TWI428374B - Adductive silicone resin composition - Google Patents

Description

Additional polyoxymethylene resin composition

The present invention relates to an excellent adhesion property to a difficult-to-bond substrate such as a polyphthalamide resin, and is excellent in a Sulfur gas barrier, and can be used for an adhesive, a plugging agent, a sealant, and the like. Addition of a polyoxymethylene resin composition.

Since the epoxy resin is excellent in heat resistance and elasticity, it is used in various applications such as an adhesive, a plugging agent, and a sealant, and the demand for an adhesive and a sealant for LEDs has recently increased. Due to the use of various engineering plastics in the LED components, the adhesion of the epoxy resin to these engineering plastics is required. However, its adhesion to engineering plastics such as polyphthalamide resin is not sufficient, so it is required to be improved. Further, in order to suppress the corrosion of silver used as the conduction and reflection metal of the LED, sulfur gas resistance is required.

[Previous Technical Literature]

[Patent Literature]

Patent Documents 1 to 4 disclose various addition-curing type epoxy resin compositions, but any of them has insufficient adhesion to engineering plastics such as polyphthalamide resins, and further improvement is required. In addition, sulfur gas resistance is not sufficient.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-2783

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-266134

[Patent Document 3] Japanese Patent Publication No. 2007-502346

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-63538

The present invention provides an excellent adhesion to a difficult-to-bond substrate such as a polyphthalamide resin, and is excellent in sulfur-blocking gas resistance, and can be used as an addition-molding polyoxyl resin for an adhesive, a plugging agent, a sealant, and the like. Composition.

The addition polyoxymethylene resin composition of the present invention comprises: an organopolyoxane (a) having at least two carbon-carbon double bonds reactive with SiH groups in one molecule, and at least two molecules in one molecule. Reaction of SiH-based organohydrogen polyoxyalkylene (b), addition reaction catalyst (c), and decane coupling agent containing (meth)acrylonyl group with decane coupling agent containing epoxy group (d) .

The addition-molded polyoxyxene resin composition of the present invention is excellent in adhesion to engineering plastics such as polyphthalamide resin. In addition, it is excellent in sulfur gas resistance, and is particularly suitable as an adhesive, a plugging agent, a sealant, and the like for various electronic components such as LEDs.

Here, each component of the addition-molding polyoxyxene resin composition of the present invention will be described. An organopolyoxane (a) having at least two carbon-carbon double bonds reactive with an SiH group in one molecule, containing at least two vinyl groups, allyl groups, and propenyl groups in one molecule An organopolyoxane having a carbon-carbon double bond such as (Propenyl), isopropenyl, butenyl, isobutenyl or hexenyl. The organopolyoxyalkylene may have a branched or cyclic structure, for example, a repeating unit in which the main chain is a diorganooxane and a terminal organotrioxane structure. The organic structure bonded to the terminal and the oxime in the repeating unit is, for example, a methyl group, an ethyl group, a phenyl group or the like. Specific examples include dimethyl polyoxyalkylene having a vinyl group at both ends.

An organohydrogenpolyoxyalkylene (b) having at least two SiH groups in one molecule is an organohydrogenpolyoxyalkylene containing two or more SiH groups in a terminal and/or repeating unit structure. The organohydrogen polyoxyalkylene may have a branched or cyclic structure, for example, a repeating unit in which the main chain is a diorganooxane and a terminal organotrioxane structure. The organic structure bonded to the terminal and the oxime in the repeating unit is, for example, a methyl group, an ethyl group, a phenyl group or the like, and two or more of these groups are replaced by hydrogen.

The addition reaction catalyst (c) is added in order to promote the hydrosilylation of the component (a) and the component (b), and a known metal, a metal compound or a metal complex having a catalytic activity of the hydrogenation reaction reaction can be used. Wait. It is especially preferred to use platinum, a platinum compound and the like. These catalysts may be used singly or in combination of two or more. In addition, the catalyst can be used in combination. The compounding amount of the addition reaction catalyst (c) is preferably from 1 to 50 ppm, more preferably from 5 to 20 ppm, based on the entire composition.

The addition-type polyoxyxene resin composition of the present invention contains, in addition to the components (a) to (c), a reaction of a decane coupling agent having a (meth) acrylonitrile group and a decane coupling agent having an epoxy group. (d). Here, if the decane coupling agent having a (meth) acrylonitrile group and a decane coupling agent having an epoxy group are substituted for (d), the components of the above (a) to (c) are mixed, and the present invention cannot be obtained. effect. That is, it is necessary to first react a decane coupling agent having a (meth) acrylonitrile group with a decane coupling agent having an epoxy group, and then mixing with the components of the above (a) to (c).

The decane coupling agent having a (meth) acrylonitrile group is a compound having a reactive thiol group such as a (meth) acrylonitrile group or an alkoxysilyl group in the molecule. Specific examples thereof include γ-methacryloxypropylmethyldimethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, and γ-methylpropenyloxypropylmethyldi Ethoxy decane, γ-methyl propylene methoxy propyl triethoxy decane, γ-propylene methoxy propyl trimethoxy decane, and the like.

The decane coupling agent having an epoxy group is a compound having a reactive thiol group such as an epoxy group or an alkoxy group in the molecule. The decane coupling agent having an epoxy group may, for example, be β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropyltriethoxydecane, and the like.

The reaction conditions of the decane coupling agent having a (meth) acrylonitrile group and a decane coupling agent having an epoxy group can be sufficiently carried out by stirring and mixing for 24 hours in an environment of 23 ° C. Similarly, it is about 8 hours in an environment of 60 ° C, about 4 hours in an environment of 80 ° C, and about 2 hours in an environment of 100 ° C to sufficiently carry out the reaction.

When a decane coupling agent having a (meth) acrylonitrile group is reacted with a decane coupling agent having an epoxy group, it can be reacted with a vinyl decane coupling agent such as vinyl trimethoxy decane or vinyl triethoxy decane. When the reactant is used as the component (d), the adhesion and the sulfur gas resistance can be further improved. However, when a decane coupling agent having a (meth) acrylonitrile group is replaced with a vinyl decane coupling agent, only a product obtained by reacting a decane coupling agent having a vinyl group with a decane coupling agent having an epoxy group is used as ( When the component is d), the effects of the present invention are not produced. Further, it is preferred to mix the component (d) in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the above-mentioned organopolysiloxane (a).

In the curable epoxy resin of the present invention, various resins and additives may be mixed in addition to the above-mentioned essential components. The viscosity, flexibility, and the like can be adjusted by mixing a diluent. Specific examples thereof include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and di-2-ethylhexyl phthalate. Diester, dimethyl ketone oil, alkyl modified ketone oil, polyether modified ketone oil and other ketone oil, dioctyl adipate, dinonyl adipate, bismuth Dialkyl acid esters, dibutyl sebacate, epoxidized soybean oil, polypropylene glycol, acrylic acid polymers, α-olefins and derivatives thereof, 2-ethylhexyl ester compounds of plant-derived fatty acids, and the like.

For the purpose of viscosity adjustment, viscosity adjustment, increment, etc., fillers such as calcium carbonate, strontium sand, talc, carbon black, titanium oxide, kaolin, cerium oxide, melamine may be added, and glass fibers may be added for reinforcing the hardening resin. For the reinforcing material, a hollow body such as a Shirasu balloon or a glass ball can be added for weight reduction and viscosity adjustment. Further, an antioxidant, a pigment, a preservative, or the like can be suitably used.

Although the embodiments of the present invention and the comparative examples are described in more detail below, the present invention is not limited thereto.

(Example)

Modulation of reactants

Γ-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503), 1 part by weight, γ-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., commodity 1 part by weight of KBM-403) was stirred and mixed for 24 hours in an environment of 23 ° C to obtain a reactant 1. Further, in addition to the above-mentioned compound, vinyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-1003) was used, and in the same manner, according to the mixing and reaction conditions of Table 1, the reactants 2 to 12 were obtained.

[Table 1]

Modulation of addition-forming polyoxyl resin composition

To 100 parts by weight of polymethylvinyl siloxane (viscosity 8.1 Pa ‧ s), 1 part by weight of the above reactant 1 was added. Next, a platinum-vinyloxirane complex as an addition reaction catalyst was added so as to be 10 ppm based on the entire composition, and 10 parts by weight of a mixed methylhydrogenpolysiloxane (viscosity 4.9 Pa ‧) was added thereto. That is, the preparation of the addition-formed polyoxynene resin composition of Example 1 was completed.

In the first embodiment, except that each reactant and each decane coupling agent were added in place of the reactant 1 in the manner described in Tables 2 and 3, the same procedure as in Example 1 was carried out, and Examples 2 to 14 were obtained. Each of the addition-molded polyoxymethylene resin compositions of Comparative Examples 1 to 7 was used.

hardness

Each of the addition-molded polyoxynene resin compositions was heated at 150 ° C for 1 hour to be hardened to obtain a test body having a thickness of 2 mm. The hardness was measured using a durometer A based on JIS K6301.

Adhesion

Each of the addition-molded polyoxynene resin compositions was coated on a polyphthalamide resin sheet (width 25 mm, thickness 2 mm) at a coating amount of 50 g/mm ² to form another polyphthalamide resin. The plate (having a width of 25 mm and a thickness of 2 mm) was bonded so as to overlap each other with a length of 25 mm, and was fixed by a clip and hardened in an environment of 150 ° C for 1 hour. After curing for 24 hours in an environment of 23 ° C, the shearing test was carried out at a tensile speed of 50 mm/min, and the strength was measured and the state of failure was confirmed. Further, a semi-gloss silver-plated SUS plate (having a width of 25 mm, a thickness of 100 μm, and a plating thickness of 3 to 7 μm) was used as the material to be adhered, and the shear strength was measured and the state of failure was confirmed in the same manner.

Corrosive

Each of the addition-molded polyoxyxene resin compositions was coated on a silver-plated copper plate, and heated at 150 ° C for 1 hour to be hardened to form a film having a thickness of 2 mm. The copper plate was sealed with a sulfur powder of 0.2 g in a 100 cc glass bottle, and allowed to stand at 60 ° C or 80 ° C for 24 hours. After the placement, the copper plate was taken out and the silicone resin film was peeled off, and the degree of corrosion of the silver plating layer was confirmed and evaluated in the following manner.

○: no corrosion

△: Partial corrosion (light black)

╳: Total corrosion (blackening)

[Table 2]

[table 3]

Each of the addition-molding polyoxyxene resin compositions of the examples has excellent adhesion to the polyphthalamide resin and is excellent in sulfur gas resistance at 60 °C. Further, in Examples 3 to 14, the semi-gloss silver-plated SUS also had excellent adhesion, and the sulfur gas resistance at 80 ° C was also excellent. On the other hand, each of the addition-molding polyoxyxene resin compositions of the comparative examples had low adhesion to the polyphthalamide resin and the semi-gloss silver-plated SUS, and the silver was corroded because of the low sulfur barrier property.

Claims (3)

An additive-formed polyoxyxene resin composition comprising: an organopolyoxane (a) having at least two carbon-carbon double bonds reactive with an SiH group in one molecule; at least two SiHs in one molecule The organic hydrogen polyoxyalkylene (b); the addition reaction catalyst (c); and the reactant (d) of the (meth)acrylonyl group-containing decane coupling agent and the epoxy group-containing decane coupling agent. The addition-type polyoxyxylene resin composition according to claim 1, wherein the reaction product (d) of the (meth)acryl fluorenyl group-containing decane coupling agent and the epoxy group-containing decane coupling agent is It is a reactant of a decane coupling agent containing a (meth) acrylonitrile group, a decane coupling agent containing an epoxy group, and a decane coupling agent containing a vinyl group. The addition-molding polyoxymethylene resin composition according to the above-mentioned item 1, wherein the component (d) is 0.1 to 20 parts by weight based on 100 parts by weight of the aforementioned organopolyoxane (a). Mixer.