TWI681992B - Addition reaction-curable resin composition and optical semiconductor device - Google Patents

Abstract

An addition reaction-curable resin composition comprising: an organic cyclic compound (A) having two or more functional groups that react with SiH groups by hydrosilylation reaction in one molecule; at least two compounds in one molecule A silicon-bonded alkenyl group reacting with SiH groups, a linear organic polysiloxane (B) having at least one silicon-bonded aryl group; at least two SiH groups in one molecule and containing at least branched organic hydrogen Polysiloxane organic hydrogen polysiloxane (C); and curing catalyst (D) required for addition reaction.

Description

Addition reaction-curable resin composition and optical semiconductor device

The present invention relates to an addition reaction-curable resin composition and an optical semiconductor device.

Conventionally, as a composition for sealing an optical semiconductor such as an LED, a silicone resin composition is used, and an addition reaction-curable silicone resin composition containing dimethylsiloxane is generally used. In particular, recently, in order to obtain high transparency and high refractive index, a phenyl-modified organopolysiloxane has been proposed as a silicone resin composition for optical semiconductor sealing (Patent Document 1 to Patent Document 5).

The optical curable silicone composition of Patent Document 1 is an optical curable silicone composition containing the following (A), (B), (C), and (D), wherein (A) has vinyl groups at both ends And other organic groups are composed of methyl and phenyl linear organic polysiloxane; (B) is composed of CH ₂ =CH(CH ₃ ) ₂ SiO _0.5 unit, (CH ₃ ) ₃ SiO _0.5 unit, PhSiO _1.5 (Where Ph is phenyl) unit, and SiO ₂ siloxane unit, and the total of CH ₂ =CH(CH ₃ ) ₂ SiO _0.5 unit and (CH ₃ ) ₃ SiO _0.5 unit is the same as SiO ₂ siloxane unit The molar ratio is 0.5 to 2.0, and all of the organic groups bonded to silicon atoms in the molecule contain 9 mol% or more of branched organic polysiloxane copolymers with phenyl groups; (C) organic groups are methyl groups Or a phenyl group and an organic hydrogen polysiloxane compatible with the components (A) and (B); (D) is a platinum-based catalyst.

In addition, the curable silicone rubber of Patent Document 2 is a curable silicone rubber composition containing the following (A), (B), (C), (D), and (E), wherein (A) is based on Expression (1) shows that it has 10~1,000,000mPa at 25℃. s viscosity linear organic polysiloxane (A-1), or a combination of the aforementioned organic polysiloxane (A-1) and a resin-structured organic polysiloxane (A-2), the aforementioned (A -2) is composed of SiO ₂ units, R ³ _k R ⁴ _p SiO _0.5 units and R ³ _q R ⁴ _r SiO _0.5 units (wherein, in the aforementioned chemical formula, R ³ is vinyl or allyl; R ⁴ is Monovalent hydrocarbon group without 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; q+r=3.) Organic Polysiloxane; (B) is an organic hydrogen polysiloxane with more than 2 SiH groups in one molecule; (C) is a metal-based condensation reaction catalyst; (D) is a platinum group metal-based addition reaction catalyst; ( E) is an organopolysiloxane containing at least two functional groups selected from alkenyl, alkoxy, and epoxy groups for imparting adhesion; and the curable silicone rubber composition is characterized by (A) Component, (B) component and (E) component all contain aromatic groups; (A) component, (A) component and (B) component mixture and (E) component difference between the maximum and minimum refractive index 0.03 or less.

In addition, the curable organic polysiloxane composition of Patent Document 3 is a curable organic polysiloxane composition composed of the following (A), (B), (C), and (D), wherein (A) is Straight-chain organic polysiloxane having at least 2 silicon atom-bonded alkenyl groups and at least one silicon atom-bonded aryl group in one molecule; (B) has at least one silicon atom-bonded alkenyl group in one molecule An aryl group bonded to at least one silicon atom and having a branched-chain organic polysiloxane represented by the formula: RSiO _3/2 (where R is a substituted or unsubstituted monovalent hydrocarbon group.) Alkane {the content ratio of (B) component to (A) component is recorded as 1/99~99/1 in weight units}; (C) is an organic polymer having at least 2 silicon atoms bonded to hydrogen atoms in one molecule Siloxane {1 to 200 parts by weight relative to the total weight of 100 parts of (A) and (B) components}; (D) is a catalyst for hydrosilylation reaction (amount that promotes curing of the composition).

In addition, the addition-curable silicone composition of Patent Document 4 is an addition-curable silicone composition containing the following (A), (B), (C), and (D), wherein (A) is in one molecule 100 parts by weight of linear organic polysiloxane containing at least one alkenyl group bonded to a silicon atom and containing 20 to 60 mole% Ph ₂ SiO _2/2 units (where Ph is phenyl); (B) It is composed of ViR ¹ SiO _2/2 unit 2~20 mol%, PhSiO _3/2 unit 10~80 mol%, Ph ₂ SiO _2/2 unit 10~80 mol%, and R ¹ ₂ SiO _2/2 unit The branched-chain organic polysiloxane composed of 0 to 30 mol% and composed of R ² ₃ SiO _1/2 units to block the remaining hydroxyl groups is 10 to 300 parts by weight (in the chemical formula, Vi is vinyl; Ph Is phenyl; R ¹ is a monovalent hydrocarbon group without an aliphatic unsaturated group; R ² is methyl or phenyl); (C) is composed of R ³ ₂ HSiO _1/2 units and SiO ₂ units, and Organic hydrogen siloxanes with a ratio of 1 to 10 SiO ₂ units in a molecule of 70% or more, of which (A) and (B) components are bonded to 1 mole of silicon atoms to an alkenyl group, SiH The amount of the bond is 0.4 to 3 moles (in the chemical formula, R ³ is a monovalent hydrocarbon group having no aliphatic unsaturated group); (D) is a catalyst for hydrosilylation reaction.

In addition, the addition-curable silicone composition of Patent Document 5 is characterized by containing at least the following (A), (B), (C), and (D) addition-curable silicone composition, wherein (A) is The organic polysiloxane is represented by the following average unit formula (1) 100 parts by mass, the unit formula (1) is: (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 {where R1 is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different (wherein 0.1 to 50 mole% of R ¹ is an alkenyl group) ; More than 10 mole% of R ¹ is aryl), X ¹ is a hydrogen atom or an alkyl group. a1 is 0.25~1; b1 is 0~0.75; c1 is 0~0.3; d1 is 0~0.1; a1+b1+c1+d1 is 1. }; (B) is the organic polysiloxane represented by the following average unit formula (2) 1~99 mass fraction, unit formula (2) is: (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 {where R ² is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different (wherein R ² 0.001 to 20 mol% is alkenyl; 10 mol% or more of R ² is aryl); X ² is a hydrogen atom or an alkyl group. a2 is 0.005~0.1; b2 is 0.5~0.95; c2 is 0.005~0.1, d2 is 0~0.1; a2+b2+c2+d2 is 1. }; (C) is represented by the following average composition formula (3) and has at least 2 Si-H bonds in one molecule, and the total of R′ and H bonded to the silicon atom is 5 mol% or more is phenyl the organohydrogen silicon alumoxane, wherein, with respect to (a) + (B) component totals 100 mass fraction, in an amount of 1 to 200 mass points, the average composition formula _{(3): R 'a' H b '} SiO _{[(4-a'-b')/2]} (In the formula, R′ is a monovalent hydrocarbon group which may be the same or different except for the aliphatic unsaturated hydrocarbon group, which may be the same or different. a′, b′ are Satisfy: 0.7≦a′≦2.1; 0.01≦b′≦1.0, and 0.8≦a′+b′≦2.7 are positive numbers.); (D) is a catalyst for hydrosilylation reaction having an amount that promotes curing of the composition .

When these addition reaction-curable silicone resin compositions are used, the silver-plated surface used as a light reflecting plate such as an LED due to corrosive gas such as gas generated by an acid component (for example, sulfur) present in the air Corrosion may occur, and sometimes the aforementioned corrosion of the silver-plated surface may be promoted during lighting or in an external high-temperature environment. If the corrosion of the silver-plated surface is promoted, the result is that the LED brightness will be reduced.

In this regard, an optical device is proposed, which is an optical device using an organic polysiloxane-based composition as a sealant (Patent Document 6), and is characterized in that the moisture permeability of the composition after curing is 30 g/m ² /24h or less, the composition is an organic polysiloxane-based composition composed of (A), (B) and (C), and the aforementioned (A) is a polysiloxane-based polyhedral structure containing an alkenyl group Polysiloxane modified polyhedral structure obtained by modifying compound (a) and compound (b) having a hydrosilyl group, the aforementioned (B) is an organic polysiloxane having two or more alkenyl groups in one molecule Alkane, (C) is an organic silicon compound having one alkenyl group or hydrosilyl group in one molecule.

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 8-134358

Patent Document 2: Japanese Patent No. 5136963

Patent Document 3: Japanese Patent No. 4409160

Patent Document 4: Japanese Patent No. 4180474

Patent Document 5: Japanese Patent No. 5524017

Patent Document 6: Japanese Patent Application Publication No. 2012-12556

However, the organic polysiloxane-based composition shown in Patent Document 6 has a problem that the oxygen permeability is high, and the gas barrier property against gases such as sulfur is insufficient.

An aspect of the present invention provides an addition reaction-curable resin composition having a low oxygen permeability and good gas barrier properties against gases such as sulfur, and an optical semiconductor device.

The present invention relates to an addition reaction-curable resin composition containing: an organic cyclic compound (A) having two or more functional groups that react with SiH groups by hydrosilylation reaction in one molecule; at least in one molecule Straight-chain organic polysiloxane (B) having two silicon-bonded alkenyl groups that react with SiH groups and at least one silicon-bonded aryl group; at least two SiH groups in one molecule, and at least contains Organic hydrogen polysiloxane (C) of branched-chain organic hydrogen polysiloxane; and curing catalyst (D) required for addition reaction. In addition, the molar ratio of the silicon atom-bonded hydrogen group in the organic hydrogen polysiloxane (C) to all the alkenyl groups in the organic cyclic compound (A) and the linear organic polysiloxane (B) is 0.1 ~4.0, the content of hydrogen atoms bonded to silicon atoms in the organic hydrogen polysiloxane (C) is 1.0 mmol/g~20.0 mmol/g; the organic cyclic compound (A) contains isocyanuric acid derivatives, The total weight of the organic cyclic compound (A), linear organic polysiloxane (B) and organic hydrogen polysiloxane (C) is 100 parts by weight, The organic cyclic compound (A) is 5 to 50 parts by weight.

The addition reaction curable resin composition of the present invention has a low oxygen permeability. In addition, the addition reaction-curable resin composition of the present invention has good gas barrier properties against gases such as sulfur.

The optical semiconductor device of the present invention encapsulates the optical semiconductor element with the cured product of the addition reaction-curable resin composition.

In the optical semiconductor device of the present invention, the optical semiconductor element is sealed with a cured product of an addition reaction-curable resin composition having a low oxygen permeability and good gas barrier properties against gases such as sulfur. Therefore, it is possible to suppress corrosion of the constituent elements of the optical semiconductor element (for example, silver plating for the reflection plate or the electrode portion). Especially for the reflective plate system, the decrease in brightness can be suppressed.

Hereinafter, embodiments of the present invention will be described.

1. An organic cyclic compound (A) having two or more functional groups that react with SiH groups by hydrosilylation reaction in one molecule

An organic cyclic compound (A) having two or more functional groups that react with SiH groups by hydrosilylation reaction in one molecule (hereinafter referred to as organic cyclic compound (A)) will cause an addition reaction-curable resin composition The cured product has a reduced oxygen permeability and improved gas barrier properties against sulfur-generated gases.

The organic cyclic compound (A) is represented by, for example, the following formula (1) Compound.

In the aforementioned formula (1), R ¹ is a monovalent organic group having 1 to 50 carbon atoms, three R ^1s may be the same or different, and at least two of the three R ^1s contain carbon that reacts with SiH groups -Carbon double bond groups. Examples of the organic cyclic compound (A) represented by formula (1) include triallyl isocyanurate, diallyl monoglycidyl isocyanurate, and monomethyl diallyl Base isocyanurate etc.

The compounding amount of the organic cyclic compound (A) is 100 parts by weight relative to the total of the organic cyclic compound (A), the linear organic polysiloxane (B) and the organic hydrogen polysiloxane (C) shown below , Preferably 5 to 50 weight points, more preferably 8 to 30 weight points.

When it is 5 parts by weight or more, the oxygen permeability of the cured product of the addition reaction-curable resin composition is further lowered, and the gas barrier property against gases such as sulfur is further improved. If it is 50 parts by weight or less, the curing reaction of the addition reaction-curable resin composition will not easily occur, and sufficient hardness will be easily obtained. If it is 8 parts by weight or more, the oxygen permeability of the cured product of the addition reaction-curable resin composition will further decrease. The gas barrier will be further improved. If it is 30 parts by weight or less, the hardness of the cured product of the addition reaction-curable resin composition will further increase.

2. Straight-chain organic polysiloxane with at least two silicon-bonded alkenyl groups that react with SiH groups and at least one silicon-bonded aryl group in one molecule (B)

Straight-chain organic polysiloxane (B) having at least two silicon-bonded alkenyl groups that react with SiH groups and at least one silicon-bonded aryl group in one molecule (hereinafter referred to as straight-chain organic polysilicon) Oxane (B)), an organic polysilicon containing at least two carbon-carbon double bonds such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl, etc. in one molecule Oxane.

In the linear organic polysiloxane (B), other organic groups bonded to silicon at the terminal or in the repeating unit include, for example, aryl groups such as phenyl, benzyl, and tolyl.

Specific examples of the linear organic polysiloxane (B) include methylphenylvinylpolysiloxane and the like. When the aryl group bonded to the silicon atom is a phenyl group, it is preferable that 1 to 70 mole% of the entire organic substituent bonded to the silicon atom is a phenyl group. If the phenyl group is 1 mol% or more, the gas barrier property against sulfur-generated gas and the like will be further improved. If the phenyl group is 70 mol% or less, the heat resistance of the cured product of the addition reaction-curable resin composition will be further improved, and the cured product will not easily turn yellow.

3. Organic hydrogen polysiloxane with at least 2 SiH groups in one molecule (C)

Organic hydrogen polysiloxane with at least 2 SiH groups in one molecule (C) (hereinafter referred to as organic hydrogen polysiloxane (C)), an organic polysiloxane containing two or more SiH groups in the terminal and/or repeating structure.

In the organic hydrogen polysiloxane (C), the content of hydrogen atoms bonded to silicon atoms is preferably 1.0 mmol/g to 20.0 mmol/g. If the hydrogen atom content is 1.0 mmol/g or more, the addition reaction-curable resin composition is easy to be excellent in curability, and the hardness of the cured product is improved. If the hydrogen atom content is 20.0 mmol/g or less, it is difficult for the surface of the cured product of the addition reaction-curable resin composition to have viscosity.

The hydrogen atom content is more preferably 1.5 mmol/g or more. If it is 1.5 mmol/g or more, the hardness of the cured product of the addition reaction-curable resin composition will further increase. The hydrogen atom content is more preferably less than 10.0 mmol/g. If it is less than 10.0 mmol/g, it is more difficult to produce viscosity on the surface of the cured product of the addition reaction-curable resin composition.

Examples of the organic group bonded to the silicon atom include methyl, ethyl, and phenyl groups. The organic hydrogen polysiloxane (C) may be, for example, linear or branched. As a specific example of the organic hydrogen polysiloxane (C), methylphenyl hydrogen polysiloxane can be mentioned.

The molar ratio of the silicon atom-bonded hydrogen group in the organic hydrogen polysiloxane (C) to all the alkenyl groups in the organic cyclic compound (A) and linear organic polysiloxane (B) is preferably 0.1 to 4.0 In the range. Within this range, the strength of the cured product of the addition reaction-curable resin composition will be further improved.

4. The curing catalyst required for the addition reaction (D)

The curing catalyst (D) required for the addition reaction promotes the organic ring Hydrogenation reaction of compound (A) with linear organic polysiloxane (B) and organic hydrogen polysiloxane (C). As the curing catalyst (D) required for the addition reaction, for example, publicly known metals, metal compounds, metal complexes and the like having catalytic activity for the hydrosilylation reaction can be used. As the curing catalyst (D) required for the addition reaction, platinum, a platinum compound, and complexes thereof are particularly preferably used.

As the curing catalyst (D) required for the addition reaction, any one of the aforementioned catalysts may be used alone, or two or more of the aforementioned catalysts may be selected and used in combination. In addition, the curing catalyst (D) required for the addition reaction and the auxiliary catalyst may be used together. The amount of the curing catalyst (D) required for the addition reaction is preferably 1 ppm to 50 ppm, and more preferably 5 to 20 ppm, relative to the entire addition reaction curable resin composition. If it is 1 ppm or more, the curability of the addition reaction curable resin composition can be further improved, and the cured product of the addition reaction curable resin composition can be further hardened. If it is 50 ppm or less, the transparency of the cured product of the addition reaction-curable resin composition will be further improved.

5. Adhesiveness-imparting agent (E)

The adhesiveness-imparting agent (E) improves the adhesiveness and the thermal shock resistance caused by repeated cooling and heating. As the adhesion-imparting agent (E), for example, an organosilicon compound containing an epoxy group or an alkoxy group or a condensate thereof can 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 particularly preferably a methoxy group. In addition to alkoxy groups, examples of the group bonded to the silicon atom in the organosilicon compound include substituted or unsubstituted 1 such as alkyl, alkenyl, aryl, aralkyl, and halogen-substituted alkyl groups. Valence hydrocarbon group; 3-glycidoxypropyl, 4-glycidoxybutyl and other glycidoxyalkyl groups; 2-(3,4-epoxycyclohexyl)ethyl, 3-(3 , 4-epoxycyclohexyl)propyl and other epoxycyclohexylalkyl groups; 4-epoxyethylbutyl, 8-epoxyethyloctyl and other monovalent containing epoxy groups such as epoxyethylalkyl Organic groups; monovalent organic groups containing propenyl groups such as 3-methacryloxypropyl; and hydrogen atoms.

In addition, the organosilicon compound preferably has a group that can react with the organic cyclic compound (A) or with the linear organopolysiloxane (B), specifically, it preferably has a silicon atom bonding Alkenyl or silicon atoms bond hydrogen atoms. In addition, from the viewpoint of providing good adhesion to various substrates, the organosilicon compound preferably has at least one monovalent organic group containing one epoxy group in one molecule.

The compounding amount of the adhesion-imparting agent (E) is preferably 100 parts by weight relative to the total of 100 parts by weight of the organic cyclic compound (A), the linear organic polysiloxane (B) and the organic hydrogen polysiloxane (C) 0.01 to 10 weight points, more preferably 0.1 to 5 weight points. If it is 0.01 weight percent or more, the thermal shock resistance will be further improved. If it is 10 parts by weight or less, the curing reaction of the addition reaction-curable resin composition is unlikely to occur, and the hardness of the cured product of the addition reaction-curable resin composition is further increased. If it is 0.1 weight percent or more, the thermal shock resistance will be further improved. If it is 5 parts by weight or less, the hardness of the cured product of the addition reaction-curable resin composition will be higher.

6. Other ingredients

The addition reaction-curable resin composition may contain a reaction inhibitor as another optional component system. Examples of reaction inhibitors include, for example, Alkynols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-ethyn-3-ol, ethynylcycloethanol; 3-methyl-3-pentene-1- Enyne, 3,5-dimethyl-3-hexene-1-enyne and other enyne compounds; 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl ring tetra Siloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, 1,3-divinyltetramethyldisilaxane, benzene And triazole.

The content of the reaction inhibitor is preferably 0.0001 to 1 relative to the total content of the organic cyclic compound (A), the linear organic polysiloxane (B) and the organic hydrogen polysiloxane (C) by 100 parts by weight. Within the range of weight points. Within this range, it is not easy to suppress the curability of the addition reaction-curable resin composition.

In addition, the addition reaction-curable resin composition may contain inorganic fillers, organic fillers, reinforcing materials such as glass fibers, shirasu-balloons, glass, etc. as other optional components within the range that does not impair the purpose of the invention. Hollow bodies such as microbeads, antioxidants, organic pigments, fluorescent pigments, corrosion inhibitors, etc. The inorganic filler has functions such as viscosity adjustment and hardness adjustment. Examples of the inorganic filler include calcium carbonate, silica sand, talc, carbon black, titanium oxide, zinc oxide, kaolin, silicon dioxide, and melamine. Reinforcing materials such as glass fibers have the function of reinforcing the addition reaction-curable resin composition, for example. Hollow bodies such as shirasu-balloons and glass beads have functions such as weight reduction and viscosity adjustment of the addition reaction-curable resin composition.

7. Optical semiconductor device

In the optical semiconductor device, the optical semiconductor element such as an optical semiconductor (for example, LED) is treated by the cured product of the addition reaction-curable resin composition Pieces are sealed.

[Example]

Next, the addition reaction-curable resin composition of the present invention will be described in more detail with examples and comparative examples.

1. Manufacture of addition reaction-curable resin composition

The compounding materials shown in Table 1 were uniformly mixed at the compounding ratio shown in Table 1, to produce the addition reaction curable resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4. The numerical unit indicating the blending amount in Table 1 is weight. Each compounding material in Table 1 is as follows.

A-1: triallyl isocyanurate.

A-2: Diallyl monoglycidyl isocyanurate.

A-3: Monomethyl diallyl isocyanurate.

B-1: Both ends are terminated by M ^Vi unit, the middle unit is composed of D unit, D ^Vi unit or the middle unit includes D unit, D ^Vi unit, viscosity is 10.5Pa.s/25℃, mass average molecular weight is 8900 Straight-chain methyl phenyl vinyl polysiloxane.

B-2: The terminal is capped by M unit and M ^Vi unit, contains D unit and T unit, the viscosity is 18.0Pa.s/25℃, and the mass average molecular weight is 1500 branched methyl phenyl vinyl polysiloxane alkyl.

C-1: The end is capped by M unit and M ^H unit, containing D unit and T unit, the viscosity is 4.5 Pa.s/25℃, the mass average molecular weight is 1500, and the content of hydrogen atoms bonded to silicon atoms is 2.08 mmol /g of branched methylphenyl hydrogen polysiloxane (organic hydrogen polysiloxane).

C-2: expressed as (M ^H ) ₃ T ₁ , a branched methyl group with a viscosity of 0.0025 Pa.s/25°C, a mass average molecular weight of 330, and a hydrogen atom content of 8.5 mmol/g bonded to a silicon atom Phenyl hydrogen polysiloxane (organic hydrogen polysiloxane).

C-3: Expressed as (M ^H ) ₂ D ₁ , a linear methyl group with a viscosity of 0.0004Pa.s/25℃, a mass average molecular weight of 290, and a hydrogen atom content bonded to a silicon atom of 6.01mmol/g Phenyl hydrogen polysiloxane (organic hydrogen polysiloxane).

D-1: Platinum-ethylene dimer complex (Pt: 12%wt).

E-1: A mixture of 3-glycidoxypropyltriethoxysilane and allyltrimethoxysilane at 9:1.

Among them, A-1, A-2 and A-3 correspond to the organic cyclic compound (A). B-1 corresponds to linear organic polysiloxane (B). C-1, C-2 and C-3 correspond to organic hydrogen polysiloxane (C). D-1 corresponds to the curing catalyst (D) required for the addition reaction. E-1 corresponds to the adhesiveness-imparting agent (E).

The following symbols are respectively expressed by the following structural formulas.

Unit M: (CH ₃ ) ₃ SiO _1/2

M ^Vi unit: (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2

M ^H unit: (CH ₃ ) ₂ HSiO _1/2

Unit D: (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

D ^H unit: (CH ₃ )HSiO _2/2

T unit: (C ₆ H ₅ )SiO _3/2

2. Evaluation of addition reaction curable resin composition

(1) Evaluation items and evaluation methods

Exterior

By curing each addition reaction-curable resin composition at 150° C. for 4 hours, a test body having a thickness of 6 mm was prepared. The appearance of the test body was evaluated visually at 23°C.

Durometer hardness

By curing each addition reaction-curable resin composition at 150° C. for 4 hours, a test body having a thickness of 6 mm was prepared. According to JIS K6253-3 (Vulcanized Rubber and Thermoplastic Rubber-Method for Determination of Hardness-Part 3: Hardness of Hardness Tester), the hardness of the tester was measured at 23°C using a type A or D hardness tester.

Refractive index

A test piece having a thickness of 1 mm was prepared by curing each addition reaction-curable resin composition at 150° C. for 4 hours. The refractive index of the test piece was measured with an Abbe refractometer 1T (manufactured by ATAGO).

extend

By curing each addition reaction curable resin composition at 150° C. for 4 hours, a test piece having a thickness of 2 mm was prepared. The elongation of the test piece was measured in accordance with JIS K6249 (Test method for uncured and cured silicone rubber 15. Tensile test). The extension unit is %.

Oxygen permeability

By curing each addition reaction-curable resin composition at 150° C. for 4 hours, a sheet with a thickness of 1 mm was prepared. The oxygen permeability of the sheet was measured in accordance with JIS K7126-1 (Plastics-Films and Sheets-Breathability Test Method-Part 1: Differential Pressure Method).

Sulfur corrosion resistance

An LED package (outer dimension 50×50 mm) with silver plating on the bottom was filled with each addition reaction-curable resin composition, and cured at 150° C. for 4 hours to be a test body. Every three of these test bodies were sealed in a 100 cc glass bottle prefilled with 1 g of sulfur powder, and left at 80° C. for 24 hours. After that, the test body was taken out, and the degree of corrosion in the silver plating on the bottom was visually observed. Based on the observation results, no corrosion was evaluated as ○, the presence of partial corrosion was evaluated as △, and the overall corrosion was evaluated as ×.

Thermal shock resistance

An LED package (outer dimension 50×50 mm) with silver plating on the bottom was filled with each addition reaction-curable resin composition, and cured at 150° C. for 4 hours to be a test body. Each of the 16 test specimens was put into a liquid tank type thermal shock tester TSB-21 (manufactured by espec), and a cycle of 100°C 5 minutes → -40°C 5 minutes was applied for 500 cycles of thermal shock . After cooling to 23 ℃. Finally, visually confirm whether there is peeling of the cured product from the LED package. The case where there is no peeling of each test body is evaluated as ○, and the case where the number of test bodies with small peeling on the LED package interface is 1 to 8 is evaluated as △, and the small or complete peeling of the LED package is evaluated The case where the number of test bodies is 9 to 16 is evaluated as ×.

(2) Evaluation results

The evaluation results are shown in Table 2.

According to the evaluation results, the following effects can be confirmed for the addition reaction curable resin compositions of Examples 1 to 4. The cured products of the addition reaction-curable resin composition of Examples 1 to 4 have a high refractive index. In addition, the addition reaction-curable resin compositions of Examples 1 to 4 do not use a compound with a special structure or organic polysiloxane, so the oxygen permeability is low, and the The gas barrier properties of the generated gas are good. Therefore, the addition reaction-curable resin compositions of Examples 1 to 4 can suppress the corrosion of the silver-plated surface used for light reflecting plates such as LEDs, and are suitable for sealing optical semiconductors such as LEDs.

In addition, the addition reaction curable resin composition of Examples 1 to 3 in which E-1 is blended further improves the effect that the cured product of the addition reaction curable resin composition is applied even if repeated thermal shocks of cold and heat are applied. It is difficult to fall off the optical semiconductor device sealed with the addition reaction-curable resin composition.

Claims (4)

An addition reaction-curable resin composition comprising: an organic cyclic compound (A) having two or more functional groups that react with SiH groups by hydrosilylation reaction in one molecule; at least two compounds in one molecule A silicon-bonded alkenyl group reacting with SiH groups, a linear organic polysiloxane (B) having at least one silicon-bonded aryl group; at least two SiH groups in one molecule, and at least containing branched chain Organic hydrogen polysiloxane (C) of organic hydrogen polysiloxane; and curing catalyst (D) required for addition reaction; silicon atom in organic hydrogen polysiloxane (C) bonds hydrogen group and organic ring The molar ratio of all the alkenyl groups in the compound (A) and the linear organic polysiloxane (B) is 0.1 to 4.0; the hydrogen atom bonded to the silicon atom in the organic hydrogen polysiloxane (C) The content is 1.0mmol/g~20.0mmol/g; the organic cyclic compound (A) contains isocyanuric acid derivatives; relative to the aforementioned organic cyclic compound (A), linear organic polysiloxane (B) And the total amount of organic hydrogen polysiloxane (C) is 100 parts by weight, and the organic cyclic compound (A) is 5 to 50 parts by weight. The addition reaction-curable resin composition as described in claim 1 further contains an adhesion-imparting agent (E). The addition reaction-curable resin composition according to claim 1 or 2, wherein in the linear organic polysiloxane (B), 1 to 70 mole% of the entire organic substituent bonded to the silicon atom is Phenyl. An optical semiconductor device in which an optical semiconductor element is sealed by a cured product of the addition reaction-curable resin composition described in any one of claims 1 to 3.