TW201114590A - Silicone rubber sheet for thermocompression bonding - Google Patents

Abstract

A silicone rubber sheet for the thermo-compression is provided to secure the heterogeneity for an epoxy conductive adhesive and an acryl conductive adhesive, and to economically produce the silicone rubber sheet. A silicone rubber sheet for the thermo-compression comprises the following: a thermo-conductive silicone rubber sheet substrate layer; and a silicon protective layer formed on one surface of the substrate layer. The silicon protective layer is formed with a silicone addition cured material, and includes more than 2 mol of silethylene group.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermocompression bonding polyoxygen used for the purpose of uniformly applying pressure simultaneously with conduction heat in a wiring connection step of an electric/electronic machine component. Rubber sheet. [Prior Art] When the liquid crystal panel is manufactured, the liquid crystal is driven, and the transparent lead electrode of the liquid crystal panel and the lead electrode of the flexible circuit board (c〇F) on which the LSI for driving is mounted are interposed with an anisotropic conductive adhesive (paste). Thermal compression bonding for electrical and mechanical bonding. At this time, it is common to apply a uniform pressure to the heat at the same time as to hold the polyoxyethylene rubber sheet between the pressurizing and heating metal tool and the COF. Further, in the single-layer thermally conductive polyoxyethylene rubber sheet, since the release property to the anisotropic conductive adhesive is insufficient, it has been proposed to laminate the polyoxyn protective layer on at least one of the thermally conductive rubber sheets. Improves the release property of the anisotropic conductive adhesive and improves workability. At this time, in the above-mentioned hot press-bonding step, the same place where the polyoxynose rubber sheet was used was repeatedly pressed and applied a few times, and then the sheet was slightly fed. That is, as much as possible of the same place where the silicone rubber sheet can be used is related to the superiority of the manufacturing cost. The anisotropic conductive adhesive that is not exposed by COF or the contact with the anisotropic conductive adhesive oozing out from the COF during pressure bonding, the polyoxyethylene rubber sheet is slowly deteriorated, so that the polyoxyxene rubber is improved. The release of the anisotropic conductive adhesive of the sheet is very important. -5- 201114590 However, the polysilicon protective layer on the surface of the thermally conductive polyoxyethylene rubber sheet used in the thermo-adhesive wiring connection step of electrical and electronic machine parts has been considered to be an anisotropic conductive object. There are no examples of development or evaluation of the types of thermosetting resins of the subsequent agents. The present inventors have confirmed that the inorganic powder (tantalum) in the polyfluorinated protective layer is reduced compared with the thermally conductive polyoxyethylene rubber sheet base material layer, and it has been confirmed that it can be improved from the past. The release property of the anisotropic conductive adhesive (hereinafter, an epoxy conductive adhesive) in which the conductive particles are dispersed in the epoxy resin (Patent Document 1: Patent No. 3 902558, Patent Document 2: JP-A-2005-297234) Bulletin). However, in recent years, the anisotropic conductive adhesive (hereinafter, H g _ conductive adhesive) which disperses the conductive particles in the acrylic resin which is popular for low-temperature short-time pressure bonding has a very strong adhesive force, regardless of the single layer. A thermally conductive polyaza rubber sheet, a multi-layer sheet provided with a protective layer thereon, which causes sticking or cracking of the sheet with a small number of press-fit times. Therefore, compared with the epoxy conductive adhesive, there is a disadvantage that the amount of use of the sheet is increased. (Prior Art Document) (Patent Document 1) Patent No. 3 902 5 5 8 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. (Problems to be Solved by the Invention) The present invention has been made in view of such circumstances, and an object thereof is to provide a thermocompression adhesive polyoxyxene rubber which not only has an epoxy conductive adhesive agent but has excellent release properties even for an acrylic conductive adhesive. Sheet. [Means for Solving the Problems] The above object of the present invention is achieved by a polyoxyxene rubber sheet which is a polyoxyethylene rubber used in a thermocompression bonding wiring connection step of an electric/electronic machine part. The sheet is a multi-layered polyoxyethylene rubber sheet composed of a thermally conductive polyoxyethylene rubber sheet base material layer and a polyoxygen protective layer provided on at least one of the surfaces thereof, characterized in that the polysilicon protective layer As a main component of the polyoxygen addition hardening compound, its composition is relative to the dimethyloxane unit ((CH3)2Si01/2) 1 〇〇 molar, and the ethylene group containing the addition reaction portion (Si- CH2-CH2-Si) 2 moles or more. In other words, the inventors of the present invention have found that the release property of the acrylic conductive receiver is related to the crosslinking density of the polyoxo component of the main component of the protective layer. However, if the cross-linking density of the thermally conductive polyoxyethylene rubber sheet of the single layer is increased, there is a problem that the flexibility is lost and the pressure-bonding failure occurs in the wiring connection step. Further, in the conventional protective layer, the liquid polyoxyethylene rubber composition having a small content of the thermal conductive agent is applied by solvent dilution, and is heat-cured. However, even if it is hardened alone, the crosslink density is insufficient in so-called polyoxyethylene swell which is soft or stretchable. In such a protective layer, the release property of the epoxy conductive adhesive is remarkably improved, but the 201114590 release property of the acrylic conductive adhesive is not improved at all compared with the substrate layer. Therefore, as a result of further investigation, in the protective layer of the present invention, the crosslinking density is separately increased to a film shape, and it is formed thinly on the thermally conductive polyoxyethylene rubber sheet base material layer, and a part of the dip dye is used. The surface modifier acts like this, thereby ensuring the softness and thermal conductivity of the entire sheet, and at the same time obtaining a sheet which only significantly increases the crosslink density near the surface. As a result, the release property of the acrylic conductive adhesive having no difference at all in the polyoxyethylene rubber sheet to date has been successfully increased to twice or more of that of the conventional product, and the present invention has been completed. Therefore, the present invention provides the following thermocompression adhesive polyoxyethylene rubber sheet. Patent Application No. 1: A hot-press adhesive poly-xylene rubber sheet is used for the thermo-adhesive wiring connection step of electrical and electronic machine parts. a thermosetting adhesive polyaza rubber sheet composed of a layer and a polysilicon protective layer provided on at least one of the surfaces thereof, characterized in that: the polyfluorene protective layer is an addition polyoxygen It is composed of a cured product, and is equivalent to dimethylene (Si-CH2-CH2-Si) 2 molar containing an addition reaction unit with respect to a dimethyloxane unit (1 Torr). Item 2: The polyoxyethylene rubber sheet according to claim 1 of the patent scope, wherein the polyoxygen protective layer contains: a diorganopolyoxyalkylene having a vinyl group in a side chain, -8 - 201114590 having a SiH group in a side chain A cured product of an organohydrogen polyoxyalkylene and a polyoxo-oxygen composition of a ruthenium-based catalyst. Patent Application No. 3: A poly-xylene rubber sheet according to claim 1 or 2, wherein the above-mentioned polyfluorene The oxygen protective layer has a thickness of 0.1//m or more and 30# m or less. Item 4: The polyoxyxene rubber sheet according to any one of claims 1 to 3, wherein the polyfluorene protective layer is an inorganic powder containing at least one selected from the group consisting of a metal, a metal oxide, a metal nitride, and a metal carbide. 5% by mass or more of 30% by mass or less. Patent Application No. 5: The polyoxyxene rubber sheet of the first to fourth aspects of the patent application, wherein the inorganic powder is a spherical fine powder of cerium oxide. The polyoxyxene rubber sheet according to any one of claims 1 to 5, wherein the fine powder cerium oxide is a spherical powder having an average particle diameter of 1 μm or more and 30 μm or less, and further sieving coarse particles of 3 5 am or more. Patent Application No. 7: Polyurethane rubber sheet according to item 1 of the patent application scope, wherein the thermal conductive polyoxyethylene rubber sheet substrate layer of the above-mentioned -9-201114590 satisfies the thermal conductivity of 0.1 W/mK or more and 5 W/mK. The thickness is not more than 5 mm and not more than 1 mm. [Effects of the Invention] The thermosetting adhesive polyoxyethylene rubber sheet of the present invention has excellent release property against an acrylic conductive adhesive. Past protective layer The multilayer polyoxyethylene rubber sheet similarly has a release property for an epoxy conductive adhesive, a glass or transparent wire electrode, and a release property to a peripheral member of the COF. Therefore, the liquid crystal panel manufacturing step can be performed. The rationalization or the cost reduction has a great effect. [The embodiment for carrying out the invention] The thermocompression adhesive polyoxyethylene rubber sheet of the present invention comprises a thermally conductive polyoxyethylene rubber sheet base material layer and at least one of them The surface of the thermally conductive polyoxyethylene rubber sheet base layer may be a known heat conductive polyoxyethylene rubber sheet used for the anisotropic conductive adhesive, and may be used to have thermal conductivity. A well-known polyoxyxene rubber composition of a chelating agent is obtained by sheet forming and hardening. A commercially available product can also be used as such a polyoxyethylene rubber composition, and for example, a polyoxyethylene rubber sheet HC-25MS manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Further, the thermal conductive polyoxyethylene rubber sheet base material layer preferably has a thermal conductivity of 0.1 W/mK or more and 5 W/mK or less, and particularly preferably 〇·5 to 5 W/mK. If the thermal conductivity is less than 0.1 W/mK, it is necessary to increase the hot-pressing temperature of 201114590 ’ or increase the viscosity-bonding time, which is disadvantageous in terms of efficiency. Even if it exceeds 5 W/mK, a particularly advantageous effect cannot be expected. Further, the thickness of the thermally conductive polyoxyethylene rubber sheet base material layer is preferably 0.05 mm or more and 1 mm or less, particularly preferably 0.1 to 0.8 mm. If it is thinner than 0.05 mm, sometimes the strength is insufficient, and if it exceeds 1 mm, in terms of heat conduction. An unfavorable situation arises. The polyfluorene protective layer of the present invention is preferably composed of a polyfluorene addition hardening compound, (A) an organic polyoxyalkylene having an alkenyl group, and (B) an organic hydrogen having a hydrogen atom directly bonded to a halogen atom. Polyoxonium oxide, (C) platinum-based catalyst: effective amount, (D) reaction control agent: effective amount, (E) is preferably selected from at least one selected from the group consisting of metals, metal oxides, metal nitrides, and metal carbides The cured product of the polyfluorene oxide composition as an essential component, and the component (A) is preferably a diorganopolyoxyalkylene having at least two alkenyl groups in one molecule, particularly preferably a vinyl group, which is a polyfluorene of the present invention. The main component of the oxygen composition (substrate polymer). The alkenyl group-containing organopolyoxyalkylene has a molecular structure in the form of a liquid at room temperature (25 t), and may be, for example, a linear chain, a branched chain, or a linear chain having a part of branches. Shape, but especially linear. Further, the alkenyl group may, for example, be an alkenyl group having a carbon number of from 2 to 8 such as an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group or a cyclohexenyl group, but it is easy to obtain from the cost. Sex, vinyl should be used. -11 - 201114590 A group of a non-substituted or substituted one-valent hydrocarbon group other than a methyl group, in addition to a methyl group, in addition to a methyl group, for example, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Base, isobutyl, tert-butyl, pentyl, neopentyl 'hexyl, heptyl, octyl, decyl, decyl, dodecyl, etc. alkyl, cyclopentyl, cyclohexyl, cycloheptane An aryl group such as a cycloalkyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a biphenyl group, a benzyl group, a phenylethyl group, a phenylpropyl group or a methylbenzyl group. A part or all of a hydrogen atom of an alkyl group and a carbon atom to which the group is bonded, and a group substituted with a halogen atom such as fluorine, chlorine or bromine, a cyano group or the like may, for example, be a chloromethyl group or a 2- Bromoethyl, 3·chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl 'cyanoethyl, 3,3,4,4,5,5,6,6,6 The carbon atom such as nonafluorohexyl group is 1 to 10, and particularly preferably has 1 to 6 carbon atoms. However, it is preferably a methyl group for reasons such as cost, availability, chemical stability, environmental load, and the like. The organopolysiloxane of the component (A) may be used alone or in combination of two or more kinds having different combinations of viscosity or composition. In this case, the viscosity of the above organopolyoxane is from 10 to 10000 mPa·s', preferably from 50 to 5,000 mPa·s', more preferably from 100 to 100 mPa·s, at a viscosity of 25 ° C obtained by a rotational viscometer. In the present invention, the organopolyoxyalkylene is preferably a dimethylpolysiloxane having two or more vinyl groups, and particularly preferably those represented by the following formula (1), especially those having a vinyl group in a side chain. . 【化1】

201114590 In the above formula (1), R is CH3 or CH=CH2. At this time, in the polyfluorene addition addition hardening which forms the protective layer of polyfluorene oxide, in order to make the dimethyloxane unit [(CH3)2SiO1/2] 100 莫 矽 矽 ethylene (Si-CH2- The ratio of CH2-Si) (crosslinking point) is 2 m or more, so when R is CH = CH2, χ = 10~1000, y=0~100, y/x=0~0.1, especially x=50~ 300, y=l~30, y/x = 0.02~0· 0 5. Further, when R is CH3, 'x=l〇~1〇〇〇, y=2~100, y/x=0.02~0.1, especially x=30~300, y=3~30, y/x= 0.02 to 0.05, but when R is CH2 = CH or CH3, it is preferred to have a vinyl group in the side chain (ie, y#〇), and when R is ch2 = ch, ygi, r is ch3, preferably y 2 2. Further, in order to enhance the mechanical strength of the protective layer of the present invention, in addition to the organopolyoxane component of the component (A), a polyoxyxylene resin may be used in combination. The polysiloxane resin is composed of R^SiOo unit (M unit) and Si〇2 unit (Q unit), or the unit and Q unit and RJSiOu unit (T unit) and/or R^SiO unit (D unit) ) MQ resin, MTQ resin, MDQ resin or MDTQ resin, but the polyoxynoxy resin used for this purpose is further preferably containing (CH2 = CH)(CH3)2SiO〇.5 unit or (CH2 = CH) (CH3) a silica-containing polysandoxy resin of the SiO unit. Further, R1 may, for example, be a monovalent hydrocarbon group (alkyl group, alkenyl group, aryl group or the like) having 1 to 8 carbon atoms, and is particularly preferably a methyl group. The content of the polysiloxane resin to be added to the component (A) is preferably 30% by mass or less based on the component (A). The polyoxyn resin generally contains a mordant (Si OH) group which has a property of reacting with a resin component in an anisotropic conductive adhesive. The amount of the polyoxymethylene resin to be added is preferably small, but if it is particularly more than 3% by mass, the influence of the reaction with the decyl group becomes large, and the release property may be lowered. -13- 201114590 (B) is an organic hydrogen polyoxyalkylene having at least two or more hydrogen atoms (ie, SiH groups) bonded to a ruthenium atom in a molecular chain side chain in one molecule, and is (A) A component that acts as a cross-linking agent. That is, the hydrogen atom of the sand atom bonded to the component (B) acts by the cobalt-based catalyst of the component (C) described later, and the alkenyl group such as a vinyl group in the component (A) and the hydroformyl group The addition reaction is carried out to obtain a crosslinked cured product having a 3-dimensional network structure containing a crosslink. As the organic group of the ruthenium atom to be bonded to the component (B), an unsubstituted or substituted monovalent hydrocarbon group other than the alkenyl group may be used, but in the same manner as the component (A), from the viewpoint of synthesis and economy It should be methyl. The structure of the component (B) is not particularly limited, and may be any of a linear chain, a branched chain, and a ring shape, but is preferably a linear chain. The component (B) is, for example, the following formula (2):

Ο Ο (wherein R 2 is a methyl group or a hydrogen atom, and at least two hydrogen atoms are bonded to the side chain of the molecular chain. Hydrogen atoms may be bonded to the end of the molecular chain. Ζ is an integer of 2 or more ° ). In this case, the SiH group is present in the side chain, and the SiH group may be present only in the side chain, but in addition to the side chain, the SiH group may be present at the end of the molecular chain, and it is preferably 2 to 200, more preferably An integer from 20 to 200. If the crucible is too small, the amount of dimethyl polysulfide in the thermally conductive rubber sheet which is hardened, volatilized or infiltrated into the substrate after application will increase, and a stable addition reaction cannot be obtained. -14- 201114590 In addition, the component (B) can be used alone or in combination of two or more. The amount of the component (B) is added. The SiH group of the component (b) is compared with the vinyl group of the component (A). The molar amount is 0.5 to 5.0 moles, preferably 0.8 to 3.0 moles. When the amount of the Si-H group of the component (B) is less than 0.5 mol with respect to the vinyl group 1 in the component (A), the hardness of the cured product cannot be sufficiently obtained. Further, when the amount exceeds 5.0 moles, many SiH groups remain, so that the release property to the heteroconductive conductive adhesive is lowered. In the present invention, the (A) component and the (B) component are hardened, and the dimethylene group containing the addition reaction portion is 1 Torr with respect to the dimethyloxane unit in the hardened material. 2 moles above. More preferably 2 to 10 moles, more preferably 3 to 5 moles. The addition reaction moiety can be obtained by alkylation of a vinyl group in the component (a) with a hydrogenation of a hydrogen atom bonded to a halogen atom in the component (B). However, the form may be, for example, terminal-end bonding. , terminal _ side chain binding, side chain-side chain binding. The contribution to the increase in crosslink density is side chain-side chain binding>end-side chain binding> end-end binding, but the general reaction rate is its reverse end-end binding>end-side chain binding>; side chain - side chain bonding. In order to increase the crosslinking density, that is, the release property of the acrylic conductive adhesive, it is effective to increase the side chain-side chain bonding, but in order to stabilize the hardenability, it is preferred to allow the terminal-side chain bonding to coexist. Further, if the crosslinking density is too high, the hardness of the protective layer becomes high, which hinders the uniform pressure transmission, or the sheet is easily broken when pressed, so care must be taken. The platinum-based catalyst of the component (C) promotes an addition reaction of a vinyl group in the component (a) with a hydrogen atom bonded to a halogen atom in the component (B), and is obtained from the composition of the present invention from -15 to 201114590. The component of the cross-linking hardened material of the three-dimensional network structure. The component (C) can be used for all of the known catalysts used in the general hydroformylation reaction. Specific examples thereof include a uranium metal monomer such as platinum (containing uranium black), ruthenium, palladium, etc., H2PtCl4 · nH20 'H2PtCl6 · nH20 'NaHPtCle * nH20 ' KHPtCl6 * nH2〇' Na2PtCl6 * nH20 , K2PtCl4 · nH20 , PtCl4 . nH20 , PtCl2 , Na2HPtCl4 · nH20 (however, n is an integer of 0-6, preferably 0 or 6), etc. Platinum chloride, chloroplatinic acid and chloroplatinate, alcohol modified chlorination a combination of platinum acid, chloroplatinic acid and olefin, platinum group metal such as platinum black or palladium, supported on alumina, ruthenium oxide, carbon, etc., ruthenium-olefin complex, chlorotri(triphenylbenzene) Phosphoric acid (Wilkinson catalyst), platinum chloride, chloroplatinic acid, or a complex of a chlorinated platinum salt and a vinyl-containing decane. Further, the uranium-based catalyst system of the component (C) may be used singly or in combination of two or more. The amount of the component (C) is not particularly limited as long as it is an effective amount required for curing the composition of the present invention, but is generally 0.1 in terms of mass of the platinum group metal element of the component (A). ~1000 PPm, preferably 0. 5~500 ppm. The reaction control agent for the component (D) is used to adjust the reaction rate of the component (A) and the component (B) which are carried out in the presence of the component (C). The component (D) can be used for all of the known addition reaction inhibitors used in the general addition reaction hardening type polyoxo composition. Specific examples thereof include an acetylene compound such as 1-ethynyl-1-cyclohexanol or 3-butyn-1-ol, -16-201114590 nitrogen compound, an organic phosphorus compound, a sulfur compound, a compound, and an organic chlorine compound. Wait. Further, the addition reaction inhibitor of the component (D) may be used singly or in combination of two or more. The amount of the component (D) varies depending on the amount of the component (C). Therefore, it cannot be defined once, but it is only necessary to adjust the effective amount of the hydroformylation reaction to the desired reaction rate. In general, the mass of the component (A) may be about 10 to 50,000 ppm. When the amount of the component (D) is too small, sufficient usable time may not be secured. When the amount is too large, the hardenability of the composition may be lowered. (E) The component is at least one selected from the group consisting of a metal, a metal oxide, a metal nitride, and a metal carbide, and imparts heat conductivity, surface slipperiness, and film thickness stability at the time of coating to the release layer of the present invention. Specific examples of the metal include silver powder, copper powder, iron powder, nickel powder, and aluminum powder. Examples of the metal oxide include oxides of zinc, magnesium, aluminum, barium, and iron. The metal nitride may be exemplified by a nitride such as boron, aluminum or tantalum, and the metal carbide may be a carbide such as ruthenium or boron. Among them, the (Ε) component is preferably a cerium oxide powder, and particularly preferably a spherical one. Using this powder, particularly excellent surface slip and film thickness stability can be obtained. Moreover, because of the low specific gravity, there is little precipitation with time, and the coating can be stabilized. The average particle diameter of the (Ε) component is preferably 1 m or more and 30 μm or less, and particularly preferably 5 to 2 0 /z m. When the average particle diameter is less than 1 v m, it is difficult to obtain surface smoothness. Further, if it exceeds 30 // m, in order to prevent the detachment of the squeegee, it is necessary to increase the thickness of the coating film, and the thermal conductivity of the entire sheet is lowered. Therefore, it is necessary to increase the pressure and the temperature of the S1 heating metal tool. Further, the average particle diameter can be obtained by the particle size distribution measuring device obtained by the laser light -17-201114590 diffraction method, and can be obtained as a weight average 》 (E) component is a polyoxygen protection. The amount in the layer is 0.1% by mass or more and 30% by mass or less. It is particularly suitable to use in the range of 5 to 30% by mass. If it is less than 0.1% by mass, it is difficult to obtain the effect of surface slip and film thickness stability, and from this point, it is recommended to be 5% by mass or more. Moreover, when it exceeds 30 mass%, the release property with respect to the anisotropic conductive adhesive will fall. However, even if the amount of the component (E) is less than 0.1% by mass, the surface of the thermally conductive rubber sheet of the substrate is provided with a concavo-convex shape, and the coating can be carried out by roughening. The method of imparting irregularities to the surface of the rubber sheet is a method of transferring the uneven polystyrene rubber composition onto the plastic film having the surface of the uneven shape during the press forming, and transferring the uneven shape. Further, there is a method in which a roller having irregularities is applied to the surface of the sheet before curing, and the unevenness is transferred, but it is not limited thereto. The coating method of the protective layer of the present invention is a material for forming a polyfluorinated protective layer (the above-mentioned polyfluorene composition) which is dissolved in a solvent such as toluene on a thermally conductive polyoxyxene rubber sheet substrate to form a doctor blade. Coating, wire bar coating, bar coating, dip coating, spray coating, etc., a method of coating and forming, and a method of removing a solvent and heat-hardening directly in the atmosphere, but it is not limited to this. Further, the heat curing is preferably 120 to 180 ° C for 3 to 10 minutes, but is not limited thereto. The conventional protective layer is mainly composed of liquid polyoxyethylene rubber, and must be diluted with a solvent. In the invention, it is also possible to apply solvent-free coating by lowering the viscosity of (A) and (B) to -18-201114590. Compared with solvent dilution coating, the speed of the coating line can be increased, which can significantly improve productivity. The thickness of the protective layer of the present invention is preferably Ο.ίμηι or more and 30 μm or less. Due to the high cross-linking composition, even if it is a thin film thickness, the surface is modified to obtain high release property. However, if it exceeds 30/zm, the thermal conductivity of the entire sheet is lowered, so it is necessary to increase the set temperature of the pressurization and heating metal tool. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples described below. (Thermal conductive polyoxyethylene rubber sheet base material layer) The substrate coated with the polyoxygen oxide protective layer was a polymerized hydrogen oxide rubber sheet HC-25MS manufactured by Shin-Etsu Chemical Co., Ltd. (thickness 0.25 mm, thermal conductivity 〇_85 W/mK) ). (Preparation of coating liquid) E S1 To 100 parts by mass of the dimethylpolysiloxane having a vinyl group (component (A)), 0.2 parts by mass of 1-ethynyl-1-cyclohexanol is added ((C) Component) 'Vinyl oxoxane complex of chloroplatinic acid (platinum content: 0.5% by mass) 0.2 parts by mass (component (D)), after kneading, adding a hydrogen atom having a direct bond to a ruthenium atom Methyl polyoxyalkylene (component (B)) and high-purity true spherical oxidation of coarse particles having an average particle diameter of 1 5 # m and 3 5 // m or more -19- 201114590 矽塡 15 15 parts by mass ((E) component). In the examples, the composition of each of the components (A) was changed and evaluated. The component (B) is an average structure which is represented by the following formula (3). The amount of addition is adjusted such that the vinyl group in the component (A) and the hydrogen atom bonded to the ruthenium atom in the component (B) become equimolar. [化3]

(3) (Coating method) The coating liquid was applied onto a substrate attached with PET by a wire bar coater, and hardened in a heating furnace at 160 ° C for 5 minutes. Further, after the PET film was peeled off, it was further heat-treated at 200 ° C for 4 hours to obtain a sample for evaluation. The film thickness is adjusted to about 1 〇 (1 m. (Assessed for the pressure-adhesion test of an anisotropic conductive adhesive). Pressurize under a pressurization of a heated metal tool heated to 300 °C (the polysilicon protective layer is facing) Next, when the pressure is applied, the sheet is attached to the outside of the tool and the glass is further removed. Further, a glass substrate to which an acrylic anisotropic conductive film is transferred is inserted, and the film is pressed at 5 MP a for 10 seconds. The glass substrate to which the new anisotropic conductive film was transferred was transferred, and the pressure was adhered. This was repeated, and the change of the sheet and the acrylic acid anisotropic conductive film was confirmed. Shown in Table 1.

-20-201114590 [Examples 1 to 3, Comparative Examples 1 to 4] For the component (A), seven types of structures represented by the following formula (4) were prepared. Further, X and y in the formula are shown in Table 1. [Chemical 4] ch3 CH2=CH-Si—〇 CH,

(4) [Comparative Examples 5 and 6] Comparative Example 1 is an evaluation result of H C - 2 5 M S used as a substrate. Further, Comparative Example 2 was a polyacetal rubber sheet HC-25MR3 manufactured by Shin-Etsu Chemical Co., Ltd. which was provided with a thick 〇.〇2 mm protective layer. [Crosslinking point] The molar number of 100 moles of oxime ethylene to dimethyl oxirane was defined. The polyoxyxyl protective layer was hydrolyzed by tetraethoxy decane and potassium hydroxide. The ethoxy group represented by the following formula (5) to (8) detected by gas chromatography analysis-FID detector analysis. The peak area of decane was calculated. The formula (5) is a component derived from a dimethyloxane unit, and the formulae (6) to (8) are components derived from a cross-linking point of iridium ethylene. The detected sensitivities are different, but are corrected from the measurement results of the known substances and converted into molar ratios. -21 - (5)201114590 [Chemical 5] CH3 CH3CH2〇-Si-〇CH2CH3 CH3 CH, CH, CH3CH2〇-Si-CH2CH2-Si-〇CH2CH3 CH, CH, (6)

CH, I OCH^CH, CH3CH2〇-'〒-CH2CH2-Si-〇CH2CH3 CH3 CH, (7) OCH2CH3 OCH0CH3 CH3CH2〇-Si-CH2CH2-Si-〇CH2CH3 CH3 CH, the following is a more detailed description of the test conditions . (Processing method of polyoxygen protective layer) The polyxyl oxide protective layer 0·1 g was cut into a small glass bottle Λ, and then added with 4 g of tetraethoxy decane and potassium hydroxide O.Olg'. After heating for 1 hour, the mixture was neutralized with carbon dioxide at room temperature, and the supernatant obtained by centrifugation (1 0000 rpm/10 min) was analyzed by gas chromatography analysis of HP-6890 (FID detector) by Agilent. . (Gas chromatography analysis conditions) Model: HP-6890 (FID detector) Column: J&W DB-5MS (film thickness l//m) 0.25 mm IDx30m Column temperature: 50 °C - (l〇 t / min) - 30 (TC (10 minutes) -22- 201114590 Note inlet temperature: 2 5 0 °C Detector temperature: 3 Ο 0 °C Carrier gas: He (5mL / min)

Sample injection amount: 2 a L

[Pressing times (1), (2)] § The number of times of gastric pressure sticking (1) is not contact with the sheet after pressure bonding, or is only lightly touched, and the sheet is separated from the acrylic anisotropic conductive film, that is, it is maintained very much. The number of times of light release. Further, the number of press-fits (2) is reduced in the release property, and the number of components of the acrylic anisotropic conductive film is clearly moved toward the sheet. [Results] In the conditions of this pressure-bonding test, the release properties of Examples 1 to 3 were maintained at up to 10 times in the number of press-fit times (1). Among them, Example 2 showing side chain-side chain crosslinking exhibited excellent release properties. If the number of cross-linking points is less than 2, the number of times of press-bonding (1) will be particularly lowered. Even if the number of times of pressing is small, the sticking of the sheet and the anisotropic conductive film can be seen. Confidence in the chemical industry (stock) single-layer sheet and multi-layer sheet 'but regardless of the single layer, the multi-layer, and even the same evaluation of each company's various sheets' pressure-resistance test results for acrylic conductive adhesives are juxtaposed, The present invention is a great contributor to the efficiency of the thermo-adhesive wiring connection step of electrical and electronic machine parts. -23- 201114590 [Table i] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 X値40 100 120 140 210 510 170 One - y値0 3 18 0 0 0 1 — Crosslinking point 3.8 3.7 8.2 1.2 0.8 0.4 1.5 — 0.5 Coating liquid solvent free solvent free solvent free solvent dilution dilution solvent free dilution adhesive number Ο 11 18 10 3 1 0 5 0 0 Number of presses (2) 36 48 33 31 29 22 30 23 22 -24-

Claims (1)

201114590 VII. Patent application scope: 1. A thermocompression adhesive polysilicon rubber sheet, which is used for the thermocompression bonding line connection step of electrical and electronic machine parts. The polysilicon rubber sheet is made of thermal conductive polyoxyethylene rubber sheet. a thermosetting adhesive polyoxyethylene rubber sheet composed of a substrate layer and a polysilicon protective layer provided on at least one of the surfaces thereof, characterized in that the polyfluorene protective layer is an addition polycondensation Oxygenated by oxygen, containing 100% of dimethyloxane unit ((CH3)2Si01/2), an ethylene (Si-CH2-CH2-Si) 2 molar containing an addition reaction moiety the above. 2. The hot-pressed polyoxyxene rubber sheet of claim 1 wherein the polyoxygen protective layer comprises: a diorganopolyoxyalkylene having a vinyl group in a side chain and a SiH group in a side chain. A hardened substance of an organic hydrogen polyoxane and a polyoxonium composition of a uranium-based catalyst. 3. The hot-pressed polyoxyethylene rubber sheet according to claim 1 or 2, wherein the polyfluorene protective layer has a thickness of 0.1 Å or more and 30 m or less. 4. The thermocompression adhesive polyoxyethylene rubber sheet according to claim 1 or 2, wherein the polyfluorene protective layer contains at least one selected from the group consisting of a metal, a metal oxide, a metal nitride, and a metal carbide. The inorganic powder is 0.1% by mass or more and 30% by mass or less. 5. The hot press adhesive polyoxyethylene rubber sheet according to claim 1 or 2, wherein the inorganic powder is spherical fine powder cerium oxide. 6. The hot-pressed polyoxyethylene rubber sheet according to claim 1 or 2, wherein the fine powder cerium oxide is a spherical powder having an average particle diameter of 1/zm or more and 30/zm or less, and further sieving 3 5 # m above the coarse particles. -25- 201114590 7. The hot-pressed adhesive sheet according to claim 1 or 2, wherein the thermally conductive polyoxyethylene rubber sheet substrate has a thickness of 0.1 W/mK or more and 5 W/mK or less and a thickness of 0.05 mm or more. The thin layer of oxygen rubber satisfies the thermal conductivity of 1 mm or less. -26- 201114590 Four designated representative maps: (1) The designated representative figure of this case is: None (2) The symbol of the symbol of this representative figure is simple: No 201114590 If there is a chemical formula in the five cases, please disclose the chemical formula that best shows the characteristics of the invention: no