TW201406863A - Polyorganometallosiloxane, curable polymer composition, cured product thereof, and optical semiconductor device - Google Patents

Abstract

A polyorganometallosiloxane comprising a metalloxy unit represented by general formula (1): M1Ox/2 (where M1 is an atom of group 4A or group 5A of the periodic table, and ''x'' is the valency of M1), a metalloxy unit represented by general formula (2): M2Oy/2 (where M2 is an atom of group 2A or group 2B of the periodic table, and ''y'' is the valency of M2), and an organosiloxane unit represented by general formula (3): R1aSiO(4-a)/2 (where R1 is an alkyl group, an alkenyl group, a phenyl group, an aralkyl group, or a hydrogen atom, and ''a'' is a number satisfying: 0 < a ≤ 3), and a curable polymer composition which contains this polyorganometallosiloxane and is cured by a hydrosilylation reaction to form a cured product with a high refractive index, high visible light transmittance, and excellent heat resistance and moisture resistance.

Description

Polyorganometalloxane, curable polymer composition, cured product thereof and optical semiconductor device

The present invention relates to a polyorganometalloxane, a curable polymer composition containing the polyorganometalloxane, a cured product of the composition, and an optical semiconductor device using the composition.

Materials having high refractive index and excellent long-term stability characteristics such as visible light transmittance, heat resistance, and moisture resistance are required in the industry as a sealant for optical semiconductor devices such as LEDs. The following composition has been proposed as the sealant: a resin composition comprising a _{polypyridoxane} resin mainly comprising a unit represented by R _m MO _(xm)/2 (wherein M is selected from the fourth to sixth cycles) An atom belonging to the group of atoms of Groups 2A to 5A of the periodic table, and R represents a group selected from a hydrogen atom, a hydroxyl group, an amine group or a substituted or unsubstituted aliphatic group, An alicyclic group, an aryl group, a heterocyclic group or a group bonded to a group of an M atom via an oxygen, x represents a valence of the M atom, and "m" represents an integer of 0 or 1 to x-1 (See Patent Document 1 below); and a curable composition comprising a formazanylated polymetalloxane having at least 2 alkenyl groups in the molecule, a hydrogen atom having at least 2 bonded ruthenium in the molecule and not A compound having a decane bond and a curing catalyst (see Patent Document 2 below).

However, such a sealant has a problem in that heat resistance and moisture resistance of the resulting cured product are insufficient, which causes discoloration of the cured product to cause discoloration or deterioration of mechanical strength under conditions of high temperature or high humidity. A problem also exists in that when attempting to increase the refractive index of the sealant, the cured product becomes hard and brittle, which results in insufficient stability and mechanical characteristics.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2000-235103A.

Patent Document 2: Japanese Unexamined Patent Application Publication No. 2009-173910A.

The object of the present invention is to provide a polyorganometalloxane having a high refractive index and excellent heat resistance, moisture resistance and compatibility with an organic polymer. Another object of the present invention is to provide a curable polymer composition which is cured by a hydrogenation reaction to form a cured product having a high refractive index and excellent visible light transmittance, heat resistance and moisture resistance. Another object of the present invention is to provide a cured product having a high refractive index and excellent visible light transmittance, heat resistance and moisture resistance. Still another object of the present invention is to provide a highly reliable optical semiconductor device using the curable polymer composition.

The polyorganometalloxane of the present invention contains a metal oxy unit represented by the following general formula (1): M ¹ O _x/2

(wherein M ¹ is an atom of Group 4A or Group 5A of the periodic table, and "x" is a valence of M ¹ ); a metal oxy unit represented by the following formula (2): M ² O _y/2

(wherein M ² is an atom of Group 2A or Group 2B of the periodic table, and "y" is a valence of M ² ); and an organic oxirane unit represented by the following formula (3): R ¹ _a SiO _{( 4-a)/2}

(wherein R ¹ is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a hydrogen atom, and "a" is satisfied: 0 < a 3 values).

Further, the curable polymer composition of the present invention contains the above polyorganometalloxane and is cured by a hydrogenation reaction.

Further, the cured product of the present invention is formed by curing a curable polymer composition.

Further, the optical semiconductor device of the present invention is formed by covering or sealing an optical semiconductor element with a cured product of the above-mentioned curable polymer composition.

Invention effect

The polyorganometalloxane of the present invention has a high refractive index and excellent heat resistance, moisture resistance and compatibility with an organic polymer. Further, the curable polymer composition of the present invention is cured by a hydrogenation reaction to form a cured product having a high refractive index and excellent visible light transmittance, heat resistance and moisture resistance. Further, the cured product of the present invention has a high refractive index and excellent visible light transmittance, heat resistance and moisture resistance. Further, the optical semiconductor device of the present invention exhibits excellent reliability.

1‧‧‧Polyphthalic acid (PPA) resin shell

2‧‧‧LED chip

3‧‧‧Internal leads

4‧‧‧bonding line

5‧‧‧Curing product of curable polymer composition

1 is a cross-sectional view of an LED of an example of an optical semiconductor device of the present invention.

First, the polyorganometalloxane of the present invention will be explained in detail.

The polyorganometalloxane of the present invention comprises a metal oxy unit represented by the formula (1): M ¹ O _x/2 , a metal oxy unit represented by the formula (2): M ² O _y/2 , and An organooxane unit represented by the formula (3): R ¹ _a SiO _(4-a)/2 .

The metal oxy unit represented by the formula (1) is a unit for increasing the refractive index of the polyorganometalloxane of the present invention. In the formula (1), M ¹ is an atom of Group 4A or Group 5A of the periodic table. In particular, M ¹ is an atom selected from atoms of Group 4A (eg, Ti, Zr, and Hf) or atoms of Group 5A (eg, V, Nb, and Ta), and is preferably Ti or Zr. In the general formula (1), "x" represents a valence of M ¹ , and its terminal differs depending on the atom type, and is an integer of 1 to 7. For example, the valence of Ti is 3 or 4, and the valence of Zr or Hf is 4.

The metal oxy unit represented by the formula (2) is a unit for improving the heat resistance and moisture resistance of the polyorganometalloxane of the present invention. In the formula (2), M ² is an atom of Group 2A or Group 2B of the periodic table. In particular, M ² is an atom selected from atoms of Group 2A (eg, Ca, Sr, and Ba) or atoms of Group 2B (eg, Zn, Cd, and Hg). In order to ensure excellent heat resistance, M ^{2 is} preferably Zn, Ca or Ba, and even more preferably Zn. In the general formula (2), "y" represents a valence of M ² , and its terminal differs depending on the atom type, and is an integer of 1 to 7. For example, the valence of Zn, Ca, and Ba is 2.

The organooxane unit represented by the formula (3) is a unit for improving the heat resistance, moisture resistance and compatibility with the organic polymer of the polyorganometalloxane of the present invention. In the formula (3), R ¹ is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a hydrogen atom. Examples of the alkyl group of R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these groups, a methyl group is preferred. Examples of the alkenyl group of R ^l include a vinyl group, an allyl group, and a butenyl group. Among these groups, preferred are vinyl groups. Examples of the aryl group of R ¹ include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, and an aryl group in which a hydrogen atom of the aryl group is substituted with an alkyl group such as a methyl group or an ethyl group; an alkoxy group, for example a methoxy or ethoxy group; or a halogen atom such as a chlorine atom or a bromine atom. Among these groups, preferred are phenyl and naphthyl groups. Examples of the aralkyl group of R ¹ include a naphthylethyl group, a naphthylpropyl group, a decylethyl group, a phenanthrylethyl group, a decylethyl group, and a hydrogen atom of an aralkyl group via an alkane such as a methyl group or an ethyl group. The aralkyl group is substituted; 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. Since the polyorganometalloxane of the present invention can have a hydrazine hydrogenation reactivity, it is preferably at least one R ¹ -alkenyl group or a hydrogen atom in the molecule.

In the general formula (3), "a" is satisfied: 0 < a The value of 3 is preferably satisfied: 1 < a A value of 3 such that the polyorganometalloxane has a large refractive index and improved compatibility with the organic polymer.

In the polyorganometalloxane of the present invention, the metal oxy unit represented by the formula (1), the metal oxy unit represented by the formula (2), and the oxirane unit represented by the formula (3) The respective content is not particularly limited, but the content of the metal oxy unit represented by the general formula (1) The ratio of the content of the oxoxane unit represented by the general formula (3) is preferably in the range of 0.01:1 to 99:1 and even more preferably in the range of 0.01:1 to 19:1. Further, the ratio of the content of the metal oxy unit represented by the general formula (2) to the content of the oxoxane unit represented by the general formula (3) is preferably in the range of 0.01:1 to 19:1 and is even better. The ground is in the range of 0.01:1 to 9:1. This is because when the content of the metal oxy unit represented by the general formula (1) is less than or equal to the lower limit of the above range, the refractive index of the polyorganometalloxane is lowered, and when the content is greater than or equal to the upper limit of the above range The compatibility of the polyorganometalloxane with the organic polymer is lowered. Further, when the content of the metal oxy unit represented by the general formula (2) is less than or equal to the lower limit of the above range, the heat resistance and moisture resistance of the polyorganometalloxane are lowered, and when the content is greater than or equal to the above range At the upper limit, the refractive index of the polyorganometalloxane is lowered and the compatibility with the organic polymer is lowered.

The method for producing the polyorganometalloxane of the present invention is not limited, but an example is a method in which the following is hydrolyzed together with a solvent (for example, water or an alcohol) and a condensation reaction is carried out: represented by the general formula (4) Metal compound M ¹ _b (X) _c

(wherein M ¹ is an atom of Group 4A or Group 5A of the periodic table, X is a hydroxyl group or a hydrolyzable group, and "b" and "c" satisfy: (the valence of M ¹ ) × b = (X The valence value) is a numerical compound represented by the general formula (5): M ² _d (Y) _e

(wherein M ² is an atom of Group 2A or Group 2B of the periodic table, Y is a hydrolyzable group, and "d" and "e" satisfy: (valence of M ² ) × d = (valence of Y) The value of ×e); and the organodecane compound represented by the general formula (6): R ¹ _a SiZ _(4-a)

(wherein R ¹ is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a hydrogen atom, a Z-based hydroxyl group or a hydrolyzable group, and "a" is satisfied: 0 < a 3 values).

In the general formula (4), the M ¹ is an atom of Group 4A or Group 5A of the periodic table, and examples thereof are the same as those of the above atoms. In the formula (4), an X-based hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group of X include alkoxy groups such as methoxy group and ethoxy group; alkenyloxy group such as isopropenyloxy group; decyloxy group such as ethoxy group; halogen group such as chlorine and bromine Sulfate group; (organic) sulfonic acid group, such as methanesulfonic acid group and tridecylbenzylsulfonic acid group; phosphoric acid group, (organo)phosphonic acid group and nitric acid group. In the general formula (4), "b" and "c" are values satisfying the following conditions: (valence of M ¹ ) × b = (valence of X) × c.

Examples of the metal compound represented by the general formula (4) include, but are not limited to, zirconium hydroxide, cesium hydroxide, cesium hydroxide, titanium alkoxide, zirconium alkoxide, cerium alkoxide, vanadium alkoxide, cerium alkoxide. , alkoxide, titanium acetate, zirconium acetate, barium acetate, vanadium acetate, barium acetate, barium acetate, zirconium methacrylate, titanium chloride, zirconium chloride, barium chloride, vanadium chloride, barium chloride, chlorination Barium, titanium sulfate, zirconium sulfate, vanadium sulfate, zirconium nitrate, cerium nitrate, cerium nitrate, titanium methanesulfonate, tridecylbenzyl titanium, titanium phosphate and titanium phosphonate.

In the general formula (5), the atom of Group 2A or Group 2B of the M ² periodic table, examples of which are the same atoms as those of the above atoms. In the formula (5), a Y-based hydrolyzable group, an example of which is the same hydrolyzable group as the above-mentioned hydrolyzable groups of X. In the general formula (5), "d" and "e" are values satisfying the following conditions: (valence of M ² ) × d = (valence of Y) × e.

Examples of the metal compound represented by the general formula (5) include, but are not limited to, calcium hydroxide, barium hydroxide, barium hydroxide, zinc hydroxide, cadmium hydroxide, calcium acetate, barium acetate, barium acetate, zinc acetate. , cadmium acetate, mercury acetate, calcium acetonate, acetonacetone oxime, acetoacetone oxime, calcium chloride, barium chloride, barium chloride, zinc chloride, cadmium chloride, mercury chloride, calcium nitrate, nitric acid Antimony, cerium nitrate, zinc nitrate, cadmium nitrate and mercury nitrate.

In the formula (6), R ¹ is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a hydrogen atom, and examples thereof are the same as those of the above-mentioned groups. In the formula (6), a Z-based hydroxyl group or a hydrolyzable group is exemplified by the same hydrolyzable group as the above-mentioned X hydrolyzable groups. In the general formula (6), "a" is 0 < a 3 values in the range.

Examples of the organodecane compound represented by the general formula (6) include, but are not limited to, trimethylmethoxydecane, trimethylethoxydecane, vinyldimethylmethoxydecane, and vinyl dimethicone. Ethoxy decane, diphenylmethyl methoxy decane, diphenylmethyl ethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl vinyl dimethyl Oxy decane, methyl vinyl diethoxy decane, methyl phenyl dimethoxy decane, methyl phenyl diethoxy decane, methyl chloro propyl dimethoxy decane, methyl trimethoxy Decane, ethyltrimethoxydecane, vinyltrimethoxydecane, phenyltrimethoxydecane, chloropropyltrimethoxydecane, 1-naphthyltrimethoxydecane,vinyldimethylnonanol and diphenyl Methyl decyl alcohol.

In the above production method, the amount of the metal compound represented by the formula (4), the metal compound represented by the formula (5), and the organodecane compound represented by the formula (6) is not limited, but Preferably, the metal oxy unit represented by the formula (1), the metal oxy unit represented by the formula (2), and the oxirane unit represented by the formula (3) are in the obtained polyorganometalloxane. The amount is in the range of the above range.

Further, in the above production method, the hydrolysis is carried out at room temperature or under heat, but from the viewpoint of the reaction rate, it is preferred to add an acid or a base as a catalyst. Examples of useful acids include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, and phosphoric acid. Further, examples of the usable base include organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, aqueous ammonia, tetramethylammonium hydroxide, alkoxydecane having an amine group, and aminopropyl group. Trimethoxydecane.

Next, the curable polymer composition of the present invention will be explained in detail.

The curable polymer composition of the present invention contains the above polyorganometalloxane and is cured by a hydrogenation reaction. Examples of the curable polymer composition include: (A) an organopolyoxyalkylene having at least 2 alkenyl groups in the molecule; (B) a hydrogen atom having at least 2 bonded fluorenes in the molecule. An organopolyoxane; (C) a hydrogenation reaction catalyst; and (D) a polyorganometalloxane comprising a metal oxy unit represented by the following formula (1): M ¹ O _x/2

(wherein M ¹ is an atom of Group 4A or Group 5A of the periodic table, and "x" is a valence of M ¹ ); a metal oxy unit represented by the following formula (2): M ² O _y/2

(wherein M ² is an atom of Group 2A or Group 2B of the periodic table, and "y" is a valence of M ² ); and an organic oxirane unit represented by the following formula (3): R ¹ _a SiO _{( 4-a)/2}

(wherein R ¹ is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a hydrogen atom, and "a" is satisfied: 0 < a 3 values).

Component (A) is an organopolyoxane having at least 2 alkenyl groups in the molecule. Examples of the alkenyl group in the component (A) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group. Among these groups, preferred are vinyl groups. Examples of the group bonded to the halogen atom other than the alkenyl group in the component (A) include an alkyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these groups, a methyl group is preferred. Examples of the aryl group include the aryl group in which a hydrogen atom of a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group and an aryl group 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. Among these groups, preferred are phenyl and naphthyl groups. Fang Examples of the alkyl group include a naphthylethyl group, a naphthylpropyl group, a decylethyl group, a phenanthrylethyl group, a decylethyl group, and a hydrogen atom of an aralkyl group substituted with an alkyl group such as a methyl group or an ethyl group. An aralkyl 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. From the viewpoint of the objective of increasing the refractive index of the component (A), the component (A) preferably has an aryl group or an aralkyl group, and even more preferably has a group other than the alkenyl group in the component (A). A phenyl or naphthyl group serves as a group bonded to a ruthenium atom.

Examples of the component (A) include an organopolyfluorene unit represented by the general formula: R' ₃ SiO _1/2 and an organic polyfluorene represented by the general formula: R'R"SiO _2/2 . Oxyalkane; comprising a oxoxane unit represented by the formula: R' ₃ SiO _1/2 and a decane represented by the formula: R'R"SiO _2/2 and the formula: R' ₂ SiO _2/2 a unit of an organopolyoxane; comprising a fluorinated alkane unit represented by the formula: R' ₂ R"SiO _1/2 and an organopoly unit represented by the formula: R' ₂ SiO _2/2 Oxystane; comprising a oxoxane unit represented by the formula: R' ₂ R"SiO _1/2 , a oxoxane unit represented by the formula: R' ₂ SiO _2/2 and a formula: R'R" An organopolyoxane of a oxoxane unit represented by SiO _2/2 ; comprising a fluorinated alkane unit represented by the formula: R' ₂ R"SiO _{1/2 and} represented by the formula: R'SiO _3/2 An organopolyoxane of a oxoxane unit; comprising a fluorinated alkane unit represented by the general formula: R' ₃ SiO _1/2 and an organic polyfluorene represented by the general formula: R"SiO _3/2 oxyalkyl; comprises the formula: Si siloxane units R "SiO _3/2 and represented by the general formula of:: silicon siloxane units R _'3 SiO _1/2 of represented by the general formula R'SiO _3/2 Silicon Silicon organopolysiloxane alumoxane the alumoxane shows the unit; comprises the formula: 'Silicon siloxane units ₂ R "SiO _1/2 of represented by the general formula: R' R ₂ SiO _2/2 siloxane represents of silicon a unit and an organopolyoxane of the oxirane unit represented by the formula: R'SiO _3/2 ; comprising a oxoxane unit represented by the formula: R' ₂ R"SiO _1/2 , by the formula: a fluorinated alkane unit represented by R' ₂ SiO _2/2 and an organopolyoxyalkylene represented by the formula: R'SiO _3/2 ; comprising the formula: R'R"SiO _2/2 a oxoxane unit and an organopolyoxane represented by the formula: R'SiO _3/2; and a oxoxane unit represented by the formula: R' ₂ R"SiO _1/2 An organopolyoxane of the oxirane unit represented by the formula: SiO _4/2 ; comprising a oxoxane unit represented by the formula: R' ₃ SiO _1/2 , of the formula: R' ₂ R"SiO _{1 a} oxoxane unit represented by _/2 and an organopolyoxane of the oxirane unit represented by the formula: SiO _4/2 ; and a mixture of two or more types thereof. In the above formula, the R' system An alkyl group, an aryl group or an aralkyl group, examples of which are the same groups as the above-mentioned groups. In the above formulas, R" Alkenyl group, examples of the above-described system the same groups their group.

Component (B) is an organopolyoxane having at least two hydrogen atoms bonded to the molecule in the molecule. Examples of the group bonded to the halogen atom other than the hydrogen atom in the component (B) include an alkyl group, an aryl group and an aralkyl group, and examples thereof are the same groups as the above-mentioned groups. From the viewpoint of the objective of increasing the refractive index of the component (B), the component (B) preferably has an aryl group or an aralkyl group, and even more preferably has a hydrogen atom other than the hydrogen atom in the component (B). A phenyl or naphthyl group serves as a group bonded to a ruthenium atom.

Examples of the component (B) include an organopolyoxane unit represented by the general formula: R' ₃ SiO _1/2 and an oxoxane unit represented by the formula: R'HSiO _2/2 . a polyoxane unit represented by the formula: R' ₃ SiO _1/2 and an organopoly group represented by the formula: R'HSiO _2/2 and a fluorinated alkane unit represented by the formula: R' ₂ SiO _2/2 a siloxane comprising: a fluorinated alkane unit represented by the formula: R' ₂ HSiO _1/2 and an organopolyoxyalkylene represented by the formula: R' ₂ SiO _2/2 ; Formula: R' ₂ HSiO _1/2 represents a oxoxane unit, a oxirane unit represented by the formula: R' ₂ SiO _2/2 and a fluoran oxide unit represented by the formula: R'HSiO _2/2 An organopolyoxane; comprising a oxoxane unit represented by the general formula: R' ₂ HSiO _1/2 and an organopolyoxyalkylene represented by the oxirane unit represented by the formula: R'SiO _3/2 ; a oxoxane unit represented by the general formula: R' ₃ SiO _1/2 and an organopolyoxyalkylene represented by the oxirane unit represented by the formula: HSiO _3/2 ; including the general formula: R' ₃ SiO _{1/ 2} is a oxoxane unit, a oxoxane unit represented by the formula: HSiO _{3/2 and} represented by the formula: R'SiO _3/2 An organopolyoxane of a oxoxane unit; comprising a oxoxane unit represented by the formula: R' ₂ HSiO _1/2 , a oxoxane unit represented by the formula: R' ₂ SiO _2/2 An organopolyoxane of the oxoxane unit represented by R'SiO _3/2 ; comprising a oxoxane unit represented by the formula: R'HSiO _{2/2 and} represented by the formula: R'SiO _3/2 An organopolyoxane of a oxoxane unit; comprising a oxoxane unit represented by the formula: R' ₂ HSiO _1/2 and an organopolyoxyalkylene represented by the oxime unit represented by the formula: SiO _4/2 ; The invention includes a oxoxane unit represented by the general formula: R' ₃ SiO _1/2 , a fluoran oxide unit represented by the formula: R' ₂ HSiO _1/2 and a siloxane unit represented by the formula: SiO _4/2 . An organopolyoxane; a mixture of two or more types thereof. In the above formulae, R' is an alkyl group, an aryl group or an aralkyl group, and examples thereof are the same groups as the above-mentioned groups.

Component (C) is a hydrogenation reaction catalyst, and specific examples thereof include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Component (C) is preferably based on a platinum catalyst so that the curing of the composition of the invention can be significantly accelerated. Examples of platinum-based catalysts include platinum fine powder, hydrochloroplatinic acid, an alcohol solution of chloroplatinic acid, a platinum-alkenyl alkoxylate complex, a platinum-olefin complex, and a platinum-carbonyl complex. More preferably, it is a platinum-alkenyl alkoxylate complex.

Component (D) contains a metal oxy unit represented by the general formula (1): M ¹ O _x/2 , a metal oxy unit represented by the general formula (2): M ² O _y/2 , and a general formula (3): Polyorganometalloxane of an organooxane unit represented by R ¹ _a SiO _(4-a)/2 . Component (D) is as described above. When component (D) is a polyorganometalloxane of at least one R ¹ alkenyl group in the molecule, component (D) may undergo a hydrazine hydrogenation reaction with a hydrogen atom bonded to the group in (B). When component (D) is a polyorganometalloxane of at least one R ¹ -based hydrogen atom in the molecule, component (D) may undergo a hydrazine hydrogenation reaction with the alkenyl group in component (A).

The content of the component (B) is not particularly limited, but when the component (D) does not contain an alkenyl group and a hydrogen atom bonded to the oxime, the content is preferably such that the bond in the component (B) is 矽The hydrogen atom is in an amount ranging from 0.2 mol to 5 mol and even more preferably from 0.5 mol to 2 mol, relative to the total of 1 mol of the alkenyl group in the component (A). When the component (D) has an alkenyl group, the content is preferably such that the hydrogen atom bonded to the oxime in the component (B) is a total of 1 mol of the olefin in the component (A) and the component (D). The amount is in the range of from 0.2 mol to 5 mol and even more preferably in the range of from 0.5 mol to 2 mol. Further, when the component (D) has a hydrogen atom bonded to ruthenium, the content is preferably such that the total hydrogen atom of the bonded ruthenium in the component (B) and the component (D) is relative to the component (A) a total of 1 mol of alkenyl in the range of 0.2 mol to 5 mol and even more preferably 0.5 mol to Amount within the range of 2 mol. This is because when the content of the component (B) is greater than or equal to the lower limit of the above range, the curing of the obtained composition becomes sufficient, and when the content is less than or equal to the upper limit of the above range, the physical properties of the obtained cured product are improved. .

The content of the component (C) is not particularly limited as long as the curing of the composition can be accelerated. In particular, the content is preferably such that the catalytic metal in the component (C) is in the range of 0.01 ppm to 500 ppm, more preferably in the range of 0.01 ppm to 100 ppm, by weight, relative to the composition, and Even more preferably in an amount ranging from 0.01 ppm to 50 ppm.

The content of the component (D) is not particularly limited, but it is preferably from 1 wt.% to 99 wt.% of the total amount of the component (A), the component (B) and the component (D) and even more Preferably 10%.% to 90wt.%. This is because when the content of the component (D) is less than the lower limit, the refractive index is insufficient, and when the content is more than the upper limit, the resulting cured product becomes brittle.

An example of another curable polymer composition of the present invention is a curable polymer composition comprising: (E) a polyorganometalloxane comprising a metal oxy unit represented by the following general formula (1) :M ¹ O _x/2

(wherein M ¹ is an atom of Group 4A or Group 5A of the periodic table, and "x" is a valence of M ¹ ); a metal oxy unit represented by the following formula (2): M ² O _y/2

(wherein M ² is an atom of Group 2A or Group 2B of the periodic table, and "y" is a valence of M ² ); and an organic oxirane unit represented by the following formula (3): R ¹ _a SiO _{( 4-a)/2}

(wherein R ¹ is an alkyl group, an alkenyl group, an aromatic group-containing group or a hydrogen atom, and "a" is satisfied: 0 < a a value of 3); wherein at least two R ¹ are alkenyl groups in the molecule; (B) an organopolyoxyalkylene having at least 2 hydrogen groups bonded to the molecule; and (C) a hydrogenation reaction catalyst.

Component (E) includes a metal oxy unit represented by the general formula (1): M ¹ O _x/2 , a metal oxy unit represented by the general formula (2): M ² O _y/2 , and a general formula (3): Polyorganometalloxane of an organooxane unit represented by R ¹ _a SiO _(4-a)/2 , wherein at least two R ¹ -alkenyl groups in the molecule. Component (E) is as described above. Since component (E) has at least two alkenyl groups in the molecule, component (E) can undergo a hydrogenation reaction with a hydrogen atom bonded to the group in component (B).

Component (B) is an organopolyoxyalkylene having at least two hydrogen atoms bonded to the molecule in the molecule, examples of which are the same as those of the above examples.

Component (C) is a hydrogenation reaction catalyst, and examples thereof are the same as those of the above examples.

The content of the component (B) is not particularly limited, but it is preferably such that the hydrogen atom of the bonded oxime in the component is in the range of 0.2 mol to 5 mol with respect to 1 mol of the alkenyl group in the component (E). Within and even more preferably in an amount ranging from 0.5 mol to 2 mol. This is because when the content of the component (B) is greater than or equal to the lower limit of the above range, the curing of the obtained composition becomes sufficient, and when the content is less than or equal to the upper limit of the above range, the physical properties of the obtained cured product are improved. .

The content of the component (C) is not particularly limited as long as the curing of the composition can be accelerated. In particular, the content is preferably such that the catalytic metal in the component (C) is in the range of 0.01 ppm to 500 ppm, more preferably in the range of 0.01 ppm to 100 ppm, by weight, relative to the composition, and Even more preferably in an amount ranging from 0.01 ppm to 50 ppm.

The curable polymer composition of the present invention may also contain (F) a phosphor as another optional component. Examples of this component (F) include yellow, red, green, and blue light-emitting phosphors widely used in light-emitting diodes (LEDs), such as oxide phosphors, oxynitride phosphors, nitride phosphors, A mixture of a sulfide phosphor, an oxysulfide phosphor, and two or more types of such phosphors. Examples of oxide phosphors include YAG green to yellow luminescent phosphors based on yttrium, aluminum and garnet containing cerium ions, TAG yellow luminescent phosphors based on cerium, aluminum and garnet containing cerium ions, and cerium or lanthanum containing cerium or lanthanum The green to yellow citrate luminescent phosphor of the ion. Examples of oxynitride phosphors include red to green sialon luminescent phosphors based on cerium, aluminum, oxygen and nitrogen containing cerium ions. Examples of nitride phosphors include CASN red luminescent phosphors based on calcium, cerium, aluminum, cerium and nitrogen containing cerium ions. Examples of the sulfide phosphor include a ZnS-based green phosphor containing copper ions or aluminum ions. Examples of the oxysulfide phosphor include a Y ₂ O ₂ S-based red light-emitting phosphor containing barium ions.

The content of the component (F) is not particularly limited, but it is preferably in the range of from 0.1 wt.% to 70 wt.% and even more preferably from 1 wt.% to 20 wt.% in the composition.

The curable polymer composition of the present invention may also contain a tackifier for improving the adhesion of the composition. An organic ruthenium compound having at least one alkoxy group bonded to a ruthenium atom in the molecule is suitable as the tackifier. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group. Among these groups, a methoxy group is preferred. Examples of the group other than the alkoxy group bonded to the ruthenium atom in the organic ruthenium compound include a substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group and a halogenated alkyl group; A monovalent organic group containing an epoxy group, such as 3-glycidoxypropyl, 4-glycidoxybutyl or a similar glycidoxyalkyl group; 2-(3,4-epoxycyclohexyl) Ethyl, 3-(3,4-epoxycyclohexyl)propyl or similar epoxycyclohexylalkyl; 4-oxiranylbutyl, 8-oxiranyloctyl or similar ring An oxyethanealkyl group; a monovalent organic group containing an acrylic group, such as 3-methylpropenyloxypropyl; and a hydrogen atom. The organic ruthenium compound preferably has a hydrogen atom bonded to an alkenyl group or a bonded ruthenium. The organogermanium compound also preferably has at least one monovalent organic group containing an epoxy group in the molecule to allow good adhesion to various base materials. Examples of the organic ruthenium compound include organic decane compounds, organic A siloxane oligomer and an alkyl phthalate. Examples of the molecular structure of the organic siloxane oxide oligomer or alkyl phthalate include a linear structure, a partially branched linear structure, a branched structure, a cyclic structure, and a network structure. Among these structures, a preferred one is a linear, branched, and network structure. Examples of the organic phosphonium compound include a decane compound such as 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and 3-methylpropene oxime. a oxypropyltrimethoxydecane; a mixture of the following compounds: a oxoxane compound having at least one of a hydrogen atom bonded to hydrazine or a hydrogen atom bonded to hydrazine in the molecule and an alkoxy group bonded to hydrazine; a at least one alkoxy group-containing decane compound or a decane compound and a siloxane compound having at least one of a hydrazine having a bonded hydrazine and a hydrazine bonded in the molecule; a polymethyl phthalate Polyethyl phthalate; and polyethyl phthalate containing an epoxy group.

The content of the tackifier is not particularly limited, but it is preferably in the range of 0.01 part by weight to 10 parts by weight per 100 parts by weight of the total composition.

For example, the following reaction inhibitors may be included as optional components in the curable polymer composition of the present invention: an alkynol such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1 -hexyn-3-ol or 2-phenyl-3-butyn-2-ol; an enyne compound such as 3-methyl-3-penten-1-yne or 3,5-dimethyl-3 -hexene-1-yne; or 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, 1,3,5,7-tetramethyl- 1,3,5,7-tetrahexenylcyclotetraoxane or benzotriazole.

The content of the reaction inhibitor is not limited, but it is preferably 0.0001 part by weight to 5 parts by weight per 100 parts by weight of the composition of the invention.

The following ingredients may be included as an optional component in the curable polymer composition of the present invention in an amount which does not impair the object of the present invention: an inorganic filler such as ceria, glass, alumina or zinc oxide; polymethacrylate Resin and the like; fine powder of organic resin; heat resistant agent, dye, pigment, flame retardant, solvent and the like.

The curable polymer composition of the present invention allows curing to be carried out at room temperature or under heating, but it is preferred to heat the composition to achieve rapid curing. The heating temperature is preferably 50 ° C to 200 ° C.

The curable polymer composition of the present invention can be used as an adhesive, a potting agent, a protective agent, a coating agent, an underfill for electrical/electronic applications, or as a molding. Specifically, the composition is particularly suitable as an adhesive, a potting agent, a protective agent, a coating agent, an underfill for a semiconductor element used in optical applications due to a high optical transmittance of the composition, and is used for a molding of a lens, or the like.

Next, the cured product of the present invention will be explained in detail.

The cured product of the present invention is formed by curing a curable polymer composition. The shape of the cured product of the present invention is not particularly limited, and the cured product can be disposed to a state in which the cured product covers or seals the optical semiconductor element or the like. Further, the cured product of the present invention can be disposed as an independent product, and examples thereof include a tabular product and a film-like product.

The optical semiconductor device of the present invention will now be explained in detail.

The device is characterized in that the optical semiconductor element is covered or sealed by the cured product of the above curable polymer composition. An example of such an optical semiconductor component is a light emitting diode (LED) wafer. Examples of the optical semiconductor device include a light emitting diode (LED), an optical coupler, and a CCD.

Fig. 1 shows a cross-sectional view of a surface mount type LED which is an example of the optical semiconductor device of the present invention. In the LED illustrated in FIG. 1, the LED chip 1 is die bonded to the lead frame 2, and the LED chip 1 and the lead frame 3 are bonded by wire bonding wires. This LED wafer 1 is covered by the cured product 5 of the above curable polymer composition.

An example of a method of producing the surface mount type LED illustrated in FIG. 1 is a method of bonding an LED chip 1 to a lead frame 2, bonding the LED chip 1 and the lead frame 3 by a gold bonding wire 4, and the above The cured polymer composition is applied to the LED wafer 1, and then the composition is cured by heating at 50 ° C to 200 ° C.

Instance

The polyorganometalloxane, the curable polymer composition, the cured product, and the optical semiconductor device of the present invention will be explained in further detail using practical examples. The characteristics of the polyorganometalloxane, the curable polymer composition, and the cured product are measured as follows. In a practical example, Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and Naph represents a naphthyl group.

Refractive index of polyorganometalloxane: polyorganometalloxane is dissolved by polyphenylmethyloxane (viscosity at 25 ° C, refractive index: 1.545) to achieve the desired concentration (% by volume), and The refractive index is calculated from the refractive index of the mixture.

Appearance of the cured product: The transparency of the cured product was confirmed by visual inspection.

Refractive index of the cured product: The refractive index of the cured product was measured using a 稜鏡-coupled method. A 632.8 nm laser source was used for the measurement.

Heat resistance of cured product: Appearance was confirmed after the cured product was allowed to stand in an oven at 150 ° C for 100 hours.

Moisture resistance of cured product: Appearance was confirmed by allowing the cured product to stand in a constant temperature, high humidity oven (85 ° C, relative humidity: 85%) for one week.

Reference example 1

First, 10 g (40.3 mmol) of 1-naphthyltrimethoxynonane, 2.7 g (26.4 mmol) of vinyl dimethyl decyl alcohol, 5.8 g (27.1 mmol) of diphenylmethyl decyl alcohol, 20 g of toluene, and 0.04 g (0.71 mmol) potassium hydroxide was loaded into the reaction vessel and heated to reflux for one hour. Then, the mixture was cooled to room temperature, and a mixture of 1.2 g (66.6 mmol) of water and 10 g of methanol was added. Distill the mixture under normal pressure while heating until the reaction temperature reaches The mixture was allowed to react at this temperature for 2 hours at 120 °C. The mixture was then cooled to room temperature, and a neutralization reaction was carried out by adding 0.08 g (1.3 mmol) of acetic acid. After the resulting salt was filtered off, the low-boiling substance was removed from the resulting clear solution under reduced pressure while heating, and 14.3 g of a colorless, clear, viscous liquid was obtained (yield: 94%).

As a result of NMR analysis, the organic polyoxane represented by the following average unit formula was determined: (ViMe ₂ SiO _1/2 ) _0.28 (Ph ₂ MeSiO _1/2 ) _0.28 (NaphSiO _3/2 ) _0.44

The organic polyoxyalkylene had a weight average molecular weight (Mw) of 1,000, a degree of dispersion (Mw/Mn) of 1.05, and a refractive index of 1.603.

Reference example 2

First, 10 g (40.3 mmol) of 1-naphthyltrimethoxynonane, 4.2 g (13.5 mmol) of 1,3-divinyl-1,3-diphenyldimethyldioxane and 20 g of toluene were loaded to The reaction vessel was premixed and charged with 2.2 g (122.1 mmol) of water and 10 g of methanol. Then, 0.069 g (0.46 mmol) of trifluoromethanesulfonic acid was charged while stirring and heating under reflux for 2 hours. Then, the mixture was distilled under normal pressure while heating until the temperature reached 85 ° C, and the mixture was allowed to react at this temperature for 1 hour. Then, 0.06 g (1.1 mmol) of potassium hydroxide was loaded. The mixture was distilled under normal pressure while heating until the reaction temperature reached 120 ° C, and the mixture was allowed to react at this temperature for 1 hour. The mixture was cooled to room temperature, and a neutralization reaction was carried out by adding 0.09 g (1.5 mmol) of acetic acid. After filtering out the salt produced, the low-boiling substance was removed from the obtained clear solution under reduced pressure while heating, and 10.3 g of a colorless clarified viscosity of more than 10,000 Pa was obtained. Viscous liquid of s (yield: 90.4%).

As a result of NMR analysis, the organic polyoxane represented by the following average unit formula was determined: (MeViPhSiO _1/2 ) _0.40 (NaphSiO _3/2 ) _0.60

The organic polyoxyalkylene had a weight average molecular weight (Mw) of 1,000, a degree of dispersion (Mw/Mn) of 1.08, and a refractive index of 1.622.

Practical example 1

First, 49.3 g (0.173 mol) of titanium tetraisopropoxide, 15 g of ethanol, 45 g of toluene, and 10.01 g (0.046 mol) of zinc acetate dihydrate were mixed, and 24.1 g (0.099 mol) of diphenyldimethoxydecane was additionally added. . Then, a mixture of 11.5 g of 0.1 N diluted hydrochloric acid and 64.0 g of ethanol was slowly added dropwise to the mixture, and after completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then, the mixture was heated to reflux for 1 hour. The solvent was distilled under reduced pressure while heating to obtain 33.5 g of a colorless solid (yield: 92%) having a refractive index of 1.670.

The reaction rate of the solid alkoxycarbenyl group was determined by NMR to be 99.4 mol%, and the solid metal oxy unit (M ¹ ) was determined: metal oxy unit (M ² ): organic decane The polyorganometalloxane (1) of the unit molar ratio TiO _4/2 : ZnO _2/2 : Ph ₂ SiO _2/2 = 0.55: 0.15: 0.30 (=1.83: 0.50:1).

The obtained polyorganometalloxane (1) was heated in an oven at 220 ° C for 1 hour, but only a slight yellowing was observed.

Practical example 2

First, 81.9 g (0.175 mol) of a 70 wt.% n-propanol solution of tetrapropoxy zirconium, 30 g of ethanol, 90 g of toluene, and 10.1 g (0.046 mol) of zinc acetate dihydrate were mixed, and an additional 24.1 g (0.099 mol) of two was added. Phenyldimethoxydecane. Then, a mixture of 9.1 g of 0.1 N diluted hydrochloric acid and 82.0 g of ethanol was slowly added dropwise to the solution. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour. Then, the mixture was heated to reflux for 1 hour. The solvent was distilled while heating under reduced pressure, and 441.9 g of a colorless solid (yield: 94.5%) having a refractive index of 1.647 was obtained.

The reaction rate of the alkoxycarbenyl group of the solid was determined by NMR to be 99.1 mol%, and the solid metal oxy unit (M ¹ ) was determined: metal oxy unit (M ² ): organic decane The weight of the unit molar ratio ZrO _4/2 : ZnO _2/2 : Ph ₂ SiO _2/2 = 0.55: 0.15: 0.30 (=1.83: 0.50:1) of the polyorganometalloxane (2).

The obtained polyorganometalloxane (2) was heated in an oven at 220 ° C for 1 hour, but No discoloration was observed.

Practical example 3

First, 0.88 g (4.0 mmol) of zinc chloride dihydrate was loaded into a mixed solution of 20 g of toluene and 10 g of ethanol and stirred. When 2.87 g (10.1 mmol) of tetraisopropyltitanium was added to the solution and stirred, a colorless clear solution was obtained. Then, 2 g of a toluene solution containing 0.76 g (3.53 mmol) of diphenylmethylnonanol was charged, and it was stirred at room temperature for 30 minutes. Then, a mixture of 0.39 g (21.6 mmol) of water and 2 g of ethanol was slowly added dropwise to the solution. After the completion of the dropwise addition, the solution was gradually heated, and the low-boiling substance was removed by distillation. When the temperature of the reaction solution reached 110 ° C, the distillation was stopped, and heat aging was performed at 110 ° C for 1 hour. Thus, 14 g of a toluene solution of an organometallic oxane (3) was obtained with a solid concentration of 13.3 wt.%.

The metal oxy unit (M ¹ ): the metal oxy unit (M ² ): the organooxane unit molar ratio of the organometallic fluorene ( ³ ) is TiO _4/2 : ZnO _2/2 : Ph ₂ MeSiO _1/2 = 0.57: 0.23: 0.20 (= 2.85: 1.15: 1).

Practical example 4

First, 0.88 g (4.0 mmol) of zinc chloride dihydrate was loaded into a mixed solution of 20 g of toluene and 10 g of ethanol and stirred. When 2.87 g (10.0 mmol) of tetraisopropyltitanium was added to the solution and stirred, a colorless clear solution was obtained. Then, 2 g of a toluene solution containing 0.57 g (2.65 mmol) of diphenylmethylnonanol was charged, and it was stirred at room temperature for 30 minutes. Then, a mixture of 0.40 g (22.3 mmol) of water and 2 g of ethanol was slowly added dropwise to the solution. After the completion of the dropwise addition, the solution was gradually heated, and the low-boiling substance was removed by distillation. When the temperature of the reaction solution reached 110 ° C, the distillation was stopped, and heat aging was performed at 110 ° C for 1 hour. Thus, 14.4 g of a toluene solution of polyorganometalloxane (4) was obtained with a solid concentration of 11.7 wt.%. The metal oxy unit (M ¹ ): the metal oxy unit (M ² ): the organooxane unit molar ratio of the organoorganometal _fluorene (4) is TiO _4/2 : ZnO _2/2 : Ph ₂ MeSiO _1/2 = 0.61: 0.24: 0.15 (= 4.07: 1.60: 1).

Comparative example 1

The reaction was carried out in the same manner as in Practical Example 1, except that the zinc acetate of Practical Example 1 was not used. However, when the reaction mixture was heated after the addition of 0.1 N of dilute hydrochloric acid, the mixture lost fluidity and gelation occurred.

Comparative example 2

In the case where zinc acetate of Practical Example 1 was not used, the corresponding polyorganometalloxane (5) without any gelation can be prepared by reducing the amount of 0.1 N dilute hydrochloric acid from 11.5 g to 8 g.

However, when the polyorganometalloxane (5) was heated in an oven at 220 ° C for 1 hour in the same manner as in Practical Example 1, the solution turned dark brown.

Practical examples 5 to 7

Vinyl dimethyl decyl alcohol was added to a 50 wt.% toluene solution of polyorganometalloxane (1) prepared in Practical Example 1 to form respective load compositions shown in Table 1, and the solution was Heat at 80 ° C for 3 hours.

Then, the solvent was distilled while being reduced under reduced pressure to prepare polyorganometalloxanes (6) to (8). The molar ratio of the metal oxy unit (M ¹ ):metal oxy unit (M ² ):organooxane unit in the polyorganometalloxane is shown in Table 1.

Practical example 8

Vinyl dimethyl sterol was added to a 50 wt.% toluene solution of the polyorganometalloxane (2) prepared in Practical Example 2 to form the respective loaded compositions shown in Table 1, and the solution was Heat at 80 ° C for 3 hours.

Then, the solvent was distilled while being reduced under reduced pressure to prepare a polyorganometalloxane (9). The molar ratio of the metal oxy unit (M ¹ ):metal oxy unit (M ² ):organooxane unit in the polyorganometalloxane is shown in Table 1.

Practical Examples 9 to 12 and Comparative Example 3

A polyorganometalloxane (15 wt.% solution in toluene), a vinyl functional polyorganosiloxane and a SiH functional polyorganosiloxane were mixed at the mixing ratios shown in Table 2. Then, the 1,3-divinyltetramethyldioxane platinum complex was mixed in an amount of 2 ppm by weight of the platinum metal with respect to the solid content to prepare a solution of the curable polymer composition.

A solution of this curable polymer composition was added dropwise to a glass plate, and it was allowed to stand at 40 ° C throughout the day and night to evaporate toluene, and a colorless clear solid film was obtained. Then, the film was heated at 150 ° C for 1 hour to obtain a colorless clarified cured product. According to the fact that the product did not dissolve when immersed in toluene, the product did solidify.

The evaluation results of the curable polymer composition and its cured product are shown in Table 2. The SiH/Vi ratio in Table 2 indicates the total vinyl group in the vinyl functional polyorganosiloxane, and the hydrogen atom bonded to the SiH functional polyorganosiloxane in the 1 mol of the curable polymer composition. The number of ears.

Practical examples 13 to 23

A polyorganometalloxane (15 wt.% solution in toluene), a vinyl functional polyorganosiloxane and a SiH functional polyorganosiloxane were mixed at the mixing ratios shown in Tables 3 to 5. Then, a 1,3-divinyltetramethyldioxanane platinum complex was mixed in an amount of 2 ppm by weight based on the platinum metal relative to the solid content to prepare a solution of the curable polymer composition.

A solution of this curable polymer composition was added dropwise to a glass plate, and it was allowed to stand at 40 ° C throughout the day and night to evaporate toluene, and a colorless clear solid film was obtained. Then, the film was heated at 150 ° C for 1 hour to obtain a colorless clarified cured product. According to the fact that the product did not dissolve when immersed in toluene, the product did solidify.

The evaluation results of the curable polymer composition and the cured product thereof are shown in Tables 3 to 5. The SiH/Vi ratios in Tables 3 to 5 represent the total vinyl groups in the polyorganometalloxane and the vinyl functional polyorganosiloxane, and the SiH functional polyorganosiloxane, per 1 mol of the curable polymer composition. The number of moles of hydrogen atoms in the middle bond.

Practical example 24 Production of surface mount light-emitting diodes (LEDs)

The MKO4545C LED chip 2 measuring 1 mm × 1 mm on each side of Bridgelux was mounted on each side of I-Chiun Precision Industry Co., Ltd. to measure a 5 mm × 5 mm TTI-5074 LED lead frame. The periphery of the lead frame is sealed with a polyphthalamide (PPA) resin shell. Then, the LED chip 2 and the internal leads 3 are electrically connected by a gold bonding wire 4 having a thickness of 1.5 mils.

Then, 3 g of the curable polymer composition obtained in Practical Example 14 and 0.105 g of a yttrium-aluminum-garnet-based fluorescent substance (product name: NTAG4851) manufactured by Intermatix Co., Ltd. were mixed to prepare a sealant. After deaeration of the sealant, 14.3 mg of a sealant was injected into a polyphthalamide (PPA) resin case 1 using a dispenser, and cured by heating at 150 ° C for 1 hour to form a pattern. Surface mount type light emitting diode (LED) as illustrated in 1.

Industrial applicability

The polyorganometalloxane of the present invention is cured by a hydrogenation reaction to form a cured product having a high refractive index and excellent visible light transmittance, heat resistance and moisture resistance, and thus can be used as an adhesive for electrical/electronic applications. , encapsulant, protective coating or underfill. Specifically, the visible light transmittance is high, which makes the product suitable as a sealant or a covering agent for an LED element or as a lens forming material.

1‧‧‧Polyphthalic acid (PPA) resin shell

2‧‧‧LED chip

3‧‧‧Internal leads

4‧‧‧bonding line

5‧‧‧Curing product of curable polymer composition

Claims (10)

A polyorganometalloxane comprising a metal oxy unit represented by the following formula (1): M ¹ O _x/2 wherein the atom of Group 4A or Group 5A of the M ¹ periodic table, and “x a valence of M ¹ ; a metal oxy unit represented by the following formula (2): M ² O _y/2 wherein the M ² is an atom of Group 2A or Group 2B of the periodic table, and "y" is M ^a valence of ² ; and an organooxane unit represented by the following formula (3): R ¹ _a SiO _(4-a)/2 wherein R ¹ is an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a hydrogen atom. And "a" is satisfied: 0<a The value of 3. The polyorganometalloxane of claim 1, wherein M ¹ is selected from the group consisting of atoms of Ti and Zr, and M ² is selected from the group consisting of Zn, Ca and Ba. The polyorganometalloxane of claim 1, wherein the ratio of the content of the metal oxy unit represented by the general formula (1) to the content of the oxirane unit represented by the general formula (3) is 0.01:1. The ratio of the content of the metal oxy unit represented by the general formula (2) to the content of the oxirane unit represented by the general formula (3) is from 99:1 to 19:1. A curable polymer composition curable by a hydrogenation reaction, the composition comprising the polyorganometalloxane of any one of claims 1 to 3. The curable polymer composition of claim 4, which comprises the following components (A), component (B), component (C), and component (D): (A) having at least 2 in each molecule Alkenyl organopolyoxane; (B) an organopolyoxane having at least 2 bonded hydrogen atoms in the molecule; (C) a hydrogenation reaction catalyst; and (D) a polyorganometallic ruthenium according to any one of claims 1 to 3. Oxytomane. The curable polymer composition of claim 4, comprising the following component (E), component (B), and component (C): (E) the polyorganometallic according to any one of claims 1 to 3. a oxane, wherein at least two R ¹ -alkenyl groups in the molecule; (B) an organopolyoxane having at least two hydrogen groups bonded to the molecule; and (C) a hydrogenation reaction catalyst. The curable polymer composition of claim 4, which further comprises (F) a phosphor. A cured product formed by curing a curable polymer composition as claimed in claim 4. An optical semiconductor device formed by covering or sealing an optical semiconductor element with a cured product of the curable polymer composition as claimed in claim 4. The curable polymer composition of claim 7, wherein component (F) is present in an amount of from 0.1 wt.% to 70 wt.%, based on the total weight of the curable polymer composition.