 3-tetramethyldisiloxane complex (an amount such that platinum metal is contained in a weight unit of 10 ppm with respect to the entire composition) was mixed to obtain a sealing material composition for an LED.

Example 4
Organopolysiloxane P-4 (10 g) which is the component (A), organopolysiloxane P-18 (10 g) which is the component (B) and 1,3-divinyl-1,1,3, which is the component (C) A 3-tetramethyldisiloxane complex (an amount such that platinum metal is contained in a weight unit of 10 ppm with respect to the entire composition) was mixed to obtain a sealing material composition for an LED.

Example 5
Organopolysiloxane P-5 (10 g) which is the component (A), organopolysiloxane P-19 (10 g) which is the component (B) and 1,3-divinyl-1,1,3, which is the component (C) A 3-tetramethyldisiloxane complex (an amount such that platinum metal is contained in a weight unit of 10 ppm with respect to the entire composition) was mixed to obtain a sealing material composition for an LED.

Example 6
Organopolysiloxane P-1 (10 g) which is component (A), organopolysiloxane P-28 (10 g) which is component (B) and 1,3-divinyl-1,1,3, which is component (C) A 3-tetramethyldisiloxane complex (an amount such that platinum metal is contained in a weight unit of 10 ppm with respect to the entire composition) was mixed to obtain a sealing material composition for an LED.

Example 7
Organopolysiloxane P-14 (10 g) as component (A), organopolysiloxane P-15 (10 g) as component (B) and 1,3-divinyl-1,1,3,3 as component (C) A 3-tetramethyldisiloxane complex (an amount such that platinum metal is contained in a weight unit of 10 ppm with respect to the entire composition) was mixed to obtain a sealing material composition for an LED.

Comparative Example 1
Organopolysiloxane P-14 (10 g) which is component (A), organopolysiloxane P-28 (10 g) which is component (B) and 1,3-divinyl-1,1,3,3 which is component (C) The composition was obtained by mixing 3-tetramethyldisiloxane complex (the amount by which platinum metal is 10 ppm by weight with respect to the entire composition).

The results are shown in Tables 1 and 2.

As shown in Table 1, all of the cured products obtained from the sealing material compositions for LEDs prepared in Examples 1 to 7 have heat-resistant transparency, high sulfuration resistance, and discoloration of the silver substrate is observed. It was not done. In addition, high adhesion to the LED substrate was shown.
On the other hand, as shown in Table 2, the cured products obtained from the composition prepared in Comparative Example 1 were not all satisfactory in heat resistance transparency, resistance to sulfurization and adhesion.
Specifically, in Comparative Example 1 in which a polyorganosiloxane containing no biphenylyl group was used, the sulfurization resistance was insufficient. Therefore, it was judged that it could not be used as a sealing agent composition for LED.

  From the above results, the sealing material composition for an LED according to the present invention has high heat resistance and high resistance to sulfidation, and therefore exhibits high adhesion to the LED substrate without corroding the silver-plated electrode of the LED substrate. It turned out that it is suitable as a sealing material of the LED element in LED device.

  The LED encapsulant composition according to the present invention has high heat resistance and high resistance to sulfurization, so it does not corrode the silver-plated electrode of the LED substrate and exhibits high adhesion to the LED substrate, thus the LED device It is suitable as a sealing material of the LED element in the above, or a silver electrode of a liquid crystal end portion or a protective agent of silver plating of a substrate.

Claims (6)

(A) A linear organopolysiloxane having three structural units represented by the following formula (1) and having at least two alkenyl groups bonded to a silicon atom in one molecule,
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ ₂ SiO _2/2 ) _c (1)
(Wherein, R ¹ represents an alkenyl group having 2 to 12 carbon atoms, R ² represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and R ³ represents a number of carbon atoms R 6 represents an aryl group of 6 to 20 or an alkyl group having 1 to 12 carbon atoms, R ⁴ represents an aryl group having 6 to 20 carbon atoms or biphenylyl group, and R ⁵ represents an aryl group having 6 to 20 carbon atoms or 2 R 12 represents an alkyl group having 1 to 12 carbon atoms, two R ⁶ each represent an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and a, b and c each represent 0. 01 ≦ a ≦ 0.5, 0.01 ≦ b ≦ 0.7, 0.1 ≦ c ≦ 0.9, and a + b + c = 1.
(B) A linear organopolysiloxane having three structural units represented by the following formula (2) and having at least two hydrogen atoms bonded to a silicon atom in one molecule,
(R ⁷ R ⁸ R ⁹ SiO _1/2 ) _d (R ¹⁰ R ¹¹ SiO _2/2 ) _e (R ¹² ₂ SiO _2/2 ) _f (2)
(Wherein, R ⁷ represents a hydrogen atom, R ⁸ represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and R ⁹ represents an aryl group having 6 to 20 carbon atoms or R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms, R ¹⁰ represents an aryl group having 6 to 20 carbon atoms, or biphenylyl group, R ¹¹ represents an aryl group having 6 to 20 carbon atoms or 1 to 12 carbon atoms And R ¹² represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and d, e and f each represent 0.01 ≦ d ≦ 0.5. , 0.01 ≦ e ≦ 0.7, 0.1 ≦ f ≦ 0.9, and d + e + f = 1.
And (C) a sealing material composition for an LED, comprising a hydrosilylation reaction catalyst, wherein at least one of R ⁴ in the formula (1) and R ¹⁰ in the formula (2) represents a biphenylyl group. Formula (1) R ⁴ in is a phenyl group or a biphenylyl group, LED encapsulating composition of claim 1. Formula (2) R ¹⁰ represents a phenyl group or a biphenylyl group, according to claim 1 or LED encapsulating composition of claim 2 in.   Furthermore, the sealing material composition for LED as described in any one of the Claims 1 thru | or 3 containing the (D) adhesion imparting agent.   A cured product obtained from the sealing material composition for an LED according to any one of claims 1 to 4.   The LED apparatus by which the LED element was sealed by the hardened | cured material of Claim 5.