KR20060099448A - Curable silicone rubber composition and method for producing composite molded product of liquid crystal polymer and silicone rubber - Google Patents

Abstract

The present invention

(A) aliphatic unsaturated bond-containing organopolysiloxane,

(B) organohydrogenpolysiloxanes,

(C) (meth) acrylate compound which contains one or more acryloyl group or methacryloyl group, and is compatible with the said (A) component,

(D) Platinum Group Metal-Based Catalysts

It contains the curable silicone rubber composition for adhesion | attachment to a liquid crystal polymer characterized by including.

According to the silicone rubber composition of this invention, the hardened | cured material which provides effective adhesiveness with respect to the board | substrate of the liquid crystal polymer (LCP) which was very difficult to adhere | attach until now can be obtained. Since the silicone rubber composition of this invention can provide the hardened | cured material excellent in transparency especially, it is effective for the adhesion of the liquid crystal polymer substrate used for various optical display packages, and is useful for the application to the board | substrates for various light related devices.

Curable Silicone Rubber Composition, Liquid Crystal Polymer, Silicone Rubber

Description

CURABLE SILICONE RUBBER COMPOSITION AND PROCESS FOR THE PREPARATION OF COMPOSITE MOLDED BODY OF LIQUID-CRYSTAL POLYMER AND SILICONE RUBBER}

[Patent Document 1] Japanese Patent No. 3313238

[Patent Document 2] Japanese Patent Application Laid-Open No. 7-25987

[Patent Document 3] Japanese Unexamined Patent Publication No. 2002-327126

[Patent Document 4] Japanese Patent Application Laid-Open No. 2002-338833

TECHNICAL FIELD This invention relates to the curable silicone rubber composition of the addition curing type especially used for adhesion | attachment to a liquid crystal polymer, and relates to the curable silicone rubber composition with favorable adhesiveness with respect to the liquid crystal polymer (LCP) which is a thermoplastic plastic. The present invention also relates to a method for producing a composite molded body of a liquid crystal polymer and a silicone rubber.

The silicone rubber composition is used in various applications because it forms a cured product having excellent properties such as weather resistance and heat resistance and rubber properties such as hardness and elongation.

In recent years, LCP (liquid crystal polymer) has been considered as a material for various packages as a thermoplastic having excellent heat resistance. This is because the nylon resin, which has been used a lot since the solder reflow temperature is high, does not have sufficient heat resistance and cannot solve problems such as discoloration.

However, the conventional silicone rubber composition cannot firmly adhere to a package made of LCP, and many defects occur in that peeling occurs at the interface between the package and the silicone rubber easily in a temperature cycle or storage at high temperature and high humidity.

In general, in the addition-curable silicone rubber composition, the adhesion is improved by the addition of various silane coupling agents, but LCP has no effect as a conventional tackifier, and the adhesion to some extent by the addition of some additives. Although there is a silicone rubber material having improved properties, it cannot be said that adhesiveness is sufficient in practical use, and furthermore, since it is not transparent, it cannot be used for applications for optical devices.

Moreover, the following literature is mentioned as a prior art concerning this invention.

[Patent Document 1] Japanese Patent No. 3313238

[Patent Document 2] Japanese Patent Application Laid-Open No. 7-25987

[Patent Document 3] Japanese Unexamined Patent Publication No. 2002-327126

[Patent Document 4] Japanese Unexamined Patent Application Publication No. 2002-338833.

This invention is made | formed in view of the said situation, and the addition hardening type silicone rubber composition for adhesion | attachment to a liquid crystal polymer which provides the hardened | cured material which has sufficient adhesive strength and transparency with respect to LCP, and a composite of a liquid crystal polymer and a silicone rubber It aims at providing the manufacturing method of a molded object.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, (A) aliphatic unsaturated bond containing organopolysiloxane, such as an alkenyl group, (B) organohydrogenpolysiloxane, (C) acryloyl group, or methacryloyl group The board | substrate of the liquid crystal polymer (LCP) which is a thermoplastic plastic which contains one or more, and the silicone rubber composition which contains the (meth) acrylate compound compatible with the said (A) component, and (D) platinum group metal type catalyst is very difficult to adhere | attach. Effective adhesiveness can be provided, and the hardened | cured material was found to have sufficient transparency, and came to complete this invention.

Therefore, the present invention

(A) aliphatic unsaturated bond-containing organopolysiloxane,

(B) organohydrogenpolysiloxanes,

(C) (meth) acrylate compound which contains one or more acryloyl group or methacryloyl group, and is compatible with the said (A) component,

(D) Platinum Group Metal-Based Catalysts

A curable silicone rubber composition for adhesion to a liquid crystal polymer, and a method for producing a composite molded body of a liquid crystal polymer and silicone rubber by laminating and curing the silicone rubber composition on a liquid crystal polymer substrate, comprising To provide.

Best Mode for Carrying Out the Invention

The aliphatic unsaturated bond-containing organopolysiloxane (A) which is the base polymer component of the present invention is an aliphatic unsaturated bond represented by an alkenyl group having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms such as two or more vinyl groups and allyl groups in one molecule. It is preferable to have two or more in the molecule preferably. In this case, as the component (A), a molecule having two or more alkenyl groups in the molecule (A-1), the main chain including repetitions of diorganosiloxane units, and both ends of the molecular chain sealed with a triorganosiloxy group Organopolysiloxanes of a chain organopolysiloxane and a resin structure having two or more alkenyl groups in the (A-2) molecule (that is, a three-dimensional mesh-like structure), and include (A-1) component and (A-2 The component) may be used alone, but it is particularly preferable to use the component (A-1) and the component (A-2) together.

The component (A-1) is preferably an organopolysiloxane having a viscosity of 10 to 1,000,000 mPa · s, particularly 100 to 100,000 mPa · s, at 23 ° C., and above all, both ends of the molecular chain represented by the following general formula (1). It is a linear organopolysiloxane which has 1 or more alkenyl groups on the silicon atom of each, and as mentioned above, it is preferable at workability, sclerosis | hardenability, etc. as the viscosity in 23 degreeC is 10-1,000,000 mPa * s. In addition, a viscosity is a measured value by a rotational viscometer. The linear organopolysiloxane may also contain a small amount of branched structure (trifunctional siloxane units) in the molecular chain.

(Wherein R ¹ is the same or different from each other and is an unsubstituted or substituted monovalent hydrocarbon group, R ² is the same or different from each other and is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds, k, m is 0 or a positive integer and k + m is the number which makes the viscosity in this organopolysiloxane at 23 degreeC from 10 to 1,000,000 mPa * s.)

Here, as the monovalent hydrocarbon group of R ¹ , those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, are preferable, and specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl groups Aryl groups such as phenyl, tolyl, xylyl and naphthyl groups, benzyl, phenylethyl and phenyl, such as alkyl groups such as pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl and decyl groups Aralkyl groups such as aralkyl groups such as propyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups and octenyl groups, and some or all of the hydrogen atoms of these groups Substituted by halogen atoms, such as fluorine, bromine, and chlorine, and a cyano group, For example, halogen substituted alkyl groups, such as a chloromethyl group, a chloropropyl group, a bromoethyl group, and a trifluoropropyl group, cyanoethyl group, etc. are mentioned. have.

Moreover, as a monovalent hydrocarbon group of R <^2> , a C1-C10, especially 1-6 are preferable, and the same thing as the specific example of said R <^1> can be illustrated, but an alkenyl group is not contained.

k and m are generally 0 or a positive integer satisfying 0 <k + m≤10,000, preferably 5≤k + m≤2,000, more preferably 10≤k + m≤1,200, and 0 < k / (k + m) ≦ 0.2, preferably an integer satisfying 0 <k / (k + m) ≦ 0.1.

Specific examples of the component (A-1) include the following.

(Wherein t is an integer of 8 to 2,000.)

(Wherein k and m are as described above.)

The organopolysiloxane (silicone resin) of the resin structure of the component (A-2) can also be used alone or in combination with the linear organopolysiloxane of the component (A-1) as the component (A).

The organopolysiloxane (A-2) of the resin structure (namely, three-dimensional mesh-like structure), with SiO _{2 ^{units, R 3 n R 4 p SiO}} 0 .5 units and ^{_{R 3 q R 4 r SiO 0}} .5 units Organopolysiloxane having a resin structure, provided that R ³ is a vinyl group or an allyl group, R ⁴ is a monovalent hydrocarbon group containing no aliphatic unsaturated bonds, n is 2 or 3, and p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3, and q + r = 3.

Moreover, as a monovalent hydrocarbon group of R <^4> , the C1-C10 same thing as said R <^2> , especially the thing of 1-6 are mentioned.

Here, the SiO ₂ unit as a ^{_{unit, R 3 n R 4 p SiO}} 0 .5 when considered in units of b ^{_{units, R 3 q R 4 r SiO}} 0 .5 units of the unit c, the molar ratio

(b + c) /a=0.3 to 3, in particular 0.7 to 1

c / a = 0.01 to 1, in particular 0.07 to 0.15

It is preferable that it is, and it is preferable that this organopolysiloxane has a weight average molecular weight of 500-10,000. In addition, a weight average molecular weight is the measured value by polystyrene conversion using gel permeation chromatography (GPC).

In addition, the organopolysiloxane of the resin structure, in addition to the a unit, b unit, and c unit, difunctional siloxane unit or trifunctional siloxane unit (that is, organosilsesquioxane unit) impairs the object of the present invention It may contain a small amount further in the range which does not make it.

The organopolysiloxane of such a resin structure can be synthesize | combined easily by combining silane or siloxane compound which becomes each unit member so that the said molar ratio may be carried out by co-hydrolysis in presence of an acid, for example.

Here, as said a unit member, a sodium silicate, an alkyl silicate, a polyalkyl silicate, silicon tetrachloride, etc. can be illustrated.

In addition, the following can be illustrated as a b unit member.

In addition, the following can be illustrated as a c unit member.

The organopolysiloxane (A-2) of the said resin structure is mix | blended in order to improve the physical strength of the hardened | cured material, and the adhesiveness of a surface, It is 20-70 mass% with respect to the total amount of the said (A) component, Especially 30-60 mass% It is preferable to mix | blend so that it may contain, and when the compounding quantity of organopolysiloxane of resin structure is too small, the said effect is not fully achieved, when too much, the viscosity of a composition will become high remarkably, or a crack will be easy to generate | occur | produce in hardened | cured material, etc. There is a risk of disadvantage.

The organohydrogenpolysiloxane which is (B) component acts as a crosslinking agent, and hardened | cured material is formed by addition reaction of the SiH group in the said component, and alkenyl groups, such as the vinyl group in (A) component. Such organohydrogenpolysiloxane may be any one having two or more, in particular three or more, hydrogen atoms (ie, SiH groups) bonded to silicon atoms in one molecule, and in particular, represented by the following average compositional formula (2) In one molecule, two or more hydrogen atoms (SiH groups) bonded to silicon atoms (usually 2 to 300), preferably 3 or more (for example, 3 to 300, more preferably 3 to 150) Dogs).

H _a (R ⁵ ) _b SiO _{(4-ab) / 2}

(Wherein R ⁵ is the same or different and does not contain an aliphatic unsaturated bond and is an unsubstituted or substituted monovalent hydrocarbon group, a and b are 0.001 ≦ a <2, 0.7 ≦ b ≦ 2, and 0.8 ≦ a A number satisfying + b≤3.)

Herein, R ⁵ in the general formula (2) is the same or different and does not contain an aliphatic unsaturated bond, and is preferably an unsubstituted or substituted C1-C10 monovalent hydrocarbon group having 1 to 7 carbon atoms, for example, a methyl group. an aryl group of a lower alkyl group, a phenyl group and the like, such as, those illustrated as substituents R ² in the above formula (I). A and b are numbers satisfying 0.001 ≦ a <2, 0.7 ≦ b ≦ 2, and 0.8 ≦ a + b ≦ 3, preferably 0.05 ≦ a ≦ 1, 0.8 ≦ b ≦ 2, and 1 ≦ It is a number which becomes a + b <2.7. There is no restriction | limiting in particular in the position of the hydrogen atom couple | bonded with the silicon atom, It may be the terminal of a molecule | numerator, or may be halfway.

Examples of the organohydrogenpolysiloxane include tris (dimethylhydrogensiloxy) methylsilane, tris (dimethylhydrogensiloxy) phenylsilane, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7 Tetramethylcyclotetrasiloxane, both terminal trimethylsiloxy group blocking methylhydrogenpolysiloxane, both terminal trimethylsiloxy group blocking dimethylsiloxane and methylhydrogensiloxane copolymer, both terminal dimethylhydrogensiloxy group blocking dimethylpolysiloxane, both terminal dimethylhydrogen Siloxy group blocking dimethylsiloxane, methyl hydrogen siloxane copolymer, both terminal trimethylsiloxy group blocking methyl hydrogen siloxane, diphenyl siloxane copolymer, both terminal trimethylsiloxy group blocking methyl hydrogen siloxane, diphenyl siloxane, dimethylsiloxane copolymer, (CH _{3) 2} HSiO _1/2 units and copolymers composed of SiO _{4/2 units, (CH 3) 2 HSiO 1} /2 units and SiO _4/2 units and (C ₆ H ₅₎ there may be mentioned copolymers consisting of SiO _3/2 units.

Moreover, the compound like what is represented by the following structure can also be used.

The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched and three-dimensional mesh structures, but the number (or degree of polymerization) of silicon atoms in one molecule is 3 to 1,000, especially about 3 to 300. Can be used.

Such organohydrogenpolysiloxanes typically hydrolyze chlorosilanes such as R ⁵ SiHCl ₂ , (R ⁵ ) ₃ SiCl, (R ⁵ ) ₂ SiCl ₂ , (R ⁵ ) ₂ SiHCl (R ⁵ is as above) and Can be obtained by equilibrating the siloxane obtained by hydrolysis.

Moreover, the compounding quantity of this organohydrogenpolysiloxane is the hardening effective amount of the said (A) component, Especially its SiH group is 0.1-4.0 per total amount of the alkenyl group (for example, vinyl group) in (A) component, Especially preferably, It is preferably used in a molar ratio of 1.0 to 3.0, more preferably 1.2 to 2.8. If it is less than 0.1, hardening reaction does not advance and it is difficult to obtain a silicone rubber hardened | cured material, and when it exceeds 4.0, since unreacted SiH group remains in a large quantity in hardened | cured material, rubber property becomes a cause which changes with time. There is a case.

Component (C) acryloyl group (CH ₂ = CH-CO-) or meta group in methacrylate _{(CH 2 = C (CH 3} ) -CO-) containing at least one, and said component (A) are compatible with It is a (meth) acryl compound. In addition, the (meth) acryl compound may be a monomer or may be an oligomer or polymer of the (meth) acryl compound having one or two or more remaining (meth) acryloyl groups in a molecule, or may be a polyester. Although one terminal and / or both ends of a polyether, polycarbonate compound, etc. may be sealed with a (meth) acryloyl group, it becomes compatible with the aliphatic unsaturated bond containing organopolysiloxane which is (A) component, and becomes transparent. It should be possible. Here, a (meth) acryl compound represents an acryl compound or a methacryl compound.

Especially as said (C) component, the following can be illustrated.

For example, lauryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene Monofunctional (meth) acrylates such as glycol mono (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 5- Diacrylic acid ester of ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxane (trade name: Kayarard R-604, manufactured by Nippon Kayaku) Or its corresponding methacrylic acid ester, 2-propenoic acid (octahydro-4,7-methane-1H-indenylyl) bis (methylene) ester (trade name: Kayarard R-684, manufactured by Nippon Kayaku) or its corresponding In the molecule, such as bifunctional (meth) acrylates, such as methacrylic acid ester, It does not contain an atom, and the ester part may also contain a hydroxyl group and / or an ether bond oxygen atom, and is a monovalent or divalent hydrocarbon group having 4 to 30 carbon atoms, preferably about 8 to 20 carbon atoms, The (meth) acrylate compound which is monofunctional or bifunctional, is compatible with the said (A) component and / or (B) component, and can provide a transparent composition is suitable.

The blending amount of the component (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass based on 100 parts by mass in total of the component (A) and the component (B). When the compounding quantity of (C) component is too small, adhesiveness with respect to a base material, especially a liquid crystal polymer may become inferior, and when too large, it may adversely affect the hardness and surface adhesiveness of hardened | cured material.

The platinum group metal catalyst of (D) component which is a hardening catalyst of the composition of this invention is as showing below.

This catalyst component is mix | blended in order to produce the addition hardening reaction of the composition of this invention, Although it is a platinum type, a palladium type, a rhodium type thing, it is platinum type, such as platinum, platinum black, chloroplatinic acid, etc. from a viewpoint of cost, etc., for example, H ₂ PtCl ₆ and _{mH 2 O, K 2 PtCl 6} , KHPtCl 6 and _{mH 2 O, K 2 PtCl 4} , K 2 PtCl 4 and mH ₂ O, PtO ₂ and mH ₂ O (m is a positive integer And the like, and a complex of these and hydrocarbons such as olefins, alcohols or vinyl group-containing organopolysiloxanes, and the like, and these can be used alone or in combination of two or more thereof. The blending amount of these catalyst components may be a so-called catalytic amount, and is usually used in the range of 0.1 to 1,000 ppm, preferably 0.5 to 200 ppm, in terms of platinum group metal (mass) relative to the total amount of the components (A) to (C). .

In order to provide adhesiveness further, the composition of this invention can mix | blend an adhesion | attachment adjuvant as (E) component. As such an adhesion aid, in one molecule, a hydrogen atom (SiH group) bonded to a silicon atom, an alkenyl group (for example, Si-CH = CH ₂ group) bonded to a silicon atom, an alkoxysilyl group (for example, trimeth) Linear or cyclic silicon containing two or more, preferably two or three, functional groups selected from oxysilyl groups) and epoxy groups (e.g., glycidoxypropyl groups, 3,4-epoxycyclohexylethyl groups) Organosiloxane oligomers having 4 to 50 atoms, preferably 4 to 20 atoms, or organooxysilyl-modified isocyanurate compounds represented by the following general formula (3) and / or hydrolyzed condensates thereof (organosiloxanes: It is preferable to mix | blend adhesion | attachment adjuvant, such as a modified isocyanurate compound) as an arbitrary component as needed.

<Formula 3>

(Wherein, R ⁶ is a monovalent hydrocarbon group containing an organic group or an aliphatic unsaturated bond represented by the following general formula (4), at least one is an organic group of the general formula (4).

<Formula 4>

(In formula, R <^7> is a hydrogen atom or a C1-C6 monovalent hydrocarbon group, s is an integer of 1-6, especially 1-4.)

In this case, as the monovalent hydrocarbon group containing an aliphatic unsaturated bond of R ⁶ , a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, cyclohexenyl group or the like And alkenyl groups having 2 to 8, particularly 2 to 6, carbon atoms. Examples of the monovalent hydrocarbon group for R ⁷ include an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group and cyclohexyl group, vinyl group, C1-C8, especially 1-6 monovalent hydrocarbon groups, such as the same alkenyl group and the same aryl group which were illustrated as said R <^6> , such as an allyl group, a propenyl group, and an isopropenyl group, are mentioned preferably, It is an alkyl group.

As an adhesion | attachment adjuvant which is (E) component, the compound represented by a following formula is illustrated.

(Wherein m and n are each positive integers in which m + n satisfies 2 to 50, preferably 4 to 20).

In such an organosilicon compound, as a compound which is especially excellent in the adhesiveness of the hardened | cured material obtained, it is preferable that it is an organosilicon compound which has a silicon atom bond alkoxy group, an alkenyl group, or a silicon atom bond hydrogen atom (SiH group) in 1 molecule.

In this invention, the compounding quantity of the adhesion | attachment adjuvant which is said (E) component (optional component) is 10 mass parts or less normally (that is, 0-10 mass parts) with respect to a total of 100 mass parts of (A) component and (B) component. ), Preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass. If the amount of the component (E) is too small, the adhesiveness to the substrate may be poor. If the amount of the component (E) is too small, the hardness and the surface adhesion of the cured product may be adversely affected.

Although the silicone rubber composition of this invention is manufactured by mixing each component mentioned above uniformly, of course, it can also use as a one-component composition by adding a small amount of hardening inhibitors, such as acetylene alcohol. This composition is instantly cured by heating if necessary, has high transparency, and adheres very well to package materials such as LCP and metal substrates, and thus is widely used as a general purpose application in semiconductor packages such as LEDs, photodiodes, CCDs and CMOS. Can be.

Although the silicone rubber composition of this invention is effective for the adhesive use with respect to a liquid crystal polymer (LCP) in this way, it does not restrict | limit especially as a liquid crystal polymer here, It is not limited to any liquid crystal polymer conventionally known, including a polyester-type liquid crystal polymer. Applicable

<Example>

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, in a following example, a part shows a mass part and a viscosity is a value in 23 degreeC. In addition, Vi represents a vinyl group.

Example 1

Formula (i)

(i)

(i)

Polysiloxane (VF) in 50 parts, SiO ₂ units of 50 mol% represented _{by, (CH 3) 3 SiO 0} .5 units 42.5 of methyl vinyl resin structure comprising in mol% and Vi ₃ SiO _{0 .5} 7.5% mole units of the siloxane (VMQ) 50 parts by volume of the amount of SiH group is 1.5 times mole with respect to the total amount of vinyl groups in said (VF) and (VMQ) component (ii)

(ii)

(ii)

0.05 parts of an octyl alcohol-modified solution of organohydrogenpolysiloxane and chloroplatinic acid represented by 0,5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3 1.0 parts of diacrylic acid esters of dioxane (trade name: Kayarard R-604, manufactured by Nippon Kayaku) were added to prepare a silicone rubber composition. The composition was heat-molded at 150 ° C./4 hr to form a cured product, and tensile strength, hardness (measured using a type A spring tester) and elongation rate were measured according to JIS K 6301. Further, a silicone rubber composition is applied to a polyester-based liquid crystal polymer (trade name: Sumika, Sumitomo Chemical Co., Ltd.) substrate, the same liquid crystal polymer substrate is disposed thereon, the composition is cured, and the liquid crystal polymer substrate Shear adhesion to the substrate of the cured product sandwiched was measured. Each measurement result is shown in Table 1.

Example 2

R-604 used in Example 1 was changed to 2-propenoic acid (octahydro-4,7-methane-1H-indenylyl) bis (methylene) ester (trade name: Kayarard R-684, manufactured by Nippon Kayaku) A silicone rubber composition was produced with the same composition as in Example 1 except that the cured product was formed, and the results obtained in the same manner as in Example 1 are shown in Table 1.

Example 3

Except for changing the R-604 used in Example 1 to lauryl acrylate, a silicone rubber composition was prepared by the same composition as in Example 1, the cured product was formed, and the results measured in the same manner as in Example 1 are shown in Table 1. Indicated.

Example 4

Formula (iii) to the composition used in Example 1

(iii)

(iii)

Except having added 0.5 part of the adhesion | attachment adjuvant shown by the following, the silicone rubber composition was manufactured by the same composition as Example 1, the hardened | cured material was formed, and the result measured similarly to Example 1 is shown in Table 1.

Example 5

Formula (iv) to the composition used in Example 1

(iv)

(iv)

Except having added 1.0 part of the adhesion | attachment adjuvant shown by the following, the silicone rubber composition was manufactured with the composition similar to Example 1, the hardened | cured material was formed, and the result measured similarly to Example 1 is shown in Table 1.

 Comparative Example 1

Except not adding R-604 of Example 1, the silicone rubber composition was manufactured by the same composition as Example 1, the hardened | cured material was formed, and the result measured similarly to Example 1 is shown in Table 1.

Comparative Example 2

Except not adding R-604 of Example 1, the silicone rubber composition was manufactured by the same composition as Example 4, the hardened | cured material was formed, and the result measured similarly to Example 1 is shown in Table 1.

[Examples 6 to 9]

Except having changed the R-604 of Example 1, the lauryl acrylate of Example 3, and the adhesion | attachment adjuvant (iv) used in Example 5 to the quantity shown in Table 2, the thing of the same composition as Example 1 is implemented. Table 2 shows the results measured in the same manner as in Example 1.

According to the silicone rubber composition of this invention, the hardened | cured material which provides effective adhesiveness with respect to the board | substrate of LCP which was very difficult to adhere | attach until now can be obtained. Since the silicone rubber composition of this invention can provide the hardened | cured material excellent in transparency especially, it is effective for the adhesion of the liquid crystal polymer substrate used for the package of various optical displays, and is useful for the application to the substrate for various light related devices.

Claims (7)

(A) organopolysiloxane containing an aliphatic unsaturated bond, (B) organohydrogenpolysiloxanes, (C) (meth) acrylate compound which contains one or more acryloyl group or methacryloyl group, and is compatible with the said (A) component, (D) Platinum Group Metal-Based Catalysts Curable silicone rubber composition for adhesion | attachment to a liquid crystal polymer characterized by including the. The resin of claim 1, wherein the component (A) has a linear organopolysiloxane having two or more alkenyl groups in the molecule (A-1) and a resin structure having two or more alkenyl groups in the molecule (A-2). Curable silicone rubber composition which uses a combination of poly-polysiloxane. (A-1) A component is represented by following General formula (1), (A-2) component is SiO ₂ units, R ³ _n R ⁴ _p SiO _{0 .5} units and ^{_{R 3 q R 4 r SiO 0}} .5 units (where, in the general formula, R ³ is a vinyl group or allyl group, R ⁴ is a monovalent hydrocarbon group containing no aliphatic unsaturated bond, n is 2 or 3, p is 0 or 1, n + p = 3, q is 0 or 1, r is 2 or 3 and, q + r = 3 Lim) is made of, the SiO ₂ unit of a unit, R ³ _n R ⁴ _p SiO _{0 .5} units of b units, R ³ _q R ⁴ _r SiO _{0 .5} units of the unit c In the case of molar ratio (b + c) /a=0.3 to 3 c / a = 0.01 to 1 Curable silicone rubber composition which is a silicone resin of. <Formula 1>

(Wherein R ¹ is the same or different from each other and is an unsubstituted or substituted monovalent hydrocarbon group, R ² is the same or different from each other and is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds, k, m is 0 or a positive integer and k + m is the number which makes the viscosity in this organopolysiloxane at 23 degreeC from 10 to 1,000,000 mPa * s.) Curable silicone rubber composition of Claim 2 or 3 whose content of (A-2) component is 20-70 mass% in (A) component. The component (C) according to any one of claims 1 to 3, wherein the component (C) is lauryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, diethylene glycol mono (meth). ) Acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth ) Acrylate, di (meth) acrylic acid ester of 5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxane or 2-propeno A curable silicone rubber composition which is an icic acid (octahydro-4,7-methane-1H-indenylyl) bis (methylene) ester. (E) Adhesion aids, The hydrogen atom (SiH group) couple | bonded with the silicon atom, the alkenyl group couple | bonded with the silicon atom, the alkoxy silyl group, the epoxy group in any one of Claims 1-3. Linear or cyclic organosiloxane oligomers containing 4 to 50 silicon atoms, or an organooxysilyl-modified isocyanurate compound represented by the following general formula (3) containing two or more functional groups selected from: Curable silicone rubber composition which further mix | blended a hydrolysis condensate. <Formula 3>

(Wherein, R ⁶ is a monovalent hydrocarbon group containing an organic group or an aliphatic unsaturated bond represented by the following general formula (4), at least one is an organic group of the general formula (4). <Formula 4>

(In formula, R <^7> is a hydrogen atom or a C1-C6 monovalent hydrocarbon group, s is an integer of 1-6, especially 1-4.) The manufacturing method of the composite molded object of a liquid crystal polymer and silicone rubber containing the process of laminating | stacking and hardening | curing the silicone rubber composition of any one of Claims 1-3 on a liquid crystal polymer substrate.