JP2007191698A - Epoxy/silicone hybrid resin composition and cured material from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy/silicone hybrid resin composition being solid at a normal temperature, which exhibits improved workability in cast molding because the composition is solid at a normal temperature, and which gives a cured material having excellent heat and light resistance as compared to a conventional epoxy resin, to thereby offer a great deal of advantages in the industry. <P>SOLUTION: The epoxy/silicone hybrid resin composition comprises (A) an organosilicon compound having at least one hydroxy group bonded to a silicon atom, (B) an epoxy resin free of a phenylene ether skeleton and (C) an aluminum-based curing catalyst. At least one of the components (A) and (B) is solid at a normal temperature. And the composition is also solid at a normal temperature. A cured material is obtained by subjecting the composition to cast molding. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an epoxy / silicone hybrid resin composition suitable for casting and having excellent heat resistance and light resistance as compared with an epoxy resin, and a cured product thereof.

  Until now, solid resin at room temperature has been used as a material for cast molding because of its good workability. Among these, epoxy resins excellent in electrical characteristics, moisture resistance, light transmission, heat resistance, and the like are used as sealing resins for semiconductors and optical semiconductors.

  On the other hand, the present inventors have a suitable epoxy / silicone hybrid resin composition as a sealing resin for optical semiconductors, which has no surface tack, is excellent in adhesiveness, and has better heat resistance and light resistance than an epoxy resin. A light-emitting semiconductor device that has been coated using this and has high light emission efficiency has been provided (see Japanese Patent Application Laid-Open No. 2005-158766).

  However, conventionally, there has been no report on an aspect suitable as a solid epoxy / silicone hybrid resin composition suitable for casting.

JP 2005-158766 A

  The present invention has been made in view of the above circumstances, and solidifies an epoxy-silicone hybrid resin composition that has been a low-viscosity or viscous liquid at room temperature so as to improve workability in casting. Moreover, it aims at providing the hardened | cured material of the said composition excellent in heat resistance and light resistance.

  As a result of intensive studies to achieve the above object, the present inventor has (A) an organosilicon compound having one or more silicon atom-bonded hydroxyl groups in one molecule, (B) an epoxy resin having no phenylene ether skeleton, And (C) an epoxy-silicone hybrid resin composition containing an aluminum-based curing catalyst as an essential component, by making at least one of the component (A) and the component (B) solid at room temperature. It has been found that a solid material having no tack property at room temperature suitable for casting molding such as transfer molding, particularly a powdered material, and a cured product of this composition has excellent heat resistance and light resistance. Is.

  In particular, the component (A) has (A ′) a group containing multiple bonds that can participate in one or more hydrosilylation reactions in one molecule, and one or more silicon atom-bonded hydroxyl groups. An epoxy-silicone hybrid resin composition which is an organosilicon compound and further comprises (D) an organohydrogenpolysiloxane and (E) a platinum group metal catalyst together with the components (A ′), (B) and (C) Wherein at least one of the component (A ′), the component (B) and the component (D) is solid at room temperature, and the component (A) is one per molecule in the molecule (AD). An organosilicon compound having a group containing multiple bonds that can participate in the hydrosilylation reaction, having one or more silicon atom-bonded hydrogen atoms, and having one or more silicon atom-bonded hydroxyl groups; In addition to the component, the component (B) and the component (C), (E) an epoxy-silicone hybrid resin composition using a platinum group metal catalyst in combination, at least one of the component (AD) and the component (B) is at room temperature. In this case, the composition can be made solid at room temperature suitable for cast molding, and an epoxy resin that combines a curing reaction by hydrosilylation and a curing reaction of an epoxy resin in such a curing reaction. It has been found that the cured product of the silicone hybrid resin composition is particularly excellent in heat resistance and light resistance, and has led to the present invention.

Therefore, the present invention essentially comprises (A) an organosilicon compound having one or more silicon atom-bonded hydroxyl groups in one molecule, (B) an epoxy resin not having a phenylene ether skeleton, and (C) an aluminum-based curing catalyst. An epoxy-silicone hybrid resin composition contained as a component, wherein at least one of the component (A) and the component (B) is solid at room temperature, and the composition is solid at room temperature Epoxy / silicone hybrid resin composition,
(A ′) an organosilicon compound having a group containing multiple bonds that can participate in one or more hydrosilylation reactions in one molecule and having one or more silicon atom-bonded hydroxyl groups, (B) a phenylene ether skeleton An epoxy / silicone hybrid resin composition containing, as essential components, an epoxy resin not having (C) an aluminum-based curing catalyst, (D) an organohydrogenpolysiloxane, and (E) a platinum group metal-based catalyst, An epoxy / silicone hybrid resin composition, wherein at least one of the component (A ′), the component (B), and the component (D) is solid at room temperature, and the composition is solid at room temperature;
(AD) one molecule having a group containing multiple bonds that can participate in one or more hydrosilylation reactions, one or more silicon atom-bonded hydrogen atoms, and one or more silicon atom-bonded hydroxyl groups An organosilicon compound having (B) an epoxy resin having no phenylene ether skeleton,
(C) An epoxy-silicone hybrid resin composition containing an aluminum-based curing catalyst and (E) a platinum group metal-based catalyst as essential components, wherein at least one of the (AD) component and (B) component is at room temperature An epoxy / silicone hybrid resin composition, which is solid and the composition is solid at room temperature, and a cured product obtained by casting the epoxy / silicone hybrid resin composition I will provide a.

  The epoxy / silicone hybrid resin composition that is solid at room temperature of the present invention is solid at room temperature, so that the workability in cast molding is improved, and the cured product has excellent heat resistance and light resistance compared to conventional epoxy resins. The industrial merit is great.

Hereinafter, the present invention will be described in more detail.
The epoxy-silicone hybrid resin composition of the present invention is
(A) an organosilicon compound having one or more silicon atom-bonded hydroxyl groups in one molecule;
(B) An epoxy resin not having a phenylene ether skeleton and (C) an aluminum-based curing catalyst are contained as essential components, and at least one of the (A) component and the (B) component is at room temperature (ie, 25 ° C., the same applies hereinafter) ) And the composition is solid at room temperature.

Particularly, (A) component (A ′) an organosilicon compound having one or more groups containing multiple bonds that can participate in hydrosilylation reaction in one molecule and one or more silicon atom-bonded hydroxyl groups Together with the components (A ′), (B) and (C),
(D) contains organohydrogenpolysiloxane and (E) platinum group metal catalyst as essential components, and at least one of (A ′) component, (B) component and (D) component is solid at room temperature, And what the composition is solid at normal temperature is preferable.

The component (A) has (AD) one or more groups containing multiple bonds that can participate in hydrosilylation reaction in one molecule, one or more silicon-bonded hydrogen atoms, and 1 In the case of an organosilicon compound having one or more silicon atom-bonded hydroxyl groups, together with the (AD) component and the (B) and (C) components,
(E) A platinum group metal catalyst as an essential component, at least one of the (AD) component and the (B) component is solid at room temperature, and the composition is preferably solid at room temperature.

  Component (A) is an organosilicon compound having one or more silicon atom-bonded hydroxyl groups in one molecule. Among them, (A ′) multiple bonds that can participate in one or more hydrosilylation reactions in one molecule. An organosilicon compound having a group to be contained and having at least one silicon atom-bonded hydroxyl group is preferred.

Examples of such compounds include organo (poly) siloxanes, organosylalkylenes, organosylarylenes and the like. Particularly, in the case of organo (poly) siloxanes, the following average composition formula (1)
R ¹ _a R ² _b (HO) _c (R ³ O) _d SiO _{(4-abcd) / 2} (1)
Wherein R ¹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group having an aliphatic unsaturated bond, and R ² is the same or different, substituted or non-substituted without aliphatic unsaturated bond. A substituted monovalent hydrocarbon group, R ³ is the same or different substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, a, b and d are each 0 or a positive number; c is a positive number, but in the case of the component (A ′), a> 0, and a + b + c + d <4.)
It is possible to use the one shown in.

In this case, R ¹ , R ² and R ³ each preferably have 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms. Specific examples of R ¹ include alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, and butenyl group, acryloxy group, methacryloxy group, and the like. Representative examples of R ² include alkyl groups such as methyl, ethyl, propyl, butyl, and cyclohexyl groups, aryl groups such as phenyl and tolyl groups, aralkyl groups such as benzyl groups, and organic groups having an oxirane ring. It is mentioned as a typical thing. Examples of R ³ include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, and aryl groups such as phenyl group.

  When the component (A) (component (A ′)) is an organopolysiloxane, in the above formula (1), a, b, c and d are 0 ≦ a ≦ 0.5, particularly 0 ≦ a ≦ 0. .25 (provided that a> 0 in the case of the component (A ′)), 0 <b ≦ 2.4, particularly 0.5 ≦ b ≦ 2, 0 <c ≦ 0.5, particularly 0.01 ≦ c ≦ It is preferable that 0.2, 0 ≦ d ≦ 0.5, particularly 0 ≦ d ≦ 0.2, and a + b + c + d is 0.8 ≦ a + b + c + d ≦ 3, particularly 1 ≦ a + b + c + d ≦ 2.5.

  In addition, as the component (A), (AD) one molecule has a group containing multiple bonds that can participate in one or more hydrosilylation reactions, one or more silicon atom-bonded hydrogen atoms, and Also preferred are organosilicon compounds having one or more silicon-bonded hydroxyl groups. The (AD) component is a group containing a silicon atom-bonded hydrogen atom (SiH group) in one molecule and a multiple bond that can participate in a hydrosilylation reaction in another molecule, such as an aliphatic unsaturated group such as a vinyl group. It is cured by an addition reaction (hydrosilylation) with a valent hydrocarbon group.

Examples of such compounds include organo (poly) siloxanes, organosylalkylenes, organosylarylenes and the like. Particularly, in the case of organo (poly) siloxanes, the following average composition formula (2)
^{_{H e R 1 f R 2 g}} (HO) h (R 3 O) j SiO (4-efghj) / 2 (2)
Wherein R ¹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group having an aliphatic unsaturated bond, and R ² is the same or different, substituted or non-substituted without aliphatic unsaturated bond. A substituted monovalent hydrocarbon group, R ³ is the same or different substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, e, f and h are positive numbers, g, Each j is 0 or a positive number, and e + f + g + h + j <4.)
It is possible to use the one shown in. Specific examples of R ¹ , R ² and R ³ are the same as those exemplified in the above formula (1).

  When the (AD) component is an organopolysiloxane, in the above formula (2), e, f, g, h, j are 0 <e ≦ 0.5, particularly 0 <e ≦ 0.25, 0 <F ≦ 0.5, especially 0 <f ≦ 0.25, 0 <g ≦ 2.4, especially 0.5 ≦ g ≦ 2, 0 <h ≦ 0.5, especially 0.01 <h ≦ 0. 2, 0 ≦ j ≦ 0.5, particularly 0 ≦ j ≦ 0.2, and e + f + g + h + j is preferably 0.8 ≦ e + f + g + h + j ≦ 3, particularly 1 ≦ e + f + g + h + j ≦ 2.5.

  The silicon atom-bonded hydroxyl group (silanol group) -containing organo (poly) siloxane can be produced by (co) hydrolysis or partial hydrolysis of a hydrolyzable silane.

Examples of organopolysiloxanes containing silicon atom-bonded hydroxyl groups (silanol groups) include (CH ₃ ) ₂ (OH) SiO _1/2 , (CH ₃ ) ₂ SiO, CH ₃ (C ₆ H ₅ ) (OH) SiO _{1/2 , CH 3 SiO 3/2, (C} 6 H 5) SiO 3/2, CH 3 (C 6 H 5) SiO, C 3 H 7 (CH 3) SiO, (CH 2 = CH) (C 6 H 5 ) (OH) SiO _1/2 , C ₆ H ₅ (CH ₂ ═CH) (CH ₃ ) SiO _1/2 , (CH ₂ ═CH) (CH ₃ ) SiO, (CH ₂ ═CH) (C ₆ H _{5) SiO, C 6 H 5} (OH) SiO, including _{(CH 3) 2 SiO, (} C 6 H 5) 2 SiO, C 6 H 5 (CH 3) siloxane units selected from such ₂ SiO _1/2 And may contain a small amount of SiO ₂ units. This type of organopolysiloxane can be obtained by hydrolyzing the organochlorosilane corresponding to the siloxane unit and further condensing the hydroxyl groups to leave the required amount of hydroxyl groups.

As the component (A) (component (A ′), component (AD)), one having a branched or three-dimensional network structure containing a trifunctional siloxane unit or a tetrafunctional siloxane unit (SiO ₂ ) in the molecule is used. Is preferred.

  Thus, the silicon atom-bonded hydroxyl group-containing organopolysiloxane is liquid to solid, but the silicon atom-bonded hydroxyl group content is 0.5 to 15% by mass, particularly 1.5 to 10% by mass. preferable. If the content is less than 0.5% by mass, the reactivity with the epoxy group is poor, and if it exceeds 15% by mass, the organopolysiloxane may not be stably produced.

  In addition to these organo (poly) siloxanes, organosilalkylene, organosilarylene, and silanol group-containing organopolysiloxane having a silethylene or silphenylene bond can also be used in the present invention.

  In addition, it is preferable that the organosilicon compound of (A) component contains organopolysiloxane especially. Among the organosilicon compounds, those having an aliphatic unsaturated hydrocarbon group such as an alkenyl group as the group containing multiple bonds that can participate in the hydrosilylation reaction in the molecule (A ′) component or (AD) component However, when the component (A ′) is used as the component (A), the component (D) and the component (E) are included as essential components, and the component (AD) is included as the component (A). When used, the component (E) is contained as an essential component.

  The epoxy resin having no phenylene ether skeleton of the component (B) does not have a phenylene ether skeleton, for example, bisphenols such as bisphenol A and bisphenol F, which are raw materials for epoxy resins, and phenyleneoxy groups derived from biphenyldiols. Although it depends on the proportion of the epoxy resin in the total organic resin, an epoxy resin that is solid at room temperature or liquid with a viscosity of 100 Pa · s or more is preferable. Types include hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated biphenyl type epoxy resin oligomer and polymer, alicyclic epoxy resin, etc. with good heat resistance and light resistance. However, it is not limited to these as long as the epoxy resin does not have a phenyl ether skeleton.

  The ratio of the epoxy resin to the total organic resin (that is, the sum of the components (A), (B) and (D), (the sum of the components (A) and (B) when the component (D) is not used)) is It is preferable that it is 5-90 mass%. If this ratio is less than 5% by mass, the effect of epoxy addition is insufficient, and the cured product strength may not be sufficiently obtained. On the other hand, when this ratio exceeds 90% by mass, the epoxy content increases. For example, in discoloration in a heat resistance test and a light resistance test, there is no significant difference from a simple epoxy resin. For this reason, it is 20-80 mass% more desirably.

  The (C) component aluminum-based curing catalyst is a curing catalyst for polymerizing silanol groups and epoxy groups. Specifically, aluminum trihydroxide, aluminum alcoholates, aluminum acylates, salts of aluminum acylates, aluminosiloxy compounds And an organic or inorganic aluminum compound selected from the group consisting of aluminum chelates, and the compounding amount is a so-called catalytic amount. For example, the total amount of components (A), (B) and (C), When the component (A ′) is used, the total amount of the components (A ′), (B), (C), (D) and (E), and when the component (AD) is used, (AD), (B), It is 0.05-10 mass% with respect to the total amount of (C) and (E) component, Preferably it can be 0.3-5 mass%. If this amount is less than 0.05% by mass, a sufficient curing rate may not be obtained, and if it exceeds 10% by mass, curing may be too fast to produce the intended light emitting semiconductor device. .

  The (D) component organohydrogenpolysiloxane acts as a cross-linking agent, and includes a SiH group in the (D) component and a group containing multiple bonds that can participate in the hydrosilylation reaction in the (A ′) component. For example, it is cured by addition reaction (hydrosilylation) with an aliphatic unsaturated monovalent hydrocarbon group such as a vinyl group. In addition, when the (AD) component is used, the (D) component can be added as necessary. In this case, the SiH group in the (D) component and the hydrosilylation reaction in the (AD) component are used. Addition reaction (hydrosilylation) with a group containing multiple bonds that can participate, for example, an aliphatic unsaturated monovalent hydrocarbon group such as a vinyl group, can supplement the curing reaction.

Such organohydrogenpolysiloxane is, for example, the following average composition formula (3)
H _k R ⁴ _m (HO) _n (R ⁵ O) _p SiO _{(4-kmnp) / 2} (3)
(Wherein R ⁴ is the same or different substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, and R ⁵ is the same or different substituted or unsubstituted hydrogen containing no aliphatic unsaturated bond. (It is a monovalent hydrocarbon group, and k> 0, m> 0, n ≧ 0, p ≧ 0, and k + m + n + p <4.)
And one having at least 2, preferably 3 or more hydrogen atoms (SiH groups) bonded to a silicon atom in one molecule.

Here, R ⁴ in the above formula (3) is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 7 carbon atoms, such as a lower alkyl group such as a methyl group, a phenyl group, etc. And those exemplified for the substituent R ² in the above formula (1). R ⁵ in the above formula (3) is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and the same as R ^{3 in the} above formula (1). Can be mentioned.

  k, m, n, p are 0 <k ≦ 1, especially 0.001 ≦ k ≦ 0.8, 0 <m ≦ 3, especially 0.5 ≦ m ≦ 2.3, 0 ≦ n ≦ 1, It is preferable that 0 ≦ n ≦ 0.5, 0 ≦ p ≦ 3, particularly 0 ≦ p ≦ 1.5, and k + m + n + p is 1 ≦ k + m + n + p <4, particularly 1.5 ≦ k + m + n + p ≦ 2.7. Is preferred. The position of the hydrogen atom bonded to the silicon atom is not particularly limited, and may be at the end of the molecule or in the middle.

  Specifically, for example, end-capped organos such as terminal trimethylsilyl group or triphenylsilyl group-capped organo (eg methyl) hydrogen polysiloxane, terminal dimethylhydrogensilyl group-capped organo (eg methyl) hydrogen polysiloxane, etc. (For example, methyl) hydrogen polysiloxane, tetramethyltetrahydrogencyclotetrasiloxane, pentamethyltrihydrogencyclotetrasiloxane, tri (dimethylhydrogensiloxane) methylsilane, and the like.

Moreover, a compound as shown by the following structure can also be used.

The component (D) may be linear, branched, cyclic, or network-like in terms of molecular structure. Such organohydrogenpolysiloxanes are usually R ⁴ SiHCl ₂ , (R ⁴ ) ₃ SiCl, (R ⁴ ) ₂ SiCl ₂ , (R ⁴ ) ₂ SiHCl (R ⁴ is as described above). Such chlorosilanes are hydrolyzed, or HSi (OR ⁵ ) ₃ , R ⁴ Si (OR ⁵ ) ₃ , R ⁴ SiH (OR ⁵ ) ₂ , (R ⁴ ) ₂ Si (OR ⁵ ) ₂ , (R ⁴ ) ₃ Dimer or oligomer such as alkoxysilane or dihydrogentetramethyldisiloxane such as Si (OR ⁵ ), (R ⁴ ) ₂ SiH (OR ⁵ ) (where R ⁴ and R ⁵ are as described above). It can be obtained by hydrolysis.

  In addition, the compounding amount in the epoxy-silicone hybrid resin composition of the organohydrogenpolysiloxane of the component (D) is the curing with respect to the hydrosilylation reaction of the group containing multiple bonds that can participate in the hydrosilylation reaction of the component (A ′). In an effective amount, in particular, 0.1 to 4 per total amount of aliphatic unsaturated groups such as vinyl groups such as vinyl groups such as SiH groups containing multiple bonds that can participate in the hydrosilylation reaction in component (A ′). 0.0, more preferably 0.5 to 3.0, and still more preferably 0.8 to 2.4 molar ratio. If this ratio is less than 0.1, the curing reaction does not proceed and it may be difficult to obtain a cured product. If it exceeds 4.0, a large amount of unreacted SiH groups remain in the cured product. There is a risk that the physical properties change over time. In addition, in the case of using the (AD) component, when adding the (D) component, the SiH group of the (AD) component and the (D) component and the multiple bond that can participate in the hydrosilylation reaction of the (AD) component What is necessary is just to make ratio with the group to contain into the said range.

The (E) component platinum group metal-based catalyst is blended in order to cause the addition curing reaction of the composition of the present invention, and there are platinum-based, palladium-based, and rhodium-based ones. From the point of view, platinum-based materials such as H ₂ PtCl ₆ · xH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · xH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · xH ₂ O, PtO ₂ · xH ₂ O , PtCl ₄ · xH ₂ O, PtCl ₂ , H ₂ PtCl ₄ · xH ₂ O (where x is a positive integer), and complexes of these with hydrocarbons, alcohols or vinyl group-containing organopolysiloxanes, etc. These can be exemplified, and these can be used alone or in combination of two or more. The compounding amount of these catalyst components may be a so-called catalyst amount, and is usually a platinum group metal equivalent per the total amount of the components (A ′), (B) and (D), or (AD) and (B). (Mass) is used in the range of 0.1 to 1,000 ppm, preferably 1 to 300 ppm.

  In the epoxy-silicone hybrid resin composition of the present invention, at least one of the component (A) and the component (B), when the component (A ′) is used, the component (A ′), the component (B), and the component (D) When using at least one of the components (AD) component, at least one of the (AD) component and the (B) component is solid at room temperature, but components other than the solid component are liquid. In the case of a product, it is preferable to use a material having a viscosity of 100 Pa · s or higher (viscosity measurement with a rotational viscometer (BM type) (hereinafter the same)) at room temperature. In particular, when the component (A ′) is used, the organosilicon compound as the component (A ′) is solid at room temperature or liquid with a viscosity of 100 Pa · s or more, and the epoxy resin as the component (B) is solid at room temperature. Alternatively, it is preferable that the viscosity is 100 Pa · s or more and that at least one of the component (A ′) and the component (B) is solid at room temperature.

  In addition, although the epoxy-silicone hybrid resin composition of the present invention is solid at room temperature, in order to obtain such a solid composition, all organic resins (that is, (A), (B) and (D) The sum of the components, (when the (D) component is not used, the sum of the components (A) and (B))), the ratio of the solid components is 30% by mass or more (usually 30 to 100% by mass) In particular, the content is preferably 40 to 100% by mass.

(F) Adhesion of organosilicon compounds such as organosilanes and organopolysiloxanes having silicon atom-bonded alkoxy groups in order to improve the adhesion of the cured product obtained by curing the epoxy / silicone hybrid resin composition of the present invention You may add and mix | blend an adjuvant as an arbitrary component as needed. However, it is limited to a range that does not depart from the object of the present invention, at least to a range in which the composition is solid at room temperature. Examples of such organosilicon compounds include tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and vinyl. Alkoxysilane compounds such as trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and hydrogen atoms bonded to silicon atoms in one molecule ( SiH group), alkenyl groups bonded to silicon atom (e.g., Si-CH = CH ₂ groups), such as trialkoxysilyl groups alkoxysilyl group (e.g., such as trimethoxysilyl group), an epoxy group (eg Glycidoxypropyl group, 3,4-epoxycyclohexylethyl group) containing at least 2, preferably 2 or 3 functional groups, usually having 4 to 30 silicon atoms, particularly about 4 to 20 And a siloxane compound (organosiloxane oligomer) having a linear or cyclic structure, preferably having no silanol group.

（式中、Ｒ⁵は、下記式（５）

で表される有機基、又は脂肪族不飽和結合を含有する一価炭化水素基であるが、３個のＲ⁵のうち少なくとも１個は式（５）で表される有機基である。Ｒ⁶は水素原子又は炭素数１〜６の一価炭化水素基、ｓは１〜６、特に１〜４の整数である。） Further, as an adhesion assistant for the component (F), an organooxysilyl-modified isocyanurate compound represented by the following general formula (4) and / or a hydrolysis condensate thereof (organosiloxane-modified isocyanurate compound) is also preferably used. .

(Wherein R ⁵ represents the following formula (5)

Or a monovalent hydrocarbon group containing an aliphatic unsaturated bond, at least one of the three R ⁵ is an organic group represented by the formula (5). R ⁶ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and s is an integer of 1 to 6, particularly 1 to 4. )

In this case, the monovalent hydrocarbon group containing an aliphatic unsaturated bond represented by R ⁵ includes a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group. And alkenyl groups having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms. Examples of the monovalent hydrocarbon group for R ⁶ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group and other alkyl groups, vinyl Group, allyl group, propenyl group, alkenyl group such as isopropenyl group, aryl group such as phenyl group and the like, and monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, preferably alkyl group. .

（式中、ｍ，ｎはそれぞれｍ＋ｎが２〜５０、好ましくは４〜２０を満足する正の整数である。） Specific examples of the component (F) include the following.

(In the formula, m and n are each a positive integer satisfying m + n of 2 to 50, preferably 4 to 20.)

  Among such organosilicon compounds, compounds having particularly excellent adhesive properties of the resulting cured product have silicon atom-bonded alkoxy groups and alkenyl groups or silicon atom-bonded hydrogen atoms (SiH groups) in one molecule. An organosilicon compound is preferred.

  In this invention, the compounding quantity of the adhesion promoter of (F) component is 10 normally with respect to a total of 100 mass parts of (A) component ((A ') component, (AD) component), and (B) component. It can be blended in an amount of not more than part by mass (that is, 0 to 10 parts by mass), preferably 0.01 to 5 parts by mass, more preferably about 0.1 to 1 part by mass. If the blending amount of the component (F) is too small, the adhesion to the substrate may be inferior. If it is too large, a solid composition cannot be obtained at room temperature, the hardness of the cured product is reduced, or the surface of the cured product is reduced. The tackiness may be adversely affected.

  The epoxy / silicone hybrid resin composition of the present invention comprises (A), (B) and (C) components, or (A ′), (B), (C), (D) and (E) components, or ( AD), (B), (C), and (E) components, and optional components added as necessary ((F) component, optional components described later, etc.) are heated (melted), mixed, and finely mixed. It can be made into powder and mechanically mixed, or both can be used together.

  Mixing a composition containing the components (A ′), (B), (C), (D) and (E), or a composition containing the components (AD), (B), (C) and (E) In order to increase the workable time, it is preferable to add a trace amount of a reaction inhibitor such as a nitrogen compound such as an acetylene alcohol compound, a triazole or a nitrile compound, or a phosphorus compound, if necessary.

  Further, in a range that does not deviate from the object of the present invention, at least in a range where the composition is solid at room temperature, for example, BHT, vitamin B, etc. as antioxidants, known discoloration preventing agents, such as organophosphorus discoloration preventing agents, Photodegradation inhibitors such as hindered amines, epoxy crosslinking agents such as acid anhydrides, low molecular silicon compounds as compatibilizers, liquid vinyl siloxanes, hydrogen siloxanes, epoxy compounds, etc. Trace amounts of vinyl ethers as reactive diluents , Vinyl amides, epoxy resins different from component (B) above, oxetanes, allyl phthalates, vinyl adipate, etc., glass fiber, fumed silica, precipitated silica, other inorganic or organic A flame retardant, etc., such as fine particles, may be added. Moreover, you may color with a coloring component.

  In addition, (A ′), (B), (C), (D) and (E) components are included as essential components, or (AD), (B), (C) and (E) components are defined as essential components. The epoxy-silicone hybrid resin composition containing and curing the epoxy resin condensation and hydrosilylation addition reaction together contains the components (A), (B) and (C) as essential components. This is desirable because it is more excellent in reliability than an epoxy / silicone hybrid resin composition that forms a cured product only by condensation.

  The epoxy-silicone hybrid resin composition of the present invention is suitable as a coating protective material for semiconductor components and optical semiconductor components, and as an adhesive such as a die attach agent, and the cured product thereof is a package material or a printed circuit board material. It can be used effectively as a base material and also as a lens.

  The curing condition of the epoxy / silicone hybrid resin composition of the present invention is arbitrary from the melting point of the resin (about 50 ° C.) to 200 ° C. according to the working conditions, and the productivity and characteristics of the cured product. It can be selected as appropriate from the balance. In the case of transfer molding or compression molding, it can be produced by molding at a temperature of 100 to 180 ° C. for several tens of seconds to 5 minutes.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, Me, Ph, Vi, and Gp represent a methyl group, a phenyl group, a vinyl group, and a glycidoxypropyl group, respectively, and parts represent parts by mass.

[Example 1]
(ViMeSiO) _0.2 (PhSiO _3/2 ) _0.7 (MeSiO _3/2 ) _0.1 , 70 parts of organopolysiloxane solid at room temperature containing 5% by mass of silicon atom-bonded hydroxyl groups, hydrogenated bisphenol A type epoxy resin ( Product name: YL7031, manufactured by Japan Epoxy Resin) 30 parts were melted and mixed thoroughly, and then the organohydrogenpolysiloxane represented by (HMeSiO) _0.2 (PhSiO _3/2 ) _0.4 (Me ₂ SiO) _0.4 A catalyst amount of platinum is added so that the ratio of hydrogen atom (h) bonded to silicon atom of hydrogenpolysiloxane and vinyl group (v) of organopolysiloxane is h / v = 1.1 (molar ratio). Add catalyst and aluminum acetylacetone, mix well at 60 ° C, cool to 5 ° C, and crush the resulting solid into powder Thus, an epoxy / silicone hybrid resin composition was obtained. This powder was a solid having no tackiness even at room temperature.

  Next, the powder was molded into a tablet, a rod-shaped molded product was molded with a transfer molding machine, and the molded product was heated at 150 ° C. for 4 hours to completely cure the resin. This cured product was colorless and transparent. Moreover, when this cured product was further heated at 100 ° C. for 1000 hours and the light transmittance after heating was compared with the light transmittance of the cured product before heating, the light transmittance retention was 90% or more, and high It was transparent.

[Example 2]
(ViMeSiO) _0.3 (PhSiO _3/2 ) _0.6 (Me ₂ SiO) _0.1 , 70 parts of highly viscous organopolysiloxane containing 4% by mass of silicon-bonded hydroxyl groups, hydrogenated bisphenol A type solid at room temperature 30 parts of an epoxy resin (trade name: YL7170, manufactured by Japan Epoxy Resin) is melted and mixed well, and then an organohydrogenpolysiloxane represented by (HMeSiO) _0.2 (PhSiO _3/2 ) _0.4 (Me ₂ SiO) _0.4 Is added so that the ratio of hydrogen atom (h) bonded to the silicon atom of organohydrogenpolysiloxane and vinyl group (v) of organopolysiloxane is h / v = 1.1 (molar ratio). An amount of platinum catalyst and aluminum acetylacetone were added, mixed well at 60 ° C, cooled to 5 ° C, and the resulting solid was powdered. And pulverized to obtain an epoxy-silicone hybrid resin composition. This powder was a solid having no tackiness even at room temperature.

  Next, the powder was molded into a tablet, a rod-shaped molded product was molded with a transfer molding machine, and the molded product was heated at 150 ° C. for 4 hours to completely cure the resin. This cured product was colorless and transparent. Moreover, when this cured product was further heated at 100 ° C. for 1000 hours and the light transmittance after heating was compared with the light transmittance of the cured product before heating, the light transmittance retention was 90% or more, and high It was transparent.

[Example 3]
(ViMeSiO) _0.3 is represented by _{(PhSiO 3/2) 0.6 (Me 2} SiO) 0.1, the organopolysiloxane 70 parts of highly viscous containing silicon-bonded hydroxyl 4 wt%, alicyclic epoxy resin solid at room temperature after mixing thoroughly melted (trade name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.) 30 parts, the organohydrogen polysiloxane expressed by _{(HMeSiO) 0.2 (PhSiO 3/2)} 0.4 (Me 2 SiO) 0.4, The ratio of the hydrogen atom (h) bonded to the silicon atom of the organohydrogenpolysiloxane and the vinyl group (v) of the organopolysiloxane is h / v = 1.1 (molar ratio). Add platinum catalyst and aluminum acetylacetone, mix thoroughly at 60 ° C, cool to 5 ° C, grind the resulting solid into a powder, To obtain a sheet-silicone hybrid resin composition. This powder was a solid having no tackiness even at room temperature.

  Next, the powder was molded into a tablet, a rod-shaped molded product was molded with a transfer molding machine, and the molded product was heated at 150 ° C. for 4 hours to completely cure the resin. This cured product was colorless and transparent. Moreover, when this cured product was further heated at 100 ° C. for 1000 hours and the light transmittance after heating was compared with the light transmittance of the cured product before heating, the light transmittance retention was 90% or more, and high It was transparent.

[Example 4]
(ViMeSiO) represented by _{0.2 (HMeSiO) 0.2 (PhSiO 3/2} ) 0.6, the organopolysiloxane 70 parts of highly viscous containing silicon-bonded hydroxyl 4 wt%, the solid alicyclic epoxy resin (trade at room temperature Name: EHPE3150, manufactured by Daicel Chemical Industries, Ltd.) 30 parts were melted and mixed thoroughly, then a catalytic amount of platinum catalyst and aluminum acetylacetone were added, and the mixture was sufficiently mixed at 60 ° C and then cooled to 5 ° C. Was pulverized into a powder to obtain an epoxy / silicone hybrid resin composition. This powder was a solid having no tackiness even at room temperature.

  Next, the powder was molded into a tablet, a rod-shaped molded product was molded with a transfer molding machine, and the molded product was heated at 150 ° C. for 4 hours to completely cure the resin. This cured product was colorless and transparent. Moreover, when this cured product was further heated at 100 ° C. for 1000 hours and the light transmittance after heating was compared with the light transmittance of the cured product before heating, the light transmittance retention was 90% or more, and high It was transparent.

[Example 5]
(GpSiO _3/2 ) _0.4 (PhSiO _3/2 ) _0.6 , 70 parts of organopolysiloxane solid at room temperature containing 5% by mass of silicon-bonded hydroxyl groups, hydrogenated bisphenol A type epoxy resin solid at room temperature ( (Product name: YL7170, manufactured by Japan Epoxy Resin Co., Ltd.) 30 parts and a catalytic amount of aluminum acetylacetone were mixed in a fine powder form to obtain an epoxy / silicone hybrid resin composition. This powder was a solid having no tackiness even at room temperature.

  Next, the powder was molded into a tablet, a rod-shaped molded product was molded with a transfer molding machine, and the molded product was heated at 150 ° C. for 4 hours to completely cure the resin. This cured product was colorless and transparent. Moreover, when this cured product was further heated at 100 ° C. for 1000 hours and the light transmittance after heating was compared with the light transmittance of the cured product before heating, the light transmittance retention was 90% or more, and high It was transparent.

[Comparative Example 1]
70 parts of highly viscous organopolysiloxane represented by (ViMeSiO) _0.3 (PhSiO _3/2 ) _0.6 (Me ₂ SiO) _0.1 and containing 4% by mass of silicon atom-bonded hydroxyl group, hydrogenated bisphenol A type epoxy resin (product) Name: YL7031, manufactured by Japan Epoxy Resin) 30 parts were melted and mixed thoroughly, and then the organohydrogenpolysiloxane represented by (HMeSiO) _0.2 (PhSiO _3/2 ) _0.4 (Me ₂ SiO) _0.4 A catalyst catalyst is added in such a way that the ratio of hydrogen atom (h) bonded to silicon atom of genpolysiloxane and vinyl group (v) of organopolysiloxane is h / v = 1.1 (molar ratio). Then, aluminum acetylacetone was added, and the mixture was sufficiently mixed at 60 ° C and then cooled to 5 ° C. An attempt was made to pulverize the obtained mixture into powder, but it was somewhat tacky at room temperature and could not be made into powder.

Claims (6)

(A) an organosilicon compound having one or more silicon atom-bonded hydroxyl groups in one molecule;
(B) an epoxy resin having no phenylene ether skeleton, and (C) an epoxy-silicone hybrid resin composition containing an aluminum-based curing catalyst as an essential component,
An epoxy-silicone hybrid resin composition, wherein at least one of the component (A) and the component (B) is solid at room temperature, and the composition is solid at room temperature. (A ′) an organosilicon compound having a group containing multiple bonds that can participate in one or more hydrosilylation reactions in one molecule and having one or more silicon atom-bonded hydroxyl groups,
(B) an epoxy resin having no phenylene ether skeleton,
(C) an aluminum-based curing catalyst,
(D) An organohydrogenpolysiloxane, and (E) an epoxy-silicone hybrid resin composition containing a platinum group metal catalyst as an essential component,
An epoxy / silicone hybrid resin composition, wherein at least one of the component (A ′), the component (B) and the component (D) is solid at room temperature, and the composition is solid at room temperature.   The organosilicon compound as component (A ′) is solid or liquid with a viscosity of 100 Pa · s or higher at normal temperature, and the epoxy resin as component (B) is solid or liquid with viscosity of 100 Pa · s or higher at normal temperature. The epoxy-silicone hybrid resin composition according to claim 2, wherein at least one of the component (A ') and the component (B) is solid at room temperature. (AD) one molecule having a group containing multiple bonds that can participate in one or more hydrosilylation reactions, one or more silicon atom-bonded hydrogen atoms, and one or more silicon atom-bonded hydroxyl groups Having an organosilicon compound,
(B) an epoxy resin having no phenylene ether skeleton,
An epoxy-silicone hybrid resin composition containing (C) an aluminum-based curing catalyst and (E) a platinum group metal-based catalyst as an essential component,
An epoxy-silicone hybrid resin composition, wherein at least one of the (AD) component and the (B) component is solid at room temperature, and the composition is solid at room temperature.   The epoxy-silicone hybrid resin composition according to any one of claims 1 to 4, which is used for casting molding.   Hardened | cured material formed by cast-molding the epoxy-silicone hybrid resin composition of any one of Claims 1 thru | or 4.