TW201124477A - Polysiloxane composition and cured article thereof - Google Patents

Abstract

The objective of this invention is to provide a polysiloxane composition that gives sufficient adhesive strength to various package materials composed of thermoplastics, such as LCP (liquid crystal polymer) that is hard to be adhered, and gives a transparent cured article; and the cured article of the composition, and a semiconductor device sealed by the cured article. A polysiloxane composition is characterized by composing of the following components. (A) organopolysiloxane that contains at least two alkenyl groups in one molecule; (B) an organohydrogenpolysiloxane that contains at least two hydrogen atoms bonded with silicon atoms in one molecule; (C) a platinum group metal-based catalyst; (D) an organosiloxane containing an isocyanuric ring, which has allyl, epoxy, organosiloxanyl groups in one molecule.

Description

201124477 VI. Description of the Invention: [Technical Field] The present invention relates to an addition hardening type polyfluorene composition, and more particularly to a cured product which provides good adhesion to a thermoplastic such as a liquid crystal polymer (LCP). Polyoxyl composition and its hardened material. [Prior Art] The polyoxymethylene composition is used for various applications such as a cured product having good weather resistance, heat resistance, or rubber properties such as good hardness and elongation. Furthermore, the soldering conditions of the recent packaging have been changed to high-temperature soldering without lead, and the conventional nylon-based resin has problems such as insufficient heat resistance and discoloration. The LCP (liquid crystal polymer) of a thermoplastic having good heat resistance is used as various packaging materials. Various polyfluorene resins have been developed as sealants or adhesives for adhesion to LCP. However, due to high temperature pressure or temperature cycling and storage in a high temperature and high humidity environment, most of the defects occur in the interface between the package and the polyoxyxene resin. . In general, the addition-hardening type polyfluorene-based composition is improved in adhesion by adding various decane coupling agents (Patent Document 1 and Patent Document 2). However, such a composition cannot be sufficiently reacted to the end, and the conditions are strict. Exfoliation will occur during the test. Furthermore, it will change color when it causes a violent reaction, and it is not transparent, and it cannot be used for light purposes. Japanese Patent Publication No. 2 007-2234 (Patent Document 3) discloses a curable polyoxyxene rubber composition containing a known adhesion aid. However, this curable polyoxymethylene rubber composition is still insufficient in adhesion. [Patent Document 1] JP-A-2005-42099 (Patent Document 3) JP-A-2007-223 No. [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyfluorene-oxygen composition which is a package material which is composed of a thermoplastic such as an LCP (liquid crystal polymer) which is difficult to adhere to. A cured product having sufficient adhesive strength and having transparency; and a cured product of the composition, and a semiconductor device sealed with the cured product. [Means for Solving the Problem] The inventors of the present invention conducted thorough research to achieve the above object, and as a result, found that the molecule contains an organooxane having an epoxy group and a heteroxyl cyanide ring as an adhesion promoter. The composition provides a cured product having sufficient adhesion strength to a substrate which is difficult to adhere to various packaging materials such as LCP and the like, and which has good transparency. That is, the present invention provides a polyfluorene oxide composition characterized by containing the following components, (A) an organopolyoxane (B) having at least two alkenyl groups in one molecule and having at least 2 in one molecule a hydrogen atom bonded to a ruthenium atom -6 - 201124477 machine hydrogen polyoxyalkylene (C) lead group metal catalyst (D) having an allyl group, an epoxy group and an organic sulfoxyalkyl group in one molecule An organic siloxane having a hetero-cyanuric ring and a cured product thereof, and a semiconductor device sealed with the cured product. [Effect of the Invention] The polyoxagen composition of the present invention provides a cured product which has good transparency and exhibits good adhesion to a substrate such as LCP which is very difficult to adhere. The semiconductor device sealed by the cured material can be a semiconductor device capable of passing a rigorous reliability test. [Embodiment] (A) Alkenyl group-containing organopolyoxane The alkenyl group-containing organopolyoxane (A) of the base component of the present invention has a viscosity of 10 to 1,000,000 mPa·s at 25 ° C. It is preferably 100 to 1 00,000 m P a · s, preferably 5 0 0 to 1 0,0 0 m P a . s is preferred, but it is preferably compatible with the component (D). The organopolyoxyalkylene is preferably one or more alkenyl groups having 2 to 8 carbon atoms in one molecule, and is particularly preferably formed by repeating an alkenyl group having 2 to 6 carbon atoms. Further, both ends of the molecular chain are preferably blocked with a triorganooxyalkylene group, and a linear organopolyoxane represented by the following formula (1) is desirable. Further, the linear organopolyoxane may have a small amount of branched structure in the molecular chain. The viscosity of the organic polyoxyalkylene can be measured by rotating the viscosity of the 201124477 meter. [1] R1 R1 R2 R1

CH2=CH-Si-〇-fSi-〇)-f-Si-〇+-Si-CH=CH2 丄1 I m I η I R1 R1 R2 R1 (1) (where m and n are 〇 or positive The integer, m + n is the number of the organic polyoxyalkylene at a viscosity of 10 to 1,000,0001^3.3 at 25 ° C. Thus, "1, 11 is 0 < 111 + 11 $ 1 〇, 〇〇 〇 〇 or a positive integer, 〇 <111 + 11$ 2,000 is preferred, 0<m + n $700 is preferably an integer.) wherein R 1 is independently unsubstituted or substituted one-valent hydrocarbon group . The monovalent hydrocarbon group preferably has a carbon number of from 1 to 10, particularly preferably from 1 to 6, and specifically, a lower alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkane such as a cyclohexyl group; An aryl group such as phenyl, tolyl or xylyl; an aralkyl group such as benzyl; vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, An alkenyl group such as an octenyl group; or a group in which a part or all of hydrogen atoms of the groups are substituted with a halogen atom, a cyano group or the like, such as chloromethyl, cyanoethyl, 3,3,3-trifluoropropane Base. Wherein R2 is independently unsubstituted or substituted and does not contain a one-valent hydrocarbon group. The monovalent hydrocarbon group has a carbon number of 1 to 10, and particularly preferably, 'specifically, S' may be mentioned as a lower alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkyl group such as a cyclohexyl group; An aromatic group such as a benzyl group, a tolyl group or a xylyl group; an aromatic group such as a benzyl group; a group in which a part or all of hydrogen atoms of the groups are substituted with a halogen atom, a cyano group or the like, such as a chloromethyl group or a chlorine group; Ethyl, 3,3,3-trifluoropropyl, and the like. 201124477 Such an organic polyoxane can be exemplified by the following formula. [chemical 2] p-q

CH 3 (CH2=CH)P-Si (CH3)〇 -〇-Si^ CH3

c 丨SIC H5 6 H5 η2)·c -PH 5)3r 6H.LH3 c —SIC /l> I /IVo is pm 'The upper formula is as η, m, but the whole number is 2 - ο is q a whole number

In the formula, the ground body is more separable into N)y A 3

Η c II C2 H

H c II 2C H CH3-I丨CH3CH31—CH3 Η C 11 Η c H3I—H3 cIsIc t H3i-oH3 c——sjc n3 c- 4/Γ H3 isle H5-0H5 6 - 6 c —si-c

-2 c = H c H3I—H3 CISIC VII q + P <=

h;:0£ CISIC 1 H c = c2 H 6Η5Ϊ-0Η3c —silc / — t H3-0H3clsilc

-2 c = H c h31h3 CISIC 4 H5-0 6 .'fi c —SIC I H c II c —2 n5 6 n—CH3

6 卜 6 c — SIC

6H.L 2 c = H c H5 ch3 ch3 c6h5 ch3 H2C—CH—Si—O (-Si-〇-)~~Si—0·^—Si—CH=CH2 II m I η I ch=ch2 ch3 c6h5 Ch=ch2 201124477 ch=ch2 ch3 c6h5 ch=ch2 H2C=CH-Si-0—(-Si-0·)-^ 峑-〇)—Si—CH Two CH: CH=CH2 CH; c6h5 ch=ch2 CH =CH2 ^^3 ch=ch2 H2C=CH-Si-0—f-Si-〇4~Si—CH=CH2

I I m I ch=ch2 ch3 ch=ch2

CeHs ch3 c6h5 c6h5 H2C=CH—Si—〇—(—Si_〇)—(Si—〇)—Si_CH=CH2 ch=ch2 ch3 c6h5 n ch=ch2 (in the above formula, m and n are as described above) 5] ch3 ch3 C6H5 ch3 1 0 H2C=HC-Si-〇-fSi-〇)— I 100 fsi 〇4- -Si—CH=CH2 CH: J CH3 丄10 ch3 CH; 3 9H3 c6h5 ch3 H2C=HC— Si—〇—(—Si—〇—)-fsi—0—)—Si—CH=CH 2 丄丨.100 I 20 I ch3 ch3 c6h5 ch3 Further, the component (A) of the present invention may be a resin structure (ie, , a three-dimensional network structure) of a mixture of an organic polyoxane and an organic polyoxoxane of the formula (η). The resin-structured organopolyoxyalkylene is composed of a Si〇2 unit, a R3kR4pSiOG5 unit, and a R3qR4rSiOG.5 unit. An organic polyoxyalkylene (in the above formula, R3 is a vinyl group or an allyl group; R4 is a monovalent hydrocarbon group having no alkenyl group; k is 2 or 3, and p is an integer of 0 or 1, but k + p = 3 ; q is 0 or 1, r is an integer of 2 or 3, but q + r = 3) is preferably a resin-structured organopolyoxane. Further, R4 is a monovalent hydrocarbon group as described above for R2. Among them, a methyl group and a phenyl group are preferred. -10- 201124477 A resin-structured organic polyoxane is a The unit is si 02 unit, the b unit is the R3kR4PSiOQ.5 unit, and the c unit is the R3qR4rsiOG.5 unit, the molar ratio is preferably (b + c) /a = 0.3 〜3, 0.7~1_〇; /a = 0.01~l, 0.07~0.1 5 The preferred amount is preferably formed. Further, the organopolyoxyalkylene has a weight average molecular weight in terms of polystyrene of GPC of 50 to 10,000. Further, in addition to the above-mentioned a unit, b unit, and c unit, the organic polyoxyalkylene of the resin structure may further contain a small amount of a difunctional oxirane unit insofar as the object of the present invention is not impaired. Or a trifunctional oxoxane unit (ie, an organic sesquiterpoxy oxymethylene unit). A resin-structured organopolyoxy siloxane is a compound which is a unit source of the above-mentioned a unit, b unit, and c unit in the above molar ratio. ' For example, it can be easily synthesized by co-hydrolysis reaction in the presence of an acid. Sodium citrate, hydroxy decanoate, polyhydroxy decanoate, tetrachloride, etc. can be used as the a unit source. The following can be used as b Unit source. [Chemical 6] ch=ch2 | 4 ch=ch2 ch3 H2C=CH-Si——0 - —S i—CH=CH2 h2c= :CH—Si—Cl ch=ch2 ch=ch2 ch=ch2 ch3 I ?h3 CH=CH H2C=CH-Si——0- | —Si—CH=CH2 h2c= 1 =CH -~Si—Cl ch=ch2 CH=CH2 CH=CH: 9 H2C=CH—Si——0-| 9 —Si—CH=CH2 ch=ch2 ch=ch2 -11 201124477 The following can be used as the c unit source. [Chemical 7] CH3 ch3 CHg-Si-Ο-Si-CH3 I I 3 ch3 ch3 ch3 I 3

CHg-Si^-CI ch3 c2h6 c2h6 H2C=CH—Si-0Si—ch=ch2 ch3 ch3

Ch3 H2〇=ch—si—ci ch3 The organic polyfluorene oxide structure of the resin structure is blended to improve the physical strength and surface viscosity of the cured product. The organic polysiloxane is preferably blended in an amount of from 20 to 70% by mass in the component (A), and preferably from 30 to 60% by mass. When the blending amount of the organic polyoxyalkylene having a resin structure is too small, the above effects may not be sufficiently obtained. When the amount is too large, the viscosity of the composition is remarkably high, and cracks are likely to occur in the cured product. Further, the component (A) of the present invention is compatible with the component (D), and the phenyl content in the organopolyoxane can be appropriately adjusted to obtain an optimum refractive index. (B) Organohydrogen polyoxyalkylene organohydrogen polyoxyalkylene functions as a crosslinking agent, and an addition reaction is carried out by the SiH group in the component and the alkenyl group in the component (A) and the component (D). Hardened material. The organic hydrogen polyoxyalkylene to be used may be any one of two or more hydrogen atoms bonded to a ruthenium atom in one molecule (hereinafter referred to as a SiH group), but in particular, the following average composition is used. Formula (4). -12- 201124477 【化8】 R, S i〇(4- a _ b ... (4) (wherein R 5 is substituted or unsubstituted, and does not contain one of aliphatic unsaturated bonds a valence hydrocarbon group; a and b are those satisfying 〇.〇〇丨$ a<2, 〇7 g bS2, and 0.8$a + b$3.) shown in the molecule containing at least 2 S i Η groups Preferably, more than 3 are preferred. Here, R5 in the above formula (4) is substituted or unsubstituted independently of each other, and the number of carbon atoms which does not contain an aliphatic unsaturated bond is 丨~丨〇 In particular, a hydrocarbon group having a carbon number of 1 to 7 is preferable, and examples thereof include an example of R2 of the above formula (1), such as a lower alkyl group such as a methyl group or an aromatic group such as a phenyl group. a and b are 0.001 Sa < 2, 〇.7 SbS2, and 0.8 each a + bS3; to satisfy 〇.〇5Sa$l' 〇_8彡b彡2, and lga + b each of 2.7 is Preferably, the position of the SiH group in the molecule is not particularly limited, and may be at the end or in the middle of the molecular chain. Such an organic hydrogen polyoxyalkylene may be exemplified by tris(dimethylhydroquinone)methane, three (two). Methylhydroquinone)phenyl decane, 113,3-tetra Methyldioxane, 1,3,5,7-tetramethylcyclotetraoxane, trimethylphosphonium oxyalkylene at both ends, methyl hydrogen polyoxyalkylene, trimethyl sulfonium Alkyl chelate monomethyl oxime. Methyl hydroquinone copolymer, dimethyl hydrazine oxyalkylene chelating dimethyl polyoxane, dimethyl hydrazine at both ends Chelating dimethyl methoxy alkane • methyl hydroquinone copolypolymer, trimethyl decyloxyalkyl group at both ends, chelating methyl hydroquinone • diphenyl decane copolymer, both ends Trimethylphosphonium alkyl chelating methylhydroquinone oxime diphenyl decane dimethyl dioxane copolymer, from (CH3) 2HSi01/2 unit and Si04/2 unit-13- 201124477 a copolymer composed of a (CH3) 2HSi01/2 unit and a Si04/2 unit and a (CeH5) Si03/2 unit. The molecular structure of the organic hydrogen polyoxyalkylene may be linear. Any one of a ring-shaped, branched-chain or three-dimensional network structure, but preferably, the number of germanium atoms (or polymerization degree) used in one molecule is 3 to 1000, preferably 3 to 300, and 3 to 1〇. Especially preferred. Such organic hydrogen polyoxyalkylene can usually be used Hydrolysis of chlorosilane such as R5SiHCl2, (R5) 3SiCI, (R5) 2SiCl2 '(R5) 2SiHCl (R5 as described above), or equilibration of the hydroxane obtained by hydrolysis to obtain a linear organohydrogen polyfluorene The alkane may be mentioned by the following formula: [Chemical 9] f V f-

Hr-SiO-(SiO)c-(SiO)d-A-Hr

I, I R5 R5 ch3 ch3 h ch3 H-SiO-(SiO)c-(SiO)d-Si-H ch3 ch3 ch3 ch3 (but c and d are satisfied with 〇<c$ 1000,0<d$ 1000, 〇 <c+d$ 1000 integer 'to satisfy 〇<c + d$ 100 integers. r5 is the same as above, Γ is an integer of 1~3 ^) Branched organic hydrogen polyxide It can be cited as shown in the following formula - 14 - 201124477 [化1 ο]

H3C-Si-CH3 Η H3C-S1-CH3 ch3 ch3 0 ch3

丨. 丨. 丨. I I H—Si—O—Si—0—Si—0—Si—Si—H ch3 ? ch3 CH,

H3C-Si-CH3 H In addition, the amount of the organic hydrogen polyoxymethane blended is such that the above (A) component and (D) component can be effectively hardened, in particular, the SiH group in the organohydrogen polyoxyalkylene. The amount of the (A) component and the (D) component of the susceptibility (for example, vinyl) is preferably 1 to 4 m, and the amount of 0.1 to 4.0 m is preferably '1.0 to 3.0 is preferred' 1.2 to 2_8 . When the amount of SiH is less than the above lower limit ,, the hardening reaction cannot be performed, and it is difficult to obtain a polyfluorene cured product; when the above upper limit 値 is exceeded, the unreacted SiH group remains in the hardened material in a large amount, and the rubber property changes with time. s reason. (C) The platinum group metal catalyst is blended for accelerated addition reaction, and a platinum-based, palladium-based or lanthanide-based catalyst can be used. However, from the viewpoint of cost and the like, a uranium-based metal catalyst is used. good. The platinum group metal catalyst may, for example, be H2PtCl6 · mH20, K2PtCl6, KHPtCU · mH20, K2PtCl4, K2PtCl4 . mH20, Pt02 · mH20, 40PtCl 4 4 0 . mH 2 4 0 〇, PtCl 2 4 0, H 2 4 0 PtCl440 -15- 201124477 • mH2〇 (m is a positive integer) and so on. Further, it may be a complex of the platinum group metal catalyst with hydrogen carbide, ethanol or a vinyl group-containing organopolyoxane. For example, an ethanol modification solution of uranium uronic acid may be used, and chloroplatinic acid may be used. Oxygen-modified solution, etc. The above catalysts may be used singly or in combination of two or more. The amount of the above-mentioned (A), (B), and (D) components in the total amount of the uranium metal conversion (mass) is 0.:!~100 ppm. Preferably, 1 to 20 ppm is preferred. (D) Organic oxirane containing a heterocyanocyanine ring The polyfluorene oxide composition of the present invention has an organic siloxane having a hetero-cyanuric ring as an adhesion promoter for improving adhesion of a cured product. The organoxanthene containing an isomeric cyanide ring in the present invention is an organooxane containing an isomeric cyanide ring containing an allyl group, an epoxy group and an organic phosphonyl group in one molecule. Such an organic sand chamber containing a hetero-cyanide ring is preferably represented by the following formula (2) or (3). [1 1]

-16 - 201124477

The organononane having an iso-cyanuric ring in the present invention can be obtained, for example, by using 1,3 -diallyl-5-epoxypropyl isomeric cyanurate and an organic hydrazine represented by the following formula. The oxane is produced by an addition reaction. The addition reaction can be carried out under known conditions without particular limitation. For example, the equivalent amount of the allyl group of the organodecane to the isocyanurate compound is such that the Si_H group is 〇·1 to 1 〇 equivalent, preferably in an amount of 0.3 to 0.7 equivalent. The reaction temperature is room temperature to 250 ° C ' preferably from 50 to 180 ° C. Further, the reaction time is from 0.1 to 120 hours, preferably from 1 to 10 hours. [Chemical 1 2] OR6 Η-Si-OR6 OR6 (wherein R6 is an alkyl group having 1 to 10 carbon atoms) is preferably an alkyl group having 1 to 6 carbon atoms, of which methyl or ethyl is preferred. The product obtained by the above method is obtained by adding 30 to 7% by weight of an organic decane to an allyl group of an isocyanurate compound (hereinafter referred to as a 1 adduct), 0~ 20% by weight of an organic siloxane is added to two allyl groups (hereinafter referred to as 2 adduct), 〇~50% by weight of an unadded organic decane (hereinafter referred to as unadduct) A mixture of the composition 'this mixture can be contained in the polyfluorene oxygen composition of the present invention in the state of -17-201124477>> In the present invention, (D) an organooxane having a hetero-cyanuric ring to 1 part by mass ( A) The blending amount of the component is usually from 0.1 to 1 part by mass, preferably from 0.1 to 10 parts by mass. When the lower limit 値 is not reached, the adhesion to the substrate is not good, and when it exceeds the above upper limit 値, the hardness or surface viscosity of the cured product is adversely affected. The polyxanthene composition of the present invention may contain various well-known additives as needed in addition to the above components (A) to (D). As the various additives, for example, a reinforcing inorganic chelating agent such as fuming cerium oxide or fuming titanium dioxide, a non-reinforcing inorganic cerium filling agent such as calcium carbonate, calcium citrate, titanium oxide, iron oxide, carbon black or zinc oxide may be used. Various additives may be appropriately blended within the range not impairing the object of the present invention. The polyoxymethylene composition of the present invention can be obtained by uniformly mixing the above components in accordance with a conventional method using a planetary mixer or a Shinagawa mixer. The polyfluorene oxide composition of the present invention is usually classified into two liquids so as not to be hardened, and the two liquids are mixed for hardening when used. Alternatively, a small amount of a hardening inhibitor such as an acetylene alcohol may be added as one liquid. The polyoxymethylene composition of the present invention provides a cured product having high transparency by hardening. The cured product has a very good adhesion to a packaging material such as LCP or a metal substrate. Therefore, the polyfluorene oxide composition of the present invention can be widely used as a semiconductor packaging material such as an LED, a photodiode, a CCD, or a CMOS. Further, the curing conditions are not particularly limited, and heating may be carried out at room temperature or as needed for sufficient hardening. The heating temperature is 40 to 250 ° C, preferably 60 to 2 ° C; the hardening time is 5 minutes to 10 hours, preferably 30 minutes to 6 hours. -18-201124477 [Embodiment] Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to the following examples. Further, in the following examples, the parts represent parts by mass, and Vi represents a vinyl group. The addition of an organic oxane to an allyl group of an isomeric cyanurate compound is referred to as a 1 adduct, and the addition of an organic oxane to two propylene groups is referred to as a 2 adduct. Addition of organic sand oxides is called unaddition. Further, the viscosity is measured at 25 ° C. (D) Preparation of an organic oxirane containing a hetero-cyanuric ring [Synthesis Example 1] Preparation of 5 〇. 〇g of 1,3 --propyl propyl-5-epoxypropyl iso-di- lysine ( DAMGIC, manufactured by Shikoku Chemical Industry Co., Ltd.), 30.0g ((:1130)33^, 10〇11^ toluene, Timing 25 (^[0.05% chloroplatinic acid toluene solution' to 8 〇~1 After reacting for 2 hours at 〇〇 ° C, the solvent was evaporated under reduced pressure to obtain '5 1 · 4 g of pale yellow liquid. After the product was analyzed by g PC, it was 3 6 wt. A mixture of 48% by weight of 1 adduct and 16% by weight of 2 adduct. GPC data is shown in Fig. 1. [Synthesis Example 2] Preparation of 50_0g of 1,3-diallyl_5_ ring Oxypropyl isopropyl isocyanuric acid _ (DAMGIC, manufactured by Shikoku Chemicals Co., Ltd.), 46.4 g of (C2H50) 3SiH' 100 mL of toluene, and 25 〇# of 5% chloroplatinic acid in toluene solution was added to 8 After 2~1 〇〇 °C reaction for 2 hours, the solvent was distilled under reduced pressure to remove THF from -19 to 201124, to obtain 6 4.8 g of a pale yellow liquid. After the product was analyzed by GP c, it was 34% by weight. Additive '5 1% by weight of 1 a mixture of the product and 15% by weight of the 2 adduct. Preparation of the polyfluorene composition [Example 1] 50 parts (viscosity 55 〇 m Pa·s) represented by the following formula Base oxane (VF), [Chem. 1 3]

Mixing 50 parts of a vinyl methyl oxirane (VMQ) composed of 50 mol% of SiO 2 units, 42.5 mol% of (CH 3 ) 3 SiO 〇 .5 units, and 7.5 mol % of Vi 3 SiOG 5 units, 0.25 parts of the product obtained in Synthesis Example 1, 50 parts of an organic hydrogen polyoxyalkylene represented by the following formula, [Chemical Formula 1]

5 parts of an octanol-modified solution of chloroplatinic acid (platinum content: 1% by mass) was mixed to prepare a polyfluorene-oxygen composition. This composition was poured into a model having a length of 3 x width 3 X depth of 10 (mm) and heated at 150 ° C for 4 hours to harden it to form a cured product, and the appearance was visually observed. Further, the tensile strength, hardness (measured using an A-type spring tester), and elongation 201124477 of the cured product were measured in accordance with J IS K 6 3 0 1 . Further, the shear adhesion and the aggregation failure rate were measured by the methods shown below. The results are disclosed in Table 1. [LCP Shear Adhesion] On the right side of the LCP substrate having a width of 25 mm, a composition layer having a thickness of 1 mm and a length of 1 mm, which is composed of the above-mentioned polyfluorene composition, is formed, and another LCP having a width of 25 mm is formed. The left side of the substrate was superposed thereon, and the composition layer was hardened at 150 ° C / 4 hours to prepare a sample. After the sample was allowed to stand at room temperature for 12 hours or more, the end portion of each L C P substrate (the side without the interlayer composition layer) was stretched to the left and right by a tensile tester, and the shear adhesion strength was measured. [Coagulation failure rate] Regarding the fracture surface of the sample at the time of measuring the shear adhesion strength, it is evaluated that the entire area of the fracture surface is 'agglomerated and destroyed (that is, the interface between the LCP substrate and the polysulfide hardened material is not peeled off and the polyoxygenated hardened material itself) The area ratio (percentage) of the portion of the fracture is taken as the aggregation failure rate. [Example 2] An evaluation test was carried out in the same manner as in Example 1 except that the product obtained in Synthesis Example 1 was changed to the product obtained in Synthesis Example 2. The results are disclosed in Table 1. [Example 3] Except that the blending amount of the product obtained in Synthesis Example 1 was changed to 〇 之 201124477, the results are shown in Table 1 [Comparative Example 1] except that the product obtained in Synthesis Example 1 was changed to the next The epoxy modified poly (four) of the formula ($) is in addition to the embodiment! The same method of modulation is used for the evaluation test. The results are disclosed in Table 1. [化1 5]

c. c -2 c [Comparative Example 2] Except that the product obtained in Synthesis Example 1 was changed to an organic decyloxy group (non-epoxy group) containing a hetero-cyanuric ring of the following formula (6), The evaluation test was carried out in the same manner as in Example 1. The results are disclosed in Table 1. 【化1 6】

CH

Hci ^Η2

CHO

CH CH, 〇CH, H2C — Si-〇CH3 OCH, (6) -22- 201124477 [Table 1] Example ratio _ Surface 1 2 3 1 2 SiH group / SiVi basis (Mo Erbi) 1.5 1.5 1.5 1.5 1.5 Appearance Colorless Transparent Colorless Transparent Colorless Transparent Colorless Transparent Colorless Transparent Hardness (Type A) 70 71 70 70 72 #^(%) 30 30 30 30 30 Tensile Strength (Mpa) 7 7 7 6 7 LCP Shear Adhesion (Mpa) 3 3 4 0 0 Cohesive failure rate (%) 80 80 90 0 0 It can be seen from Table 1 that the cured products of Examples 1 to 3 have good LCP shear adhesion and cohesive failure, and provide good adhesion to the LCP substrate. [Industrial Applicability] The polyfluorene oxide composition of the present invention can provide a cured product which exhibits good adhesion to a substrate which is very difficult to adhere, such as LCP, and provides a semiconductor device which can pass a strict test of reliability. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 is a GPC °-23- of a product prepared by Synthesis Example 1.

Claims (1)

201124477 VII. Patent application scope: 1. A polyfluorene oxygen composition characterized by the following components: (A) an organopolyoxane (B) containing at least two alkenyl groups in one molecule in one molecule An organohydrogen polyoxyalkylene (C) containing at least two hydrogen atoms bonded to a ruthenium atom. The platinum group metal catalyst (D) has an allyl group, an epoxy group, and an organic oxiranyl group in one molecule. An organic oxirane containing an isomeric cyanide ring. 2. The polyfluorene oxide composition of claim 1, which contains the following components, (A) 100 parts by mass of an organopolyoxyalkylene having at least 2 alkenyl groups in one molecule, (D) 0.1~ 100 parts by mass of an organic decyloxy group having a heterotrimethylene ring having a propyl group, an epoxy group and an organic decyloxy group in one molecule, and (B) an organic hydrogen grouping according to claim 1 a decane, wherein the (A) organopolyoxyalkylene and (D) an alkenyl group of an organoaluminoxane containing an iso-cyanide ring per mole of SiH-based content is 0.1 to 4.0 moles, (C) Catalyst amount of platinum group metal catalyst. 3. The polyoxymethylene composition of claim 1 or 2, wherein the component (A) is represented by the following formula (i) -24 - 201124477 [Chemical 1 R2 CH2=CH-Si-〇-fsi_0) ~~~(-ShO-)- R1 Si- R1 R2 CH: R1 :CH2 (1) (wherein R 1 is independent of each other 2 _ or substituted one-valent hydrocarbon group; R is independent of each other Unsubstituted or substituted by deuterated ' and does not contain alkenyl monovalent hydrocarbon groups; claws and 11 are 〇 or positive integers, m + n is 矽 right 裇. + Field! ^Organic polyoxyalkylene at 2 5 °C The organic polyfluorene oxide shown by the viscosity of 10~1, 〇〇〇, 〇〇〇1^&.8) is composed of SiO2 unit, R3kR4pSiO〇5 unit and R3qR4rSi〇() 5 unit. The organopolyoxyalkylene (R3 is a vinyl group or an allyl group: R4 is a monovalent hydrocarbon group without an alkenyl group; k is an integer of 2 or 3' p is 0 or 1, but k + p = 3; q is 〇 or 1, r is an integer of 2 or 3, but q + r = 3), the latter organic polyoxane content is 20 to 70% by mass in the component (A) ° 4. As claimed in the patent scope 1 or 2 of the polyoxyl composition] wherein the component (D) is represented by the following formula (2) or (3) ‘[Chemical 2] 2 S -25- 201124477 A polyxanthoxy cured product characterized by curing a polyfluorene oxide composition according to any one of claims 1 to 4. A semiconductor device characterized by being sealed with a polyoxygenated hardened article of the patent application.第 Scope 5th item -26-