JP2015183012A - addition type silicone resin composition and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an addition type silicone resin composition that has excellent adhesiveness to a difficult-to-bond substrate such as polyphthalamide resin, as well as that also has an excellent sulfur gas barrier property and furthermore has an excellent yellowing resistance under high temperature of 100°C or more, and that is useful as an adhesive agent, a sealing agent, an encapsulating agent etc., and also to provide an optical semiconductor device as sealed with the cured product.SOLUTION: Provided is an addition type silicone resin composition characterized in containing (a) organopolysiloxane that contains in one molecule at least two carbon-carbon double bonds having reactivity with SiH group, (b) organohydrogenpolysiloxane that contains in one molecule at least two SiH groups, (c) addition reaction catalyst, (d) reaction product of (d1) (meth)acryloyl group-containing silane coupling agent and (d2) epoxy group-containing silane coupling agent, and (e) triallyl isocyanurate.

Description

  The present invention has excellent adhesion to difficult-to-adhere substrates such as polyphthalamide resins, and is excellent in sulfur gas barrier properties and heat-resistant yellowing, and is useful as an adhesive, sealing agent, sealant, etc. The present invention relates to a silicone resin composition and an optical semiconductor device sealed with the cured product.

  Silicone resins have excellent heat resistance and elasticity, so they are used in various applications such as adhesives, sealing agents, and sealants. Recently, there is a demand for adhesives and sealants for optical semiconductors such as LEDs. It is increasing. On the other hand, since various engineering plastics are used for the LED member, the silicone resin is required to have adhesion to these engineering plastics. However, the actual situation is that adhesion to engineering plastics such as polyphthalamide resin is not sufficient. Further, in an optical member such as an LED member, yellowing resistance is demanded from the viewpoint of the extraction efficiency of light energy and the color of the extracted light.

  Patent Documents 1 to 4 disclose various addition-curable silicone resin compositions, all of which have a problem of insufficient adhesion to engineering plastics such as polyphthalamide resins. There is a problem that the sulfur gas barrier property is not sufficient. On the other hand, although the invention which solved these subjects is proposed in patent documents 5, there is a subject that a hardened material may turn yellow under high temperature of 100 ° C or more.

Japanese Patent Laid-Open No. 2004-2784 JP 2004-266134 A Special table 2007-502346 gazette JP 2007-63538 A JP 2012-007126 A

The problem to be solved by the present invention has excellent adhesion to difficult-to-adhere base materials such as polyphthalamide resin, is excellent in sulfur gas barrier properties, and is excellent at a high temperature of 100 ° C. or higher. Provided an addition-type silicone resin composition that has yellowing resistance and is useful as an adhesive, sealant, sealant, etc., and the substrate of an optical semiconductor device is a hardly adhesive substrate such as a polyphthalamide resin. Even if the sealing agent is not peeled off easily, the silver surface of the silver-plated reflector is less likely to corrode, and even when used at a high temperature of 100 ° C. or higher, the light energy An object of the present invention is to provide an optical semiconductor device in which the extraction efficiency does not decrease and the color of the extracted light does not change to yellow.

  In order to solve the above problems, the invention according to claim 1 is characterized in that organopolysiloxane (a) containing at least two carbon-carbon double bonds reactive with SiH group in one molecule is at least in one molecule. Reaction of organohydrogenpolysiloxane (b) containing two SiH groups, addition reaction catalyst (c), (meth) acryloyl group-containing silane coupling agent (d1) and epoxy group-containing silane coupling agent (d2) An addition-type silicone resin composition comprising the product (d) and triallyl isocyanurate (e) is provided.

  The invention according to claim 2 is characterized in that the reactant (d) comprises a (meth) acryloyl group-containing silane coupling agent (d1), an epoxy group-containing silane coupling agent (d2), and a vinyl group-containing silane coupling agent. The addition type silicone resin composition according to claim 1, wherein the addition type silicone resin composition is a reaction product of (d3).

  The invention according to claim 3 is characterized in that 0.1 to 20 parts by weight of the reactant (d) is blended with 100 parts by weight of the organopolysiloxane (a). Alternatively, an addition-type silicone resin composition described in 2 is provided.

  The invention according to claim 4 is based on 100 parts by weight of the organopolysiloxane (a), the organohydrogenpolysiloxane (b), the addition reaction catalyst (c), and the reaction product (d). The addition type silicone resin composition according to any one of claims 1 to 3, wherein 0.05 to 10 parts by weight of triallylisoianurate (e) is blended.

  According to a fifth aspect of the present invention, there is provided an optical semiconductor device which is sealed with a cured product of the addition-type silicone resin composition according to any one of the first to fourth aspects.

  The addition-type silicone resin composition of the present invention has the effect of being excellent in adhesion to engineering plastics such as polyphthalamide resin and also having excellent sulfur gas barrier properties. Moreover, it has the effect of having excellent yellowing resistance at a high temperature of 100 ° C. or higher. For this reason, there exists an effect of being especially suitable as an optical semiconductor device, such as LED, and an adhesive agent, sealing agent, sealing agent, etc. of various electronic members.

  In addition, the optical semiconductor device sealed with the cured product of the addition-type silicone resin composition of the present invention is a sealing agent even if the substrate of the optical semiconductor device is a hardly adhesive substrate such as polyphthalamide resin. A cured product of an addition type silicone resin composition of the present invention is not easily peeled off, the silver surface of a silver-plated reflector is less likely to corrode, and is used at a high temperature of 100 ° C. or higher. However, the light energy extraction efficiency does not decrease, and the color of the extracted light does not change to yellow.

  Each component of the addition-type silicone resin composition of this invention is demonstrated.

  Organopolysiloxane (a) containing at least two carbon-carbon double bonds having reactivity with SiH group in one molecule is vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, An organopolysiloxane containing at least two carbon-carbon double bonds such as a hexenyl group in one molecule. Examples of the organopolysiloxane include those having a main chain of a repeating unit of diorganosiloxane and a terminal having a triorganosiloxane structure, and may have a branched or cyclic structure. Examples of the organo group bonded to silicon in the terminal or repeating unit include a methyl group, an ethyl group, and a phenyl group. Specific examples include methylphenyl polysiloxane having vinyl groups at both ends.

  The organohydrogenpolysiloxane (b) containing at least two SiH groups in one molecule is an organopolysiloxane containing two or more SiH groups in the terminal and / or repeating structure. Examples of the organopolysiloxane include those having a main chain of a repeating unit of diorganosiloxane and a terminal having a triorganosiloxane structure, and may have a branched or cyclic structure. Examples of the organo group bonded to silicon in the terminal or repeating unit include a methyl group, an ethyl group, an octyl group, and a phenyl group, and it can be said that two or more of these are substituted with a hydrogen group. The mixing ratio of the organopolysiloxane (a) and the organohydrogenpolysiloxane (b) is such that the molar ratio of vinyl group and SiH group is (a) :( b) = 1: 0.5 to 3.0. Preferably, (a) :( b) = 1: 0.8 to 2.0.

  The addition reaction catalyst (c) is added to promote the hydrosilylation reaction of the component (a) and the component (b), and a known metal, metal compound, metal complex or the like having catalytic activity for the hydrosilylation reaction is added. 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 0.1 ppm to 1000 ppm, more preferably 0.5 to 200 ppm, and even more preferably 1 to 50 ppm with respect to the entire composition.

  In addition to the components (a) to (c), the addition-type silicone resin composition of the present invention comprises (meth) acryloyl group-containing silane coupling agent (d1) and epoxy group-containing silane coupling agent (d2). It contains a reactant (d). Here, instead of (d), the effect of the present invention can be obtained by simply mixing a (meth) acryloyl group-containing silane coupling agent and an epoxy group-containing silane coupling agent with the components (a) to (c). Cannot be obtained. That is, it is necessary that the (meth) acryloyl group-containing silane coupling agent and the epoxy group-containing silane coupling agent are reacted in advance and mixed with the components (a) to (c).

  The (meth) acryloyl group-containing silane coupling agent (d1) is a compound having a reactive silyl group such as a (meth) acryloyl group and an alkoxysilyl group in the molecule. Specifically, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane Etc.

  The epoxy group-containing silane coupling agent (d2) is a compound having a reactive silyl group such as an epoxy group and an alkoxysilyl group in the molecule. Specific examples of the epoxy group-containing silane coupling agent include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ- Examples thereof include glycidoxypropyltriethoxysilane.

  When the (meth) acryloyl group-containing silane coupling agent and the epoxy group-containing silane coupling agent are reacted, the vinyl group-containing silane coupling agent (d3) can be further reacted, and this reactant is converted into a reactant (d ) Can further improve adhesion and sulfur gas barrier properties. Specific examples of the vinyl group-containing silane coupling agent include vinyltrimethoxysilane and vinyltriethoxysilane.

  As a condition for reacting each silane coupling agent, the reaction proceeds sufficiently by stirring and mixing for about 24 hours under an atmosphere of 23 ° C. Similarly, the reaction proceeds sufficiently by stirring and mixing for about 8 hours in a 60 ° C. atmosphere, for about 4 hours in a 80 ° C. atmosphere, and for about 2 hours in a 100 ° C. atmosphere. In order to accelerate the reaction, a metal chelate catalyst may be added, and specific examples include an aluminum compound, a zirconium compound and a titanium compound. Further, water may be added. These reaction accelerators exhibit a sufficient effect when added in an amount of about 100 to 1000 ppm with respect to the reaction system.

  The (meth) acryloyl group-containing silane coupling agent (d1) and the epoxy group-containing silane coupling agent (d2) are preferably reacted at a weight ratio of (d1) :( d2) = 1: 1 to 10. The (meth) acryloyl group-containing silane coupling agent (d1), the epoxy group-containing silane coupling agent (d2), and the vinyl group-containing silane coupling agent (d3) are (d1) :( d2) :( It is preferable to make it react by d3) = 1: 1-10: 1-1.5.

  Moreover, it is preferable to mix | blend 0.1-20 weight part of reactant (d) with respect to 100 weight part of said organopolysiloxane (a), and it is more preferable to mix | blend 0.5-10 weight part. If it is less than 0.1 part by weight, the adhesion, sulfur gas barrier property and heat-and-moisture resistance will decrease, and if it exceeds 20 parts by weight, the viscosity of the composition will decrease and the hardness and mechanical strength of the cured product will decrease. The weight loss during curing of the resin increases. If it is less than 0.5 part by weight, the adhesion, sulfur gas barrier property and heat-and-moisture resistance tend to decrease, and if it exceeds 10 parts by weight, the viscosity of the composition decreases and the hardness and mechanical strength of the cured product tend to decrease. is there.

  The triallyl isocyanurate (e) used in the addition-type silicone resin composition of the present invention includes the organopolysiloxane (a), the organohydrogenpolysiloxane (b), the addition reaction catalyst (c), and the The addition type silicone resin composition comprising the reactant (d) is blended for the purpose of imparting heat-resistant yellowing. The triallyl isocyanurate (e) is blended in the amount of the organopolysiloxane (a), the organohydrogenpolysiloxane (b), the addition reaction catalyst (c), and the reactant (d) 100. It is preferable that 0.05-10 weight part is mix | blended with respect to a weight part, More preferably, 0.1-5.0 weight part is mix | blended.

  When the amount of triallyl isocyanurate (e) is less than 0.05 parts by weight, heat-resistant yellowing is insufficient, and when it exceeds 10 parts by weight, the hardness of the cured product is low. If it is less than 0.1 parts by weight, the heat-resistant yellowing tends to be insufficient, and if it exceeds 5 parts by weight, the hardness of the cured product tends to be low.

  In addition to the essential components, various resins and additives can be blended in the addition-type silicone resin composition of the present invention. Viscosity, flexibility, etc. can be adjusted by blending the diluent. Specific examples include phthalate-based diluents such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, silicone oils such as dimethyl silicone oil, alkyl-modified silicone oil, and polyether-modified silicone oil. , Dioctyl adipate, diisononyl adipate, dialkyl azelate, dibutyl sebacate, epoxidized soybean oil, polypropylene glycol, acrylic polymer, α-olefin and derivatives thereof, and 2-ethylhexyl ester compounds of vegetable oil-derived fatty acids.

  Glass fiber for reinforcing inorganic fillers and organic fillers such as calcium carbonate, cinnabar, talc, carbon black, titanium oxide, kaolin, silicon dioxide, melamine, and cured resin for the purpose of viscosity adjustment, viscosity adjustment, and weight increase A hollow body such as a shirasu balloon or a glass balloon can be added for the purpose of reducing the weight and adjusting the viscosity. In addition, antioxidants, pigments, preservatives, and the like can be used as appropriate.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and demonstrated in detail about this invention, a specific example is shown and it does not specifically limit to these.

Preparation of reactant (d) 2 parts by weight of γ-methacryloxypropyltrimethoxysilane and 8 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were mixed to obtain an initial mixture, The mixture was stirred and mixed at 80 ° C. for 3 hours to obtain a reaction product (d).

Preparation of addition-type silicone resin composition

Examples and Comparative Examples Polyvinylsiloxane A1 (viscosity 8 Pa · s / 25 ° C., vinyl group content; 1.8 to 2.1 mmol / g), polyvinylsiloxane A2 (viscosity 18.5 Pa · s) as organopolysiloxane (a) / 25 ° C., vinyl group content; 2.46 to 2.58 mmol / g), polyvinylsiloxane A3 (viscosity 18.5 Pa · s / 25 ° C., vinyl group content; 5.62 to 5.67 mmol / g), Divinylsiloxane (viscosity 7 Pa · s / 25 ° C., vinyl group content; 0.17 mmol / g) was used as the organohydrogenpolysiloxane (b), polyhydrogensiloxane B1 (viscosity 50 mPa · s / 25 ° C., SiH group) Content: 8.6 to 9.2 mmol / g), polyhydrogensiloxane B2 (viscosity 3 to 7 Pa · s / 25 ° C., SiH group content; 0.17 to 0.2) mmol / g), and a trial (is a product name, manufactured by Nippon Kasei Co., Ltd.) is used as triallyl isocyanurate (e), and the reactant (d) is added to organopolysiloxane (a) according to the formulation shown in Table 1. ) And triallyl isocyanurate (e), and then a platinum-vinylsiloxane complex (trade name Pt-VTSC-12.0 VTS Pt: 12% wt manufactured by Umicore) as an addition reaction catalyst (c), It is added so as to be 5 ppm or 10 ppm with respect to the total amount of the organopolysiloxane (a) and the organohydrogenpolysiloxane (b), then the organohydrogenpolysiloxane (b) is added, and ethynylcyclohexane is further used as a curing retarder. Hexanol is 1000 ppm or 2 based on the total amount of organopolysiloxane (a) and organohydrogenpolysiloxane (b). Addition-type silicone resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were obtained by adding and mixing to 000 ppm.

Evaluation items and evaluation methods

Hardness Each addition type silicone resin composition was cured at 150 ° C. for 4 hours to prepare a specimen having a thickness of 6 mm. The hardness was measured using a hardness meter A in accordance with JIS K6301.

PPA adhesion Each addition type silicone resin composition was applied to a polyphthalamide resin plate (width 25 mm, 2 mm thickness, length 70 mm) at an application amount of 50 g / m ² , and another polyphthalamide resin plate (width 25 mm, 2 mm). (Thickness) was laminated so as to overlap each other by 25 mm in the length direction, fixed with a clip, and cured at 150 ° C. for 1 hour. After curing for 24 hours in a 23 ° C. atmosphere, a shear test was performed at a pulling rate of 50 mm / min, and the cohesive failure of the addition-type silicone resin composition was evaluated as “good”.

Silver adhesion Each addition type silicone resin composition was applied to a semi-glossy silver-plated SUS plate (width 25 mm, 100 μm thickness, plating thickness 3 to 7 μm, length 70 mm) at a coating amount of 50 g / m ² , and another semi-glossy silver Plated SUS plates (width 25 mm, 100 μm thickness, plating thickness 3 to 7 μm, length 70 mm) were bonded so as to overlap each other in the length direction by 25 mm, fixed with clips, and cured at 150 ° C. for 1 hour. After curing for 24 hours in a 23 ° C. atmosphere, a shear test was performed at a pulling rate of 50 mm / min, and a peel strength of 0.1 N or more was evaluated as “good”.

Each addition type silicone resin composition was apply | coated and hardened | cured on the copper plate which gave sulfur gas barrier silver plating, and the film | membrane with a thickness of 2 mm was formed. The copper plate was sealed in a 100 cc glass bottle together with 0.2 g of sulfur powder, and allowed to stand at 60 ° C. or 80 ° C. for 24 hours. After leaving, the copper plate was taken out, the silicone film was peeled off, and the degree of corrosion of the silver plating was confirmed and evaluated as follows.
○: No corrosion △: Partially corroded (light black)
×: Overall corrosion (blackening)

Heat-resistant yellow-modified each addition type silicone resin composition was cured at 150 ° C. for 4 hours, and then left at 150 ° C. for 100 hours. evaluated.

Evaluation results The evaluation results are shown in Table 2.

Claims (5)

  Organopolysiloxane containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule (a) Organohydrogenpolysiloxane containing at least two SiH groups in one molecule (b) An addition reaction catalyst (c), a reaction product (d) of a (meth) acryloyl group-containing silane coupling agent (d1) and an epoxy group-containing silane coupling agent (d2), and triallyl isocyanurate (e) An addition-type silicone resin composition characterized by comprising:   The reactant (d) is a reactant of a (meth) acryloyl group-containing silane coupling agent (d1), an epoxy group-containing silane coupling agent (d2), and a vinyl group-containing silane coupling agent (d3). The addition-type silicone resin composition according to claim 1.   The addition type silicone resin according to claim 1 or 2, wherein 0.1 to 20 parts by weight of the reactant (d) is blended with 100 parts by weight of the organopolysiloxane (a). Composition.   With respect to 100 parts by weight of the mixture of the organopolysiloxane (a), the organohydrogenpolysiloxane (b), the addition reaction catalyst (c), and the reactant (d), triallylisoianurate (e The addition-type silicone resin composition according to any one of claims 1 to 3, wherein 0.05 to 10 parts by weight is blended. An optical semiconductor device sealed with a cured product of the addition-type silicone resin composition according to any one of claims 1 to 4.