JP2011208120A - Self-adhesive polyorganosiloxane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent, self-adhesive polyorganosiloxane composition having high adhesion to a base material formed from a noble-metal, such as Ag or Au, and a PPA.SOLUTION: The self-adhesive polyorganosiloxane composition includes: (A) 100 pts.wt of a polyorganosiloxane having an alkenyl group; (B) a polyorganohydrogensiloxane in such an amount that the number of hydrogen atoms is within the range of 0.1-4.0 per one alkenyl group in the component (A); (C) a platinum-based catalyst in a catalytic amount; and (D) as an adhesiveness-imparting agent, (D1) an isocyanuric acid derivative having (i) an alkoxysilyl group and/or an epoxy group, and (iii) a group containing a divalent siloxy unit represented by formula: -[(CH)SiO]-Si(CH)-(wherein, m is an integer of 1-5) and (D2) a silane or siloxane compound having alkoxy group and/or epoxy group, and no isocyanuric ring, in an amount of 0.1-10 pts.wt in total.

Description

  The present invention relates to a self-adhesive polyorganosiloxane composition, and more particularly to a self-adhesive polyorganosiloxane composition having good adhesion to a base material of a noble metal such as silver or gold.

  Silicone (polyorganosiloxane) compositions such as silicone rubber and silicone gel are used in various applications because they form cured products with excellent properties such as weather resistance, heat resistance, hardness, and elongation. .

  However, the silicone composition has lower adhesion to noble metals such as Ag, Au, Pt, Rh, and Pd used as a frame or electrode material of a semiconductor device than epoxy resin. Therefore, in a semiconductor device (package) that uses a silicone composition as a sealing material or as a die attach material, a layer of a frame or an electrode and a cured silicone layer can be obtained by applying high-temperature stress, temperature cycle, or storage at high temperature and high humidity. There is a problem that peeling easily occurs at the interface.

  Moreover, in an LED device including a light emitting element such as a light emitting diode (LED), a silicone composition having excellent heat resistance and ultraviolet resistance is used as a material for sealing the light emitting element. In particular, addition-reactive silicone compositions that are cured using hydrosilylation are widely used because they cure in a short time by heating and do not generate by-products during curing.

  However, conventional addition reaction curable silicone compositions not only have low adhesion to noble metal materials such as those described above for electrodes, but also against PPA (polyphthalamide resin) that has recently been used as a heat-resistant plastic. Adhesiveness was insufficient. Further, there is a problem in that the adhesiveness is further lowered due to heat generation from the light emitting element or application of a temperature cycle, and peeling occurs between the support base material such as PPA or ceramics or the noble metal for electrodes and the cured layer of the silicone composition. (For example, see Patent Document 1).

  In order to increase the adhesiveness of the silicone composition to a base material (frame, electrode, etc.) made of a noble metal, a primer is applied. However, this method has a problem that an extra step of applying and drying the primer is required and a load is applied to the surrounding environment due to evaporation of the solvent contained in the primer.

  Further, there is provided a silicone resin composition for semiconductor encapsulation in which an organosiloxane oligomer having a functional group selected from an alkenyl group, an alkoxysilyl group, and an epoxy group and an organooxysilyl-modified isocyanurate compound are blended (for example, , See Patent Document 2). However, this resin composition did not have sufficient adhesion to a noble metal substrate. Moreover, since transparency is not favorable, it was difficult to use for optical uses, such as a sealing layer of an LED lamp. Furthermore, the present applicant has one or more functional groups selected from an epoxy group and an alkoxysilyl group, and one kind selected from a crosslinkable vinyl group and a hydroxysilyl group (Si-H group) as an adhesion-imparting agent. It has been proposed to improve the adhesion of a noble metal to a base material using an isocyanuric acid derivative having each of the above groups (see Patent Document 3), but the transparency and the adhesion to a noble metal base material are further improved. It is demanded.

JP 2002-338833 A JP 2008-27966 A Japanese Patent Application No. 2008-233514

  The present invention has been made to solve such a problem, and is sufficient for adhesion to a base material made of a noble metal such as Ag or Au and a base material made of a hardly adhesive plastic such as PPA. It is an object of the present invention to provide a self-adhesive polyorganosiloxane composition that is suitable as a die attach material or a sealing material for a semiconductor device.

（式中、ｍは１〜５の整数である。）で表される２価のシロキシ単位含有基をそれぞれ有するイソシアヌル酸誘導体と、（Ｄ2）アルコキシ基を有しかつイソシアヌル環を含有しないシランまたはシロキサン化合物とを、合計で０．１〜１０重量部をそれぞれ含有してなることを特徴とする。 The self-adhesive polyorganosiloxane composition of the present invention comprises (A) 100 parts by weight of a polyorganosiloxane having an alkenyl group bonded to a silicon atom, and (B) a polyorganohydrogensiloxane having a hydrogen atom bonded to a silicon atom. For each alkenyl group in the component (A), the amount of the hydrogen atoms in the component is 0.1 to 4.0, (C) a catalytic amount of the platinum-based catalyst, and (D) (D1) (i) alkoxysilyl group and / or epoxy group, and (iii) formula:

(Wherein m is an integer of 1 to 5) and an isocyanuric acid derivative each having a divalent siloxy unit-containing group represented by: (D2) a silane having an alkoxy group and not containing an isocyanuric ring A total of 0.1 to 10 parts by weight of a siloxane compound is included.

  The self-adhesive polyorganosiloxane composition of the present invention has excellent adhesion to substrates made of noble metals such as Ag and Au, and substrates made of plastics such as PPA, which have been difficult to bond. Have. Therefore, in a semiconductor device using this polyorganosiloxane composition as a sealing layer or a die attach material, the adhesion between the cured layer of the polyorganosiloxane composition and the base material made of noble metal or PPA is good, and at the interface. Peeling hardly occurs and reliability is high. Moreover, since a highly transparent cured product can be obtained, a light-emitting device with high emission luminance and high reliability can be obtained when used as a sealing material for a light-emitting device such as an LED device.

  Embodiments of the present invention will be described below. The self-adhesive polyorganosiloxane composition of the embodiment of the present invention includes (A) a polyorganosiloxane containing an alkenyl group, (B) a polyorganohydrogensiloxane, (C) a platinum-based catalyst, and (D) Each containing an adhesion-imparting agent, (D) as an adhesion-imparting agent, (D1) an isocyanuric acid derivative having a specific functional group and intermediate structure in the molecule, and (D2) a silane having an alkoxy group Each contains a siloxane compound. Hereinafter, each component will be described.

[(A) component]
The polyorganosiloxane containing an alkenyl group as component (A) is the base polymer of the self-adhesive polyorganosiloxane composition of the present invention. It is preferable to use a polyorganosiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule.

  Examples of the molecular structure of the component (A) include linear, cyclic, and three-dimensional network structures (resinous). The structure such as linear or cyclic may have a branch, but the main chain is basically composed of repeating diorganosiloxane units, and both ends of the molecular chain are blocked with triorganosiloxy groups Are preferred.

  (A) As an alkenyl group couple | bonded with the silicon atom in a component, it is 2-8 carbon atoms, More preferably, it is 2-8 carbon atoms, such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group. There are four. A vinyl group is particularly preferable. When the polyorganosiloxane having an alkenyl group as component (A) is linear, the alkenyl group may be bonded to the silicon atom only at either the molecular chain end or the middle, but the molecular chain end It may be bonded to the silicon atom both in the middle and the middle.

  Examples of organic groups bonded to silicon atoms other than alkenyl groups in component (A) include alkyl groups, particularly methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, cyclohexyl groups, heptyl groups, and the like. An alkyl group having 1 to 10 carbon atoms; an aryl group, particularly an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group; an aralkyl group such as a benzyl group and a phenethyl group; a chloromethyl group , An unsubstituted or halogen-substituted monovalent hydrocarbon group such as a halogenated alkyl group such as 3-chloropropyl group and 3,3,3-trifluoropropyl group. In particular, a methyl group or a phenyl group is preferable.

  The viscosity (25 ° C.) of the component (A) is preferably 100 to 100,000 mPa · s, particularly preferably in the range of 500 to 10,000 mPa · s. When the viscosity (25 ° C.) of component (A) is within this range, the workability of the resulting composition is good and the physical properties of the cured product obtained from this composition are good. .

Specific examples of the component (A) include molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped methylvinylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethyl Siloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of molecular chain, dimethylvinylsiloxy group-blocked methylvinylpolysiloxane with molecular chain at both ends, dimethylvinylsiloxy group-blocked dimethyl with molecular chain at both ends Siloxane / methyl vinyl siloxane copolymer, both ends of molecular chain dimethyl vinyl siloxy group blocked dimethyl siloxane / methyl vinyl siloxane / methyl phenyl siloxane copolymer, tri chain siloxy at both ends of molecular chain Dimethylpolysiloxane capped, ^{_{wherein: R 1 3 SiO 0.5 (.}} . R 1 is a monovalent hydrocarbon radical unsubstituted or substituted other than alkenyl groups hereinafter) represented by siloxy units and wherein: R Siloxy unit represented by ¹ ₂ R ² SiO _0.5 (R ² is an alkenyl group; the same shall apply hereinafter) and a siloxy unit represented by the formula: R ¹ ₂ SiO and siloxy represented by the formula: SiO ₂ A polyorganosiloxane copolymer comprising units, a siloxy unit represented by the formula: R ¹ ₃ SiO _0.5 and a siloxy unit represented by the formula: R ¹ ₂ R ² SiO _0.5 and a formula: R ¹ ₂ A polyorganosiloxane copolymer comprising a siloxy unit represented by SiO, comprising a siloxy unit represented by the formula: R ¹ ₂ R ² SiO _0.5 and a siloxy unit represented by the formula: R ¹ ₂ SiO Poly Lugano copolymer, ^wherein: siloxy units of the formula represented by _R 1 _{² R} ² _{SiO ^0.5:} siloxy units of the formula represented by _R 1 2 SiO: consisting of siloxy units represented by SiO ₂ Polyorganosiloxane copolymer, siloxy unit represented by formula: R ¹ R ² SiO and siloxy unit represented by formula: R ¹ SiO _1.5 , or siloxy unit represented by formula: R ² SiO _1.5 Examples thereof include polyorganosiloxane copolymers composed of units. These can be used singly or in combination of two or more.

R ¹ in the above formula is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; Examples thereof include aralkyl groups such as benzyl group and phenethyl group; and halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group. Examples of R ² in the above formula include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group.

[Component (B)]
The polyorganohydrogensiloxane as the component (B) acts as a component that reacts with the component (A) to crosslink. The molecular structure of component (B) is not particularly limited, and various polyorganohydrogensiloxanes such as linear, cyclic, branched, and three-dimensional network structures (resinous) can be used.

  The polyorganohydrogensiloxane of component (B) has 2 or more, preferably 3 or more, hydrogen atoms bonded to silicon atoms in one molecule. That is, it has 2 or more, preferably 3 or more hydrosilyl groups (Si—H groups) in one molecule. When the polyorganohydrogensiloxane as the component (B) is linear, these Si-H groups are located at either one of the molecular chain terminal and the middle part, or both. Also good. The number (degree of polymerization) of silicon atoms in one molecule of the component (B) is preferably about 2 to 1,000, more preferably about 3 to 100.

As the component (B), an average composition formula: R ³ _a H _b SiO _{(4-ab) / 2} (wherein R ³ is an aliphatic unsaturated group and has 1 to 14 carbon atoms) Preferably, it is an unsubstituted or substituted monovalent hydrocarbon group of 1 to 10. a and b are 0.7 ≦ a ≦ 2.1, 0.001 ≦ b ≦ 1.0, and 8 ≦ a + b ≦ 3.0, more preferably a positive number satisfying 1.0 ≦ a + b ≦ 2.5).

Examples of R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, and decyl group. Alkyl groups such as phenyl groups, aryl groups such as tolyl groups, xylyl groups, naphthyl groups; aralkyl groups such as benzyl groups, phenylethyl groups, phenylpropyl groups; some or all of the hydrogen atoms in these hydrocarbon groups Examples include groups substituted with a halogen atom, such as chloromethyl group, 3-chloropropyl group, bromoethyl group, 3,3,3-trifluoropropyl group. R ³ is preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group.

Specific examples of the component (B) include molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends trimethylsiloxy group. Blocked dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane at both molecular chains, dimethylpolysiloxane / methylhydrogensiloxane blockade at both ends of molecular chain Combined, dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer at both ends of molecular chain, dimethylhydrosiloxy group-blocked methylphenyl at both ends of molecular chain Represented by _R 1 2 ^SiO: polysiloxane, ^formula: _R 1 _{3 SiO} 0.5 siloxy units of formula ^{(R 1} is as defined above that.) Represented ^by: siloxy units of the formula represented by R 1 HSiO A polyorganosiloxane copolymer comprising siloxy units, a siloxy unit represented by the formula: R ¹ ₃ SiO _0.5 and a siloxy unit represented by the formula: R ¹ ₂ HSiO _0.5 and a formula: SiO ₂ A polyorganosiloxane copolymer comprising a siloxy unit, a polyorganosiloxane copolymer comprising a siloxy unit represented by the formula: R ¹ ₂ HSiO _0.5 and a siloxy unit represented by the formula: SiO ₂ , ^formula: siloxy units of the formula represented by R 1 ^HSiO: siloxy units represented by R _{1 SiO 1.5} or formula: comprising a siloxy unit represented by _{HSiO 1.5} polyols Roh copolymer and the like. These can be used singly or in combination of two or more.

  The blending amount of the polyorganohydrogensiloxane as the component (B) is an effective curing amount of the component (A). In particular, the Si-H group of the component (B) is an alkenyl group in the component (A) (for example, (Vinyl group) is used at a blending amount of 0.1 to 4.0, more preferably 1.0 to 3.0. If it 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 Si—H groups remain in the cured product. Therefore, the physical properties of the cured product may change over time.

[Component (C)]
The platinum-based catalyst that is the component (C) is a catalyst that promotes the addition reaction (hydrosilylation reaction) between the alkenyl group in the component (A) and the Si—H group in the component (B). As the component (C), for example, chloroplatinic acid, alcohol-modified chloroplatinic acid, a coordination compound of chloroplatinic acid and olefins, vinyl siloxane or acetylene compound can be used.

  The amount of component (C) is not particularly limited as long as it is an amount effective as a catalyst for the hydrosilylation reaction, but it is 0. 0 in terms of platinum with respect to the total amount of component (A) and component (B). The range is 1 to 1,000 ppm, more preferably 1 to 500 ppm, and still more preferably 1 to 20 ppm. When the amount is within this range, the addition reaction is sufficiently accelerated, so that sufficient curing can be obtained, and this is economically advantageous.

[(D) component]
Component (D) is an adhesiveness-imparting agent that imparts self-adhesiveness to the polyorganosiloxane composition of the present invention, and contains the following isocyanuric acid derivative (D1) and (D2) an alkoxy group and / or an epoxy group. It is used in combination with a silane or siloxane compound that has and does not contain an isocyanuric ring. By using a combination of the component (D1) and the component (D2), a composition having excellent adhesion to a base material made of noble metal such as Ag or Au and a base material made of PPA can be obtained. .

（式中、ｍは１〜５の整数である。）で表される２価のシロキシ単位含有基をそれぞれ有するイソシアヌル酸誘導体である。（Ｄ1）成分について、以下に説明する。（Ｄ1）成分は、(i)アルコキシシリル基と、(ii)ビニル基またはエポキシ基と、(iii)式：−(ＣＨ_３)_２ＳｉＯ−Ｓｉ(ＣＨ_３)_２−（前記［化２］においてｍ＝１）で表される２価のシロキシ単位含有基をそれぞれ有するイソシアヌル酸誘導体とすることができる。ここで、（Ｄ1）成分は(ii)ビニル基およびエポキシ基をそれぞれ有することができる。 The component (D1) includes (i) an alkoxysilyl group and / or an epoxy group, and (iii) a formula:

(Wherein, m is an integer of 1 to 5) isocyanuric acid derivatives each having a divalent siloxy unit-containing group. The component (D1) will be described below. The component (D1) includes (i) an alkoxysilyl group, (ii) a vinyl group or an epoxy group, and (iii) a formula: — (CH ₃ ) ₂ SiO—Si (CH ₃ ) ₂ — (the above [Chemical Formula 2] In this case, the isocyanuric acid derivatives each having a divalent siloxy unit-containing group represented by m = 1) in FIG. Here, the component (D1) can have (ii) a vinyl group and an epoxy group, respectively.

  More specific examples of such component (D1) include isocyanuric acid derivatives (D1-1) to (D1-4) represented by [Chemical Formula 3] to [Chemical Formula 6]. These isocyanuric acid derivatives may be used alone or in combination of two or more. Since the isocyanuric acid derivatives (D1-1) to (D1-4) have a siloxane structure that is compatible with the base component silicone between the functional alkoxy group and the isocyanurate ring, D1) A cured product having good transparency can be obtained by using an adhesion-imparting agent.

………（Ｄ1-1）

………（Ｄ1-2）

………（Ｄ1-3）

………（Ｄ1-4）

......... (D1-1)

......... (D1-2)

......... (D1-3)

......... (D1-4)

で表されるイソシアヌル酸誘導体を使用することができる。 In addition, as the component (D1), the general formula:

The isocyanuric acid derivative represented by can be used.

（式中、Ｒは、アルコキシシリル基、エポキシ基および水素原子の中から選ばれる基であり、ｎは１〜５の整数、ｋは０〜５の整数である。）で表されるシロキシ単位含有基である。そして、Ｒ^４〜Ｒ^６のうちで少なくとも１つは、ｎ＝１、ｋ＝０でありかつＲが水素原子であるシロキシ単位含有基（テトラメチルジシロキシ基）であり、少なくとも１つは、ｎ＝１、ｋ＝２でありＲがアルコキシシリル基またはグリシドキシ基であるシロキシ単位含有基である。 Here, R ^{4 to} R ⁶ are each represented by the formula (iv):

(In the formula, R is a group selected from an alkoxysilyl group, an epoxy group, and a hydrogen atom, n is an integer of 1 to 5, and k is an integer of 0 to 5). It is a containing group. At least one of R ^{4 to} R ⁶ is a siloxy unit-containing group (tetramethyldisiloxy group) in which n = 1, k = 0 and R is a hydrogen atom, and at least one of n = 1, k = 2, and R is a siloxy unit-containing group in which an alkoxysilyl group or glycidoxy group is present.

  More specific examples of such component (D1) include isocyanuric acid derivatives (D1-5) to (D1-9) represented by [Chemical 9] to [Chemical 13]. These isocyanuric acid derivatives may be used alone or in combination of two or more. Since the isocyanuric acid derivatives (D1-5) to (D1-9) have a siloxane structure that is compatible with the base component silicone between the functional alkoxy group or glycidoxy group and the isocyanurate ring, By using such an adhesive imparting agent (D1), a cured product having good transparency can be obtained.

………（Ｄ1-5）

………（Ｄ1-6）

………（Ｄ1-7）

………（Ｄ1-8）

………（Ｄ1-9）

......... (D1-5)

......... (D1-6)

......... (D1-7)

......... (D1-8)

......... (D1-9)

  In the embodiment of the present invention, as the (D) adhesion-imparting agent, (D2) a silane or siloxane compound having an alkoxy group and / or an epoxy group and not containing an isocyanuric ring is blended together with the component (D1). . As the component (D2), it is possible to use an alkoxy group-containing silane which is usually used as a silane coupling agent. In particular, a cyclic siloxane having a methoxysilyl group represented by [Chemical Formula 14] and / or It is preferable to use the hydrolysis condensate (D2-1).

………（Ｄ2-1）

......... (D2-1)

  By blending (D2-1), the adhesion to noble metals such as Ag and PPA can be further improved. That is, by adding the alkoxy group-containing silane having the cyclic siloxane structure described above in the molecule as the component (D2), the compatibility of the component (D1) with the polymer as the component (A) can be improved. The improvement in adhesiveness can be further promoted.

………（Ｄ2-2） As the component (D2), a dialkoxysilane having an epoxy group represented by [Chemical Formula 15] and / or a hydrolysis condensate thereof (D2-2) can be preferably used. By blending such dialkoxysilane and / or its hydrolysis condensate (D2-2), it has excellent adhesion to a base material of noble metals such as Ag, and also has a base such as PPA and ceramics. A composition having good adhesion to the material can be obtained.

......... (D2-2)

  Furthermore, as the component (D2), a polysiloxane having an epoxy group (including a glycidoxy group) in the side chain can be used. Examples of the polysiloxane that can be preferably used include polysiloxanes (D2-3) to (D2-5) represented by the following [Chemical Formula 16] to [Chemical Formula 18].

………（Ｄ2-3）

………（Ｄ2-4）

………（Ｄ2-5）

......... (D2-3)

......... (D2-4)

......... (D2-5)

  In the embodiment of the present invention, the total amount of the component (D1) and the component (D2) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the component (A). The amount of component (D1) is preferably 0.05 to 9.95 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of component (A). If the amount of the component (D1) is too small, there is a possibility that good adhesion to a noble metal substrate such as Ag may not be imparted, and if the amount is too large, a cured product having sufficient strength can be obtained. There is a risk of not. Moreover, it is preferable that the compounding quantity of (D2) component shall be 0.05-9.95 weight part with respect to 100 weight part of (A) component. If the amount of component (D2) is too large, a cured product having sufficient strength may not be obtained.

  In addition to the above-described (A) component, (B) component, (C) component, and (D) component ((D1) component and (D2) component), the composition according to the embodiment of the present invention is optionally provided. Publicly known additives can be blended. For example, reinforcing inorganic fillers such as fumed silica, non-reinforcing inorganic fillers such as calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, and zinc oxide do not impair the purpose of the present invention. It can mix | blend suitably in the range.

  The self-adhesive polyorganosiloxane composition of the embodiment of the present invention is prepared by uniformly mixing the above-described components. By adding a curing inhibitor such as acetylene alcohol, the curability can be arbitrarily adjusted. It can be stored in two liquids so that the curing does not proceed, and the two liquids can be mixed and hardened during use, but can also be used as one liquid by selecting a curing inhibitor. In the case of the two-component mixed type, it is necessary to avoid using the same envelope for the (B) component polyorganohydrogensiloxane and the (C) component platinum-based catalyst because of the risk of dehydrogenation reaction. is there. The viscosity of the self-adhesive polyorganosiloxane composition of the embodiment thus obtained is preferably in the range of 100 to 20,000 mPa · s, particularly 300 to 10,000 mPa · s, as measured by a rotational viscometer at 25 ° C. A range of s is preferred.

  The composition of the embodiment of the present invention is cured by heating as necessary. The cured product has sufficient rubber hardness, and has high adhesion (adhesive strength) to a base material made of a noble metal such as Ag and a plastic such as PPA. Therefore, it can be widely used for semiconductor packages such as LED, photodiode, CCD, and CMOS. The curing conditions are not particularly limited, but are usually cured at 40 to 200 ° C., preferably 60 to 170 ° C. for 1 minute to 10 hours, preferably about 30 minutes to 6 hours.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to this Example. In addition, in the following example, a part shows a weight part and% shows weight%. The viscosity is a measured value at 25 ° C.

[Preparation of adhesiveness-imparting agent]
First, adhesiveness imparting agents (a) to (h) were respectively prepared as shown below.

(Synthesis Example 1)
In the presence of a catalytic amount of a Pt-based catalyst (a complex of chloroplatinic acid and divinyltetramethyldisiloxane), 134 g of tetramethyldisiloxane and 89 g of vinyltrimethoxysilane were subjected to a hydrosilylation reaction at a molar ratio of 1: 1. 51 g of the product (yield 71%) obtained in the presence of 37 g of 1,3,5-triallyl isocyanurate (trade name TAIC manufactured by Nippon Kasei Co., Ltd.) and a catalytic amount of Pt-based catalyst for 6 hours Hydrosilylation reaction (second hydrosilylation reaction) was performed. Thus, one trimethoxysilyl group, two vinyl groups and a divalent siloxy unit represented by the formula: — (CH ₃ ) ₂ SiO—Si (CH ₃ ) ₂ — represented by the above [Chemical Formula 3] are contained. An isocyanuric acid derivative each having one group, two trimethoxysilyl groups, one vinyl group, and the formula: — (CH ₃ ) ₂ SiO—Si (CH ₃ ) ₂ — A mixture (adhesiveness imparting agent (a)) with an isocyanuric acid derivative each having two represented divalent siloxy unit-containing groups was obtained. The yield of the second hydrosilylation reaction was 83%.

(Synthesis Example 2)
Product obtained by hydrosilylation reaction of 134 g of tetramethyldisiloxane and 89 g of vinyltrimethoxysilane at a molar ratio of 1: 1 in the presence of a catalytic amount of a Pt-based catalyst (yield 71 %) 42 g was hydrosilylated with 40 g of 1,3-diallyl-5-glycidyl isocyanurate (trade name DA-MGIC, manufactured by Shikoku Kasei Kogyo Co., Ltd.) in the presence of a catalytic amount of a Pt-based catalyst for 6 hours. Thus, one trimethoxysilyl group, one vinyl group, and a divalent siloxy unit represented by the formula: — (CH ₃ ) ₂ SiO—Si (CH ₃ ) ₂ — represented by the above [Chemical Formula 5] are contained. An isocyanuric acid derivative each having one group and one epoxy group, two trimethoxysilyl groups and one epoxy group represented by the above [Chemical Formula 6], and a formula: — (CH ₃ ) ₂ SiO—Si ( An isocyanuric acid derivative each having two divalent siloxy unit-containing groups represented by CH ₃ ) ₂ —, two trimethoxysilyl groups and one vinyl group represented by the above [Chemical Formula 4]: A mixture (adhesion imparting agent (b)) with an isocyanuric acid derivative each having two divalent siloxy unit-containing groups represented by (CH ₃ ) ₂ SiO—Si (CH ₃ ) ₂ — was obtained. The yield was 57%.

(Synthesis Example 3)
In the presence of a catalytic amount of a Pt-based catalyst (a complex of chloroplatinic acid and divinyltetramethyldisiloxane), 134 g of tetramethyldisiloxane and 89 g of vinyltrimethoxysilane were subjected to a hydrosilylation reaction at a molar ratio of 1: 1. 51 g of the product obtained (yield 71%) was subjected to hydrosilylation reaction (first reaction) in the presence of 37 g of 1,3,5-triallyl isocyanurate (trade name TAIC) and a catalytic amount of a Pt-based catalyst for 6 hours. 2 hydrosilylation reaction). Thus, a mixture of the isocyanuric acid derivative represented by [Chemical Formula 3] and the isocyanuric acid derivative represented by [Chemical Formula 4] was obtained. The yield of the second hydrosilylation reaction was 83%.

  Next, 59 g of the product of the second hydrosilylation reaction and 193 g of tetramethyldisiloxane were subjected to a hydrosilylation reaction (third hydrosilylation reaction) in the presence of a catalytic amount of a Pt-based catalyst for 10 hours, and then tetramethyl The disiloxane residue was removed by distillation. Thus, 67 g of a mixture of the isocyanuric acid derivative (D1-5) represented by the above [Chemical 9] and the isocyanuric acid derivative (D1-6) represented by the above [Chemical 10] (adhesion imparting agent (c)) was obtained. The yield of the third hydrosilylation reaction was 80%.

(Synthesis Example 4)
In the presence of a catalytic amount of Pt catalyst, 64 g of 1,3,5-triallyl isocyanurate (trade name TAIC) and 34 g of methyldimethoxysilane were subjected to a hydrosilylation reaction for 2 hours. Thus, an isocyanuric acid derivative having one methyldimethoxysilyl group and two vinyl groups represented by the following [Chemical Formula 19], and an isocyanuric having two methyldimethoxysilyl groups and one vinyl group represented by [Chemical Formula 20] A mixture with the acid derivative (adhesion imparting agent (d)) was obtained. The yield was 89%.

(Synthesis Example 5)
In the presence of a catalytic amount of Pt catalyst, 69 g of 1,3-diallyl-5-glycidyl isocyanurate (trade name DA-MGIC) and 28 g of methyldimethoxysilane were subjected to a hydrosilylation reaction for 2 hours. Thus, an isocyanuric acid derivative (adhesiveness imparting agent (e)) having an epoxy group represented by [Chemical Formula 21], a methyldimethoxysilyl group, and a vinyl group, respectively, was obtained. The yield was 95%.

(Synthesis Example 6)
One mole of the product obtained by equilibrating tetramethyldisiloxane with octamethylcyclotetrasiloxane and 2,4,6,8-tetramethylcyclotetrasiloxane in a 1: 1: 1 molar ratio is A polysiloxane represented by the above [Chemical Formula 16] was obtained by hydrosilylation reaction with 1 mol of trimethoxysilane and 2 mol of allyl glycidyl ether. This was designated as an adhesion-imparting agent (f).

(Synthesis Example 7)
One mole of the product obtained by equilibrating tetramethyldisiloxane with octamethylcyclotetrasiloxane and 2,4,6,8-tetramethylcyclotetrasiloxane in a 1: 1: 1 molar ratio is By hydrosilylation reaction with 1 mol of trimethoxysilane and 2 mol of 1,2-epoxy-4-vinylcyclohexane, the polysiloxane represented by the above [Chemical Formula 17] was obtained. This was designated as an adhesion-imparting agent (g).

(Synthesis Example 8)
A polysiloxane represented by the above [Chemical Formula 18] was obtained by hydrosilylation reaction of polyorganohydrogensiloxane and 1,2-epoxy-4-vinylcyclohexane at a molar ratio of 1: 9. This was designated as an adhesion-imparting agent (h).

Example 1
(A) 28 parts of polysiloxane composed of (CH ₃ ) ₃ SiO _1/2 unit, (CH ₃ ) (CH ₂ ═CH) SiO unit and SiO ₂ unit, and both ends of the molecular chain are blocked with dimethylvinylsiloxy groups. 100 parts of a mixture (vinyl group-containing polymer) (viscosity 7.5 Pa · s) with 72 parts of dimethylpolysiloxane, and (B) methylhydrochloride having a viscosity of 210 mPa · s blocked at both ends of the molecular chain with trimethylsiloxy groups Genpolysiloxane (content of SiH group is 9 mmol (equivalent) / g) 6.2 parts (molar (equivalent) ratio of SiH group in component (B) to vinyl group in component (A) (H / Vi) = 1.7), (C) 10 ppm of the complex of chloroplatinic acid and divinyltetramethyldisiloxane in terms of platinum metal element with respect to the total amount of components (A) and (B), and Synthesis Example 1 1.0 parts of the obtained adhesion imparting agent (a), 1.0 part of the adhesion imparting agent (i) and 0.5 part of the adhesion imparting agent (j) are mixed to prepare a polyorganosiloxane composition. did. The adhesion-imparting agent (i) is a product of the hydrosilylation reaction of 2,2,4,6,8-pentamethylcyclotetrasiloxane and 3-trimethoxysilylpropyl methacrylate. The cyclic siloxane which has the trimethoxysilyl group represented by these was used. Further, as the adhesion-imparting agent (j), dialkoxysilane (trade name TSL8355 manufactured by Momentive) having an epoxy group represented by the above [Chemical Formula 15] was used.

Example 2
(A) dimethylpolysiloxane (vinyl group-containing polymer) and (B) methylhydrogenpolysiloxane used in Example 1 were blended in the proportions shown in Table 1, and (C) platinum-based as in Example 1 A catalyst was formulated. Furthermore, as the adhesiveness imparting agent, the adhesiveness imparting agent (b) obtained in Synthesis Example 2 and the above-described adhesiveness imparting agents (i) and (j) were blended in the ratios shown in Table 1, respectively. In the same manner as in Example 1, a polyorganosiloxane composition was prepared. In Table 1, the description of the blending amount of (C) platinum-based catalyst was omitted.

Example 3
(A) dimethylpolysiloxane (vinyl group-containing polymer) and (B) methylhydrogenpolysiloxane used in Example 1 were blended in the proportions shown in Table 1, and (C) platinum-based as in Example 1 A catalyst was formulated. Further, as the adhesiveness imparting agent, the adhesiveness imparting agent (b) obtained in Synthesis Example 2 and the above-described adhesiveness imparting agent (i) were blended in the proportions shown in Table 1, respectively. Thus, a polyorganosiloxane composition was prepared.

Example 4
(A) dimethylpolysiloxane (vinyl group-containing polymer) and (B) methylhydrogenpolysiloxane used in Example 1 were blended in the proportions shown in Table 1, and (C) platinum-based as in Example 1 A catalyst was formulated. Furthermore, as the adhesiveness imparting agent, the adhesiveness imparting agent (a) obtained in Synthesis Example 1 and the above-described adhesiveness imparting agent (j) were blended in the ratios shown in Table 1, respectively, and the same as in Example 1. Thus, a polyorganosiloxane composition was prepared.

Comparative Examples 1 and 2
The (A) vinyl group-containing polymer and (B) methyl hydrogen polysiloxane used in Example 1 were blended in the proportions shown in Table 1, and (C) a platinum-based catalyst was blended in the same manner as in Example 1. Further, as the adhesion imparting agent, in Comparative Example 1, the adhesion imparting agent (d) obtained in Synthesis Example 4 and the above-described adhesion imparting agents (i) and (j) are used. The adhesion promoter (e) obtained in 5 and the above-mentioned adhesion promoters (i) and (j) were blended in the proportions shown in Table 1, and the polyorganosiloxane composition was prepared in the same manner as in Example 1. Was prepared.

Comparative Examples 3 and 4
The (A) vinyl group-containing polymer and (B) methyl hydrogen polysiloxane used in Example 1 were blended in the proportions shown in Table 1, and (C) a platinum-based catalyst was blended in the same manner as in Example 1. Further, as the adhesion imparting agent, the aforementioned adhesion imparting agents (i), (j) and the adhesion imparting agent (k) are blended in the proportions shown in Table 1, respectively, and polyorganosiloxane is prepared in the same manner as in Example 1. A composition was prepared. In addition, 1,3,5-triallyl isocyanurate (trade name TAIC) was used as the adhesion-imparting agent (k).

  Next, the compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were respectively heat-molded at 150 ° C. for 2 hours to form a cured product, and the transparency of the cured product was examined with the naked eye. . Those having high transparency were evaluated as ◯, and those having sufficient transparency were evaluated as Δ. Moreover, the adhesiveness with respect to an Ag board | substrate and a PPA board | substrate was measured by the method shown below, respectively. These results are shown in Table 1.

[Measurement of adhesion to Ag]
One end of two Ag substrates (thickness 1 mm) having a width of 25 mm is sandwiched between layers having a thickness of 1 mm made of the compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4. And the composition layer was cured by heating at 150 ° C. for 2 hours. The specimen prepared in this manner was allowed to stand at room temperature for 12 hours or more, and then both ends of the specimen were pulled with a tensile tester to measure the cohesive failure rate. Then, the case where the cohesive failure rate exceeded 60% was evaluated as ◯, the case where the cohesive failure rate was 10-60% was evaluated as Δ, and the case where the cohesive failure rate was less than 10% was evaluated as ×.

[Measurement of adhesion to PPA]
A PPA substrate (width 25 mm, thickness 1 mm) was used in place of the Ag substrate, and a test specimen was prepared in the same manner. After leaving this test body for 12 hours or more at room temperature, both ends of the test body were pulled with a tensile tester, and the cohesive failure rate was measured. Then, the case where the cohesive failure rate exceeded 60% was evaluated as ◯, the case where the cohesive failure rate was 10-60% was evaluated as Δ, and the case where the cohesive failure rate was less than 10% was evaluated as ×.

  As is clear from the results in Table 1, the polyorganosiloxane compositions obtained in Examples 1 to 4 are superior to the base material made of Ag compared to the compositions obtained in Comparative Examples 1 to 4. It has excellent adhesion to a substrate made of PPA. Moreover, transparency of cured | curing material is favorable. Therefore, it is suitable as a die attach material for a sealing layer of a light emitting device such as an LED lamp or a light emitting element (LED chip).

Example 5
(A) 28 parts of polysiloxane composed of (CH ₃ ) ₃ SiO _1/2 unit, (CH ₃ ) (CH ₂ ═CH) SiO unit and SiO ₂ unit, and both ends of the molecular chain are blocked with dimethylvinylsiloxy groups. 100 parts of a mixture (vinyl group-containing polymer) (viscosity 11.8 Pa · s) with 72 parts of dimethylpolysiloxane, and (B) methyl hydrodeoxypropylene having a viscosity of 22 mPa · s blocked at both ends of the molecular chain with trimethylsiloxy groups Genpolysiloxane (SiH group content: 9 mmol (equivalent) / g) 6.0 parts (molar (equivalent) ratio of SiH groups in component (B) to vinyl groups in component (A) (H / Vi) = 1.6), (C) 10 ppm of the complex of chloroplatinic acid and divinyltetramethyldisiloxane in terms of platinum metal element with respect to the total amount of components (A) and (B), and Synthesis Example 3 1.4 parts of the obtained adhesion-imparting agent (c), 1.4 parts of the adhesion-imparting agent (f) obtained in Synthesis Example 6 and 1.0 part of the adhesion-imparting agent (i) were mixed. A polyorganosiloxane composition was prepared.

Example 6
(A) dimethylpolysiloxane (vinyl group-containing polymer) and (B) methylhydrogenpolysiloxane used in Example 5 were blended in the proportions shown in Table 2, and (C) platinum-based as in Example 5 A catalyst was formulated. Further, as the adhesion imparting agent, the adhesion imparting agent (c) obtained in Synthesis Example 3, the adhesion imparting agent (h) obtained in Synthesis Example 8, and the adhesion imparting agent (i) 2 were blended in the proportions shown in Fig. 2, and a polyorganosiloxane composition was prepared in the same manner as in Example 5. In Table 2, the description of the blending amount of (C) platinum-based catalyst was omitted.

Example 7
(A) dimethylpolysiloxane (vinyl group-containing polymer) and (B) methylhydrogenpolysiloxane used in Example 5 were blended in the proportions shown in Table 2, and (C) platinum-based as in Example 5 A catalyst was formulated. Further, as the adhesion imparting agent, the adhesion imparting agent (c) obtained in Synthesis Example 3, the adhesion imparting agent (g) obtained in Synthesis Example 7, and the adhesion imparting agent (i) 2 were blended in the proportions shown in Fig. 2, and a polyorganosiloxane composition was prepared in the same manner as in Example 5.

  Next, the compositions obtained in Examples 5 to 7 were thermoformed under conditions of 150 ° C. for 2 hours to form a cured product, and the transparency of the cured product was examined with the naked eye. Those having high transparency were evaluated as ◯, and those having sufficient transparency were evaluated as Δ. Moreover, the adhesiveness with respect to an Ag board | substrate and a PPA board | substrate was measured by the method shown below, respectively. These results are shown in Table 2 together with the measurement results for the composition of Comparative Example 4.

[Measurement of adhesion to Ag]
One end of two Ag substrates (thickness 1 mm) having a width of 25 mm spans a length of 10 mm with a layer of 1 mm thickness made of the composition prepared in Examples 5 to 7 in between. Then, the composition layer was cured by heating at 150 ° C. for 2 hours. The specimen prepared in this manner was allowed to stand at room temperature for 12 hours or more, and then both ends of the specimen were pulled with a tensile tester to measure the cohesive failure rate. Then, the case where the cohesive failure rate exceeded 60% was evaluated as ◯, the case where the cohesive failure rate was 10-60% was evaluated as Δ, and the case where the cohesive failure rate was less than 10% was evaluated as ×.

[Measurement of adhesion to PPA]
A PPA substrate (width 25 mm, thickness 1 mm) was used in place of the Ag substrate, and a test specimen was prepared in the same manner. After leaving this test body for 12 hours or more at room temperature, both ends of the test body were pulled with a tensile tester, and the cohesive failure rate was measured. Then, the case where the cohesive failure rate exceeded 60% was evaluated as ◯, the case where the cohesive failure rate was 10-60% was evaluated as Δ, and the case where the cohesive failure rate was less than 10% was evaluated as ×.

  As is clear from the results in Table 2, the polyorganosiloxane compositions obtained in Examples 5 to 7 have superior adhesion to the base material made of Ag compared to the composition obtained in Comparative Example 4. And has excellent adhesion to substrates made of PPA. Moreover, transparency of cured | curing material is also favorable.

Claims (5)

(A) 100 parts by weight of a polyorganosiloxane having an alkenyl group bonded to a silicon atom;
(B) A polyorganohydrogensiloxane having a hydrogen atom bonded to a silicon atom is 0.1 to 4.0 hydrogen atoms in this component per alkenyl group in the component (A). Quantity,
(C) a platinum catalyst and a catalyst amount;
(D) As an adhesion-imparting agent,
(D1) (i) an alkoxysilyl group and / or an epoxy group, and (iii) a formula:

(In the formula, m is an integer of 1 to 5.)
And (D2) a silane or siloxane compound having an alkoxy group and / or an epoxy group and not containing an isocyanuric ring, each having a total of 0.1 A self-adhesive polyorganosiloxane composition characterized by containing 10 to 10 parts by weight.   The self-adhesive polyorganosiloxane composition according to claim 1, wherein the component (D1) has (ii) a vinyl group and / or an epoxy group.   The self-adhesive polyorganosiloxane composition according to claim 2, wherein the component (D1) has (ii) a vinyl group and an epoxy group, respectively. The component (D1) is represented by the formula (iv):

(In the formula, R is a group selected from an alkoxysilyl group, an epoxy group, and a hydrogen atom, n is an integer of 1 to 5, and k is an integer of 0 to 5).
The self-adhesive polyorganosiloxane composition according to claim 1, which has a siloxy unit-containing group represented by the formula:   5. The self content according to claim 1, wherein the content of the component (D1) is 0.05 to 9.95 parts by weight with respect to 100 parts by weight of the component (A). Adhesive polyorganosiloxane composition.