JP2016155954A - Additive reaction curing type resin composition and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive reaction curing type resin composition in which the index of refraction of cured matter is high, oxygen permeability is low, further, barrier properties to gas produced from sulfur or the like are satisfactory, and the surface of an optical reflection plate is not corroded, and an optical semiconductor device.SOLUTION: Provided is an additive reaction curing type resin composition comprising: (A) an organic cyclic compound having functional groups reacted with SiH groups by hydrosilylation reaction by two or more in one molecule; (B) linear organopolysiloxane having silicon-bonded alkenyl groups reacted with SiH groups by at least two in one molecule and having at least one silicon-bonded aryl group; (C) organo hydrogen polysiloxane having at least two SiH groups in one molecule; and (D) a curing catalyst required for additive reaction, and in which the molar ratio of the silicon atom-bonded hydrogen groups in the (C) organo hydrogen polysiloxane to the whole alkenyl group is 0.1 to 4.0, and an optical semiconductor device sealed therewith.SELECTED DRAWING: None

Description

  The present invention relates to an addition reaction curable resin composition and an optical semiconductor device having a low oxygen permeability and a good gas barrier property such as a gas generated from sulfur.

  Conventionally, a silicone resin composition has been used as a composition for encapsulating an optical semiconductor such as an LED, and an addition reaction curable silicone resin composition containing dimethylsiloxane is generally used. Particularly recently, phenyl-modified organopolysiloxane has been proposed as a silicone resin composition for sealing an optical semiconductor for the purpose of obtaining high transparency and refractive index (Patent Documents 1 to 5).

The curable silicone composition for optics according to Patent Document 1 is (A) a linear organopolysiloxane having vinyl groups at both ends and other organic groups consisting of a methyl group and a phenyl group, and (B) CH _2. = CH (CH ₃ ) ₂ SiO _0.5 , (CH ₃ ) ₃ SiO _0.5 , PhSiO _1.5 (where Ph is a phenyl group) and SiO ₂ siloxane units, and CH relative to SiO ₂ units ₂ = CH (CH ₃ ) ₂ SiO _0.5 units and (CH ₃ ) ₃ SiO _0.5 units have a total molar ratio of 0.5 to 2.0, and all bonded to silicon atoms in the molecule 9 mol% or more of the organic group is a branched organopolysiloxane copolymer that is a phenyl group, (C) the organic group is a methyl group or a phenyl group, and is compatible with the components (A) and (B). Organo High Logistics is a polysiloxane, and (D) an optical curable silicone composition comprising a platinum-based catalyst.

A curable silicone rubber and a semiconductor device according to Patent Document 2 are (A) a linear chain represented by the general formula (1) shown in the document and having a viscosity of 10 to 1,000,000 mPa · s at 25 ° C. Organopolysiloxane (A-1), or the above-mentioned organopolysiloxane (A-1) and a resin-structured organopolysiloxane (A-2), having a SiO ₂ unit, R ³ kR ⁴ pSiO _0.5 Unit and R ³ qR ⁴ rSiO _0.5 unit (in the above formula, R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, k is 2 or 3, p is 0 or 1, k + p = 3, q is 0 or 1, r is 2 or 3, and q + r = 3)) Combination with organopolysiloxane, (B) SiH group in one molecule Ol with two or more Nohydrogen polysiloxane, (C) metal-based condensation reaction catalyst, (D) platinum group metal-based addition reaction catalyst, and (E) at least two functional groups selected from alkenyl groups, alkoxy groups, and epoxy groups And (A) component, (B) component, and (E) component all contain an aromatic group, (A) component, (A) component, and (B) The curable silicone rubber composition is characterized in that the difference between the maximum value and the minimum value of the refractive index of the mixture of component (E) and component (E) is 0.03 or less.

Moreover, the curable organopolysiloxane composition and semiconductor device according to Patent Document 3 are (A) a linear chain having at least two silicon atom-bonded alkenyl groups and at least one silicon atom-bonded aryl group in one molecule. Organopolysiloxane, (B) having at least one silicon-bonded alkenyl group and at least one silicon-bonded aryl group in one molecule, and having the general formula: RSiO _3/2 (wherein R is substituted or non-substituted) A branched monoorganopolysiloxane having a siloxane unit represented by (the ratio of the content of this component to the component (A) is 1/99 to 99/1 by weight). (C) an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule {1 to 200 with respect to 100 parts by weight of the total of the components (A) and (B) Part by weight} and (D) a catalyst for hydrosilylation reaction (an amount that promotes curing of the present composition).

Further, the addition-curable silicone composition according to Patent Document 4 has (A) an alkenyl group bonded to at least one silicon atom in one molecule, and a Ph ₂ SiO _2/2 unit (where Ph is a phenyl group). 100 parts by weight, (B) 2 to 20 mol% of ViR ¹ SiO _2/2 units, 10 to 80 mol% of PhSiO _3/2 units, Ph ₂ SiO _2/2 consists units 10 to 80 mol% and ^R ₁ 2 _{SiO 2/2} units 0-30 mol%, a residual hydroxyl group formed by blocked with ^R ₂ 3 _{SiO 1/2} units branched organopolysiloxane; 10 to 300 parts by weight (wherein Vi is a vinyl group, Ph is a phenyl group, R ¹ is a monovalent hydrocarbon group not containing an aliphatic unsaturated group, R ² is a methyl group or a phenyl group), ( C R ³ ₂ HSiO consists _1/2 units and SiO ₂ units, organohydrogen siloxane SiO ₂ unit number ratio of 1 to 10 is 70% or more in the molecule; (A), (B) component In an amount of 0.4 to 3 moles of SiH bonds relative to 1 mole of silicon atom-bonded alkenyl group (wherein R ³ is a monovalent hydrocarbon group not containing an aliphatic unsaturated group), (D ) An addition-curable silicone composition comprising a hydrosilylation reaction catalyst.

Further, an addition-curable silicone composition according to Patent Document 5 and a semiconductor device in which a semiconductor element is coated with a cured product of the composition are at least (A) an organopolysiloxane represented by the following average unit formula (1): : 100 parts by mass, (R ¹ SiO _3/2 ) _a1 (R ¹ ₂ SiO _2/2 ) _b1 (R ¹ ₃ SiO _1/2 ) _c1 (X ¹ O _1/2 ) _d1 (1), {in formula , R 1 may be the same or different, a substituted or unsubstituted monovalent hydrocarbon group (provided that 0.1 to 50 mol% of ^{R 1} is an alkenyl group, at least 10 mol% of R 1 is aryl X ¹ is a hydrogen atom or an alkyl group. a1 is 0.25 to 1, b1 is 0 to 0.75, c1 is 0 to 0.3, d1 is 0 to 0.1, and a1 + b1 + c1 + d1 is 1. }, (B) Organopolysiloxane represented by the following average unit formula (2): 1 to 99 parts by mass, (R ² SiO _3/2 ) _a2 (R ² ₂ SiO _2/2 ) _b2 (R ² ₃ SiO _1/2 ) _c2 (X ² O _1/2 ) _d2 (2), {wherein R ² may be the same or different, a substituted or unsubstituted monovalent hydrocarbon group (provided that R ² is 0 .001～20 mol% is an alkenyl group, an over 10 mol% of ^{R 2} is an aryl group), ^{X 2} is a hydrogen atom or an alkyl group. a2 is 0.005 to 0.1, b2 is 0.5 to 0.95, c2 is 0.005 to 0.1, d2 is 0 to 0.1, and a2 + b2 + c2 + d2 is 1. }, (C) which is represented by the following average composition formula (3), has at least two Si—H bonds in one molecule, and 5 mol% or more of the total of R ′ and H bonded to the silicon atom: Organohydrogenpolysiloxane which is a phenyl group: an amount of 1 to 200 parts by mass with respect to a total of 100 parts by mass of components (A) + (B), R ′ _{a ′} H _{b ′} SiO _{[(4-a′− b ′) / 2]} (3), wherein R ′ is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, excluding the aliphatic unsaturated hydrocarbon group. , B ′ are positive numbers satisfying 0.7 ≦ a ′ ≦ 2.1, 0.01 ≦ b ′ ≦ 1.0, and 0.8 ≦ a ′ + b ′ ≦ 2.7.) And (D ) Hydrosilylation catalyst: An addition-curable silicone composition containing an amount that promotes curing of the composition.

  However, in these addition reaction curable silicone compositions, the corrosion of silver-plated surfaces used as light reflectors for LEDs and the like due to corrosive gases such as gases generated from sulfur, which are acidic components present in the air. When the lamp is turned on or in an external high temperature environment, the corrosion of the silver plating surface may be promoted, resulting in a problem that the luminance of the LED may be lowered.

In contrast, an optical device formed by using the organopolysiloxane composition as an encapsulating agent, a moisture permeability after curing of the composition is not more than 30g / m 2 / ^24h, the composition, (A) A polyhedral polysiloxane modified product obtained by modifying a compound (b) having a hydrosilyl group with respect to a polyhedral polysiloxane compound (a) containing an alkenyl group, (B) in one molecule Proposed optical device comprising an organopolysiloxane composition comprising an organopolysiloxane having two or more alkenyl groups and (C) an organosilicon compound having one alkenyl group or hydrosilyl group in one molecule. Has been.

  However, the optical device using the organopolysiloxane composition shown in Patent Document 6 must use a compound or organopolysiloxane having a special structure, and it takes time and effort to obtain the compound and the like. As a result, the composition is expensive, and the literature only shows the moisture permeability after curing of the organopolysiloxane composition, There is a case where oxygen permeability, which is an evaluation item required from the viewpoint of protection, may be high, and there is a problem that the obtained resin is a hard resin and does not sufficiently satisfy rubber elasticity.

JP-A-8-134358 Japanese Patent No. 5136963 Japanese Patent No. 4409160 Japanese Patent No. 4180474 Japanese Patent No. 5524017 JP 2012-12556 A

  The problem to be solved by the present invention is that the cured product has a high refractive index, a low oxygen permeability, and no sulfur without using a compound or organopolysiloxane having a special structure as shown in Patent Document 6. Additive reaction curable type suitable for sealing optical semiconductors such as LEDs, with good gas barrier properties such as gas generated from, without corroding the silver plating surface used in light reflectors such as LEDs The object is to provide a resin composition and an optical semiconductor device.

In order to solve the above problems, the invention according to claim 1 is an organic cyclic compound (A) having two or more functional groups that react with SiH groups by hydrosilylation reaction in one molecule;
A linear organopolysiloxane (B) having at least two silicon-bonded alkenyl groups that react with SiH groups in one molecule and having at least one silicon-bonded aryl group;
An organohydrogenpolysiloxane (C) having at least two SiH groups in one molecule;
A curing catalyst (D) necessary for the addition reaction,
The molar ratio of the silicon-bonded hydrogen groups of the organohydrogenpolysiloxane (C) to the total alkenyl groups of the organic cyclic compound (A) and the linear organopolysiloxane (B) is 0.1 to 4.0. An addition reaction curable resin composition is provided.

  In the invention of claim 2, the organic cyclic compound (A) comprises an isocyanuric acid derivative, and the total of the organic cyclic compound (A), the linear organopolysiloxane (B) and the organohydrogenpolysiloxane (C). The addition reaction curable resin composition according to claim 1, wherein the organic cyclic compound (A) is 5 to 50 parts by weight with respect to 100 parts by weight.

  The invention according to claim 3 is characterized in that in the linear organopolysiloxane (B), 1 to 70 mol% of the total organic substituents bonded to silicon atoms are phenyl groups. Item 2. An addition reaction curable resin composition according to Item 2 is provided.

  The invention according to claim 4 is characterized in that the organohydrogenpolysiloxane (C) has a content of hydrogen atoms bonded to silicon atoms of 1.0 mmol / g to 20.0 mmol / g. An addition reaction curable resin composition according to any one of Items 1 to 3 is provided.

  The invention according to claim 5 is an optical semiconductor wherein an optical semiconductor element is sealed with a cured product of the addition reaction curable resin composition according to any one of claims 1 to 4. Providing equipment.

  The addition reaction curable resin composition of the present invention has a high refractive index of a cured product, a low oxygen permeability without using a compound or organopolysiloxane having a special structure, and a gas barrier such as a gas generated from sulfur. The silver plating surface used for light reflectors, such as LED, is not corroded, and it is suitable for sealing optical semiconductors, such as LED. .

  In the optical semiconductor device according to claim 5, since the optical semiconductor element is sealed with an addition reaction curable resin composition having a low oxygen permeability and a good gas barrier property such as a gas generated from sulfur. There is an effect that silver plating, which is sometimes used for plates and electrode parts, does not corrode, and thus there is an effect that luminance does not decrease.

  Hereinafter, the addition reaction curable resin composition according to the present invention will be described in detail.

Organic cyclic compound (A) having two or more functional groups in one molecule that react with SiH groups by hydrosilylation reaction
The organic cyclic compound (A) having two or more functional groups that react with SiH groups in the molecule by hydrosilylation reaction reduces the oxygen permeability of the cured product of the addition reaction curable resin composition according to the present invention. For example, a compound represented by the following general formula (1).

In the above formula (1), R1 is a monovalent organic group having 1 to 50 carbon atoms and the three R ¹ may be the same or different and at least 2 of the three R ¹ These are groups containing carbon-carbon double bonds that react with SiH groups. Examples of these organic cyclic compounds include triallyl isocyanurate, diallyl monoglycidyl isocyanurate, and monomethyl diallyl isocyanurate.

  The amount of the organic cyclic compound (A) is 5 to 5 parts by weight based on a total of 100 parts by weight of the organic cyclic compound (A), linear organopolysiloxane (B) and organohydrogenpolysiloxane (C) shown below. The amount is preferably 50 parts by weight, more preferably 8 to 30 parts by weight. If it is less than 5 parts by weight, the oxygen permeability is increased and the gas barrier properties such as a gas generated from sulfur are lowered. If it exceeds 50 parts by weight, poor curing tends to occur and sufficient hardness cannot be obtained. If it is less than 8 parts by weight, the oxygen permeability tends to be high and gas barrier properties such as a gas generated from sulfur tend to be lowered, and if it exceeds 30 parts by weight, the hardness of the cured product tends to be lowered.

Linear organopolysiloxane (B) having at least two silicon-bonded alkenyl groups that react with SiH groups in one molecule and at least one silicon-bonded aryl group
A linear organopolysiloxane (B) having at least two silicon-bonded alkenyl groups that react with SiH groups in one molecule and having at least one silicon-bonded aryl group is a vinyl group, an allyl group, a propenyl group, An organopolysiloxane containing at least two carbon-carbon double bonds such as isopropenyl group, butenyl group, isobutenyl group, hexenyl group in one molecule, and other organoorganosiloxane bonded to silicon in a terminal or repeating unit As a group, an aryl group such as a phenyl group, a benzyl group, or a tolyl group is bonded. A specific example is methylphenylvinylpolysiloxane. When the aryl group bonded to the silicon atom is a phenyl group, 1 to 70 mol% of the whole organic substituent bonded to the silicon atom is preferably a phenyl group, and when it is less than 1 mol%, the gas generated from sulfur Insufficient gas barrier property against the above, and if it exceeds 70 mol%, the heat resistance becomes insufficient and the cured product tends to yellow.

Organohydrogenpolysiloxane having at least two SiH groups in one molecule (C)
The organohydrogenpolysiloxane (C) having at least two SiH groups in one molecule is an organopolysiloxane containing two or more SiH groups in the terminal and / or repeating structure and bonded to a silicon atom. The hydrogen atom content is preferably 1.0 mmol / g to 20.0 mmol / g, and if it is 1.0 mmol / g or more, curability is improved and hardness is easily obtained. When the content of hydrogen atoms exceeds 20.0 mmol / g, tackiness is likely to occur on the surface of the cured product. In order to obtain good hardness, the hydrogen group content ratio is more preferably 1.5 mmol / g or more. In order to make it difficult for tackiness to occur, the hydrogen atom content is more preferably less than 10.0 mmol / g. Examples of the organo group bonded to the silicon atom include a methyl group, an ethyl group, and a phenyl group. The organohydrogen polysiloxane may be, for example, linear or branched, and specific examples include methylphenyl hydrogen polysiloxane.

  The molar ratio of the silicon atom-bonded hydrogen groups of the organohydrogenpolysiloxane (C) to the total alkenyl groups of the organocyclic compound (A) and the following linear organopolysiloxane (B) is 0.1 to 4.0. If the molar ratio is less than 0.1 and more than 4.0, sufficient strength as a cured product cannot be obtained.

Curing catalyst required for addition reaction (D)
The curing catalyst (D) required for the addition reaction is added to promote the hydrosilylation reaction of the component (A), the component (B) and the component (C), and has a catalytic activity for the hydrosilylation reaction. These metals, metal compounds, metal complexes, and the like can be used. In particular, it is preferable to use platinum, a platinum compound, or a complex thereof. These catalysts may be used alone or in combination of two or more. A cocatalyst may be used in combination. The addition amount of the addition reaction catalyst (C) is preferably 1 ppm to 50 ppm, more preferably 5 to 20 ppm with respect to the entire composition. If it is less than 1 ppm, the curability is lowered and it is difficult to obtain sufficient hardness, and if it exceeds 50 ppm, the transparency after curing becomes a factor.

  In the present composition, as other optional components, alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, ethynylcyclohexanol; Enyne compounds such as 3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane Reaction inhibitors such as 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, 1,3 divinyltetramethyldisiloxane, and benzotriazole may be contained. This reaction inhibitor is within a range of 0.0001 to 1 part by weight with respect to a total of 100 parts by weight of the component (A), the component (B), and the component (C) as a content that does not suppress curability. Is preferred.

  Moreover, you may contain the adhesion imparting agent for improving the thermal shock property by the adhesiveness and repeated cooling and cooling in this composition. As this adhesion-imparting agent, an epoxy group- or alkoxy group-containing organosilicon compound, or a condensate thereof may be used. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable. The group other than the alkoxy group bonded to the silicon atom of the organosilicon compound includes a substituted or unsubstituted monovalent hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a halogen-substituted alkyl group; 3 -Glycidoxyalkyl groups such as glycidoxypropyl group and 4-glycidoxybutyl group; epoxies such as 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group Cyclohexylalkyl group; epoxy group-containing monovalent organic group such as oxiranylalkyl group such as 4-oxiranylbutyl group and 8-oxiranyloctyl group; acrylic group-containing monovalent organic group such as 3-methacryloxypropyl group Group; a hydrogen atom is exemplified. The organosilicon compound preferably has a group capable of reacting with the component (A) or the component (B), and specifically has a silicon atom-bonded alkenyl group or a silicon atom-bonded hydrogen atom. Moreover, since it can provide favorable adhesiveness to various types of substrates, the organosilicon compound preferably has at least one epoxy group-containing monovalent organic group in one molecule.

  In addition, this composition contains calcium carbonate, cinnabar sand, talc, carbon black, titanium oxide, zinc oxide, kaolin, silicon dioxide, melamine for viscosity adjustment and hardness adjustment as long as the object of the invention is not impaired. May contain inorganic fillers such as organic fillers, reinforcing materials such as glass fibers to reinforce cured resins, and hollow bodies such as shirasu balloons and glass balloons to reduce weight and adjust viscosity it can. In addition, antioxidants, organic pigments, fluorescent pigments, corrosion inhibitors, and the like can be used as appropriate.

  The optical semiconductor device according to claim 5 of the present invention has an optical semiconductor element such as an optical semiconductor (LED) by a cured product of the addition reaction curable resin composition according to any one of claims 1 to 4. This is a sealed optical semiconductor device.

  Next, the addition reaction curable resin composition of the present invention will be described in detail with reference to Examples and Comparative Examples.

Examples 1 to 4 and Comparative Examples 1 to 4
As the organic cyclic compound (A), triallyl isocyanurate (A-1), diallyl monoglycidyl isocyanurate (A-2), and monomethyldiallyl isocyanurate (A-3) are converted into linear organopolysiloxane (B). Both ends are sealed with M ^Vi units, the intermediate unit consists of D units and D ^Vi units, and the viscosity is 10.5 Pa. It is sealed with linear methylphenylvinylpolysiloxane (B-1) having a weight average molecular weight of 8,900 at s / 25 ° C., and terminal M units and M ^Vi units, and contains D units and T units. Viscosity 18.0 Pa. A branched methylphenylvinylpolysiloxane (B-2) having a mass average molecular weight of 1,500 at s / 25 ° C. is sealed as an organohydrogenpolysiloxane (C) with terminal M units and ^MH units, Contains D units and T units, and has a viscosity of 4.5 Pa.s. Branched methylphenylvinylpolysiloxane (C-1), (M ^H ) ₃ having a mass average molecular weight of 1,500 at s / 25 ° C. and a content of hydrogen atoms bonded to silicon atoms of 2.08 mmol / g Viscosity represented by T ₁ of 0.0025 Pa. Branched methylphenylhydrogen organopolysiloxane (C-2) having a mass average molecular weight of 330 at s / 25 ° C. and a content of hydrogen atoms bonded to silicon atoms of 8.5 mmol / g, and (M ^H ) ₂ D ₁ Viscosity 0.0004 Pa. A linear methylphenyl hydrogen organopolysiloxane (C-3) having a mass average molecular weight of 332 at s / 25 ° C. and a content of hydrogen atoms bonded to silicon atoms of 6.01 mmol / g is required for the addition reaction. Platinum-vinyl dimer complex (Pt: 12% wt) (D-1) was used as the curing catalyst (D), respectively, and uniformly mixed with the composition shown in Table 1 to obtain an addition reaction curable resin composition. . The numbers in Table 1 indicate parts by weight. The abbreviations are represented by the following structural formulas.

M unit: (CH ₃ ) ₃ SiO _1/2
M ^Vi unit: (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2
^MH unit: (CH ₃ ) ₂ HSiO _1/2
D unit: (CH ₃ ) ₂ SiO _2/2 or (C ₆ H ₅ ) ₂ SiO _2/2 or (CH ₂ ) (C ₆ H ₅ ) SiO _2/2
D ^Vi unit: (CH ₃ ) (CH ₂ ═CH) SiO _2/2
^DH unit: (CH ₃ ) HSiO _2/2
T unit: (C ₆ H ₅ ) ₂ SiO _3/2

Evaluation items and evaluation methods

Appearance Each addition reaction curable resin composition was cured at 150 ° C. for 4 hours to prepare a test specimen having a thickness of 6 mm, and the appearance was evaluated visually at 23 ° C.

Durometer hardness Each addition reaction curable resin composition was cured at 150 ° C. for 4 hours to prepare a specimen having a thickness of 6 mm. The durometer hardness was measured at 23 ° C. using a type A or type D durometer in accordance with JIS K6253-3 (vulcanized rubber and thermoplastic rubber—determination of hardness—part 3: durometer hardness). .

Each addition reaction curable resin composition having a refractive index was cured at 150 ° C. for 4 hours to prepare a test piece having a thickness of 1 mm and measured with an Abbe refractometer 1T (manufactured by ATAGO).

Elongation Each addition reaction curable resin composition was cured at 150 ° C. for 4 hours to prepare a test piece having a thickness of 2 mm. JIS K6249 Test method for uncured and cured silicone rubber 15. The elongation% was measured based on a tensile test.

Oxygen permeability Each addition reaction curable resin composition was cured at 150 ° C. for 4 hours to prepare a sheet having a thickness of 1 mm. According to JIS K7126-1 plastic film and sheet-gas permeability test method-part 1: differential pressure method, oxygen permeability was measured.

Each addition reaction curable resin composition is filled in an LED package (outer dimensions 50 × 50 mm) having a sulfur-corrosion resistant bottom plated with silver, and cured at 150 ° C. for 4 hours to obtain a test specimen. Three each of the test specimens were sealed in a 100 cc glass bottle pre-filled with 1 g of sulfur powder and allowed to stand at 80 ° C. for 24 hours. Thereafter, the specimen was taken out, and the degree of corrosion of the silver plating at the bottom was visually observed. The result was evaluated as o for no corrosion, Δ for partial corrosion, and x for overall corrosion.

Evaluation results The evaluation results are shown in Table 1.

In order to solve the above problems, the invention according to claim 1 is an organic cyclic compound (A) having two or more functional groups that react with SiH groups by hydrosilylation reaction in one molecule;
Have at least two SiH groups in each molecule, and containing at least branched organohydrogenpolysiloxanes, the organohydrogenpolysiloxane (C),
A curing catalyst (D) necessary for the addition reaction, and no adhesion-imparting agent,
The molar ratio of silicon atom-bonded hydrogen groups of organohydrogenpolysiloxane (C) to all alkenyl groups of organocyclic compound (A) and linear organopolysiloxane (B) is 0.1-4.0,
The organohydrogenpolysiloxane (C) has a content of hydrogen atoms bonded to silicon atoms of 1.0 mmol / g to 20.0 mmol / g,
The organic cyclic compound (A) is composed of an isocyanuric acid derivative, and the organic cyclic compound (A), the linear organopolysiloxane (B), and the organohydrogenpolysiloxane (C) are combined with 100 parts by weight of the organic cyclic compound (A). A) provides 5 to 50 parts by weight of an addition reaction curable resin composition .

The invention according to claim 2 is characterized in that the linear organopolysiloxane (B) is a phenyl group in which 1 to 70 mol% of all organic substituents bonded to silicon atoms are phenyl groups . An addition reaction curable resin composition is provided.
It is.

According to a third aspect of the present invention, there is provided an optical semiconductor device wherein the optical semiconductor element is sealed with a cured product of the addition reaction curable resin composition according to the first or second aspect. To do.

In the optical semiconductor device according to claim 3 , since the optical semiconductor element is sealed with an addition reaction curable resin composition having a low oxygen permeability and a good gas barrier property such as a gas generated from sulfur. There is an effect that silver plating, which is sometimes used for a plate or an electrode part, does not corrode, and therefore there is an effect that luminance does not decrease.

Organohydrogenpolysiloxane having at least two SiH groups in one molecule (C)
The organohydrogenpolysiloxane (C) having at least two SiH groups in one molecule is an organopolysiloxane containing two or more SiH groups in the terminal and / or repeating structure and bonded to a silicon atom. The hydrogen atom content is preferably 1.0 mmol / g to 20.0 mmol / g, and if it is 1.0 mmol / g or more, curability is improved and hardness is easily obtained. When the content of hydrogen atoms exceeds 20.0 mmol / g, tackiness is likely to occur on the surface of the cured product. In order to obtain good hardness, the hydrogen atom content is more preferably 1.5 mmol / g or more. In order to make it difficult for tackiness to occur, the hydrogen atom content is more preferably less than 10.0 mmol / g. Examples of the organo group bonded to the silicon atom include a methyl group, an ethyl group, and a phenyl group. The organohydrogen polysiloxane may be, for example, linear or branched, and specific examples include methylphenyl hydrogen polysiloxane.

In the optical semiconductor device according to claim 3 of the present invention, an optical semiconductor element such as an optical semiconductor (LED) is sealed with a cured product of the addition reaction curable resin composition according to claim 1 or 2. It is an optical semiconductor device.

Examples 1 to 4 and Comparative Examples 1 to 4
As the organic cyclic compound (A), triallyl isocyanurate (A-1), diallyl monoglycidyl isocyanurate (A-2), and monomethyldiallyl isocyanurate (A-3) are converted into linear organopolysiloxane (B). Both ends are sealed with M ^Vi units, the intermediate unit consists of D units and D ^Vi units, and the viscosity is 10.5 Pa. Linear methylphenylvinylpolysiloxane (B-1) having a weight average molecular weight of 8,900 at s / 25 ° C. is sealed with terminal M units and M ^Vi units, and contains D units and T units. Viscosity 18.0 Pa. A branched methylphenylvinylpolysiloxane (B-2) having a mass average molecular weight of 1,500 at s / 25 ° C. is sealed as an organohydrogenpolysiloxane (C) with terminal M units and ^MH units, Contains D units and T units, and has a viscosity of 4.5 Pa.s. Branched methylphenylvinylpolysiloxane (C-1), (M ^H ) ₃ having a mass average molecular weight of 1,500 at s / 25 ° C. and a content of hydrogen atoms bonded to silicon atoms of 2.08 mmol / g Viscosity represented by T ₁ of 0.0025 Pa. Branched methylphenylhydrogen organopolysiloxane (C-2) having a mass average molecular weight of 330 at s / 25 ° C. and a content of hydrogen atoms bonded to silicon atoms of 8.5 mmol / g, and (M ^H ) ₂ D ₁ Viscosity 0.0004 Pa. A linear methylphenyl hydrogen organopolysiloxane (C-3) having a mass average molecular weight of 290 at s / 25 ° C. and a content of hydrogen atoms bonded to silicon atoms of 6.01 mmol / g is required for the addition reaction. Platinum-vinyl dimer complex (Pt: 12% wt) (D-1) was used as the curing catalyst (D), respectively, and uniformly mixed with the composition shown in Table 1 to obtain an addition reaction curable resin composition. . The numbers in Table 1 indicate parts by weight. The abbreviations are represented by the following structural formulas.

M unit: (CH ₃ ) ₃ SiO _1/2
M ^Vi unit: (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2
^MH unit: (CH ₃ ) ₂ HSiO _1/2
D unit: (CH ₃ ) ₂ SiO _2/2 or (C ₆ H ₅ ) ₂ SiO _2/2 or (CH ₃ ) (C ₆ H ₅ ) SiO _2/2
D ^Vi unit: (CH ₃ ) (CH ₂ ═CH) SiO _2/2
^DH unit: (CH ₃ ) HSiO _2/2
T unit: (C ₆ H ₅ ) SiO _3/2

Claims (5)

An organic cyclic compound (A) having two or more functional groups that react with SiH groups by hydrosilylation reaction in one molecule;
A linear organopolysiloxane (B) having at least two silicon-bonded alkenyl groups that react with SiH groups in one molecule and having at least one silicon-bonded aryl group;
An organohydrogenpolysiloxane (C) having at least two SiH groups in one molecule;
A curing catalyst (D) necessary for the addition reaction,
The molar ratio of the silicon-bonded hydrogen groups of the organohydrogenpolysiloxane (C) to the total alkenyl groups of the organic cyclic compound (A) and the linear organopolysiloxane (B) is 0.1 to 4.0. An addition reaction curable resin composition.   The organic cyclic compound (A) is composed of an isocyanuric acid derivative, and the organic cyclic compound (A), the linear organopolysiloxane (B), and the organohydrogenpolysiloxane (C) are combined with 100 parts by weight of the organic cyclic compound (A). The addition reaction curable resin composition according to claim 1, wherein A) is 5 to 50 parts by weight.   3. The addition reaction curable resin composition according to claim 1, wherein the linear organopolysiloxane (B) comprises 1 to 70 mol% of all organic substituents bonded to silicon atoms as phenyl groups. object.   The content of hydrogen atoms bonded to silicon atoms in the organohydrogenpolysiloxane (C) is 1.0 mmol / g to 20.0 mmol / g. The addition reaction curable resin composition described. An optical semiconductor device, wherein an optical semiconductor element is sealed with a cured product of the addition reaction curable resin composition according to any one of claims 1 to 4.