CN1680506A

CN1680506A - Thermal pressed silicon rubber sheets and manufacture thereof

Info

Publication number: CN1680506A
Application number: CNA2005100628810A
Authority: CN
Inventors: 樱井郁男; 桥本毅
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2004-04-07
Filing date: 2005-04-05
Publication date: 2005-10-12
Anticipated expiration: 2025-04-05
Also published as: JP2005297234A; CN100480350C; KR20060045518A; TW200536895A

Abstract

The invention provides a silicone rubber sheet for thermocompression bonding which does not stick the periphery without dusting powder, does not adhere to an anisotropic electrically conductive adhesive, is excellent in surface releasing properties and durability, is provided with flexibility, and is inexpensive, and to provide a method for manufacturing the same. The silicone rubber sheet for thermocompression bonding is manufactured by providing the second silicone rubber layer prepared by molding and curing a composition comprising (F) an organopolysiloxane, (G) a silicone powder, preferably, (H) a carbon black with a volatile content of <=0.5 mass% or (I) a fine powder silica with a specific surface area of >=50 m<SP>2</SP>/g, and (J) a curing agent, on one face or both faces of the first silicone rubber layer prepared by molding and curing a composition comprising (A) an organopolysiloxane with an average degree of polymerization of >=200, (B) a carbon black with a volatile content of <=0.5 mass%, (C) a fine powder silica with a specific surface area of >=50 m<SP>2</SP>/g, (D) one or more selected from metals, metal oxides, metal nitrides, or metal carbides, and (E) a curing agent.

Description

Thermal pressed silicon rubber sheets and manufacture method thereof

Technical field

The present invention relates to be used for even stressed thermal pressed silicon rubber sheets in transferred heat, especially, relate to and have good release property, be used for or pressed the thermal pressed silicon rubber sheets of sticking thing adhesion with on every side device feature, particularly, relate to when the moulding of veneer sheet and flexible printed board, when perhaps importing the anisotropic conductive tackiness agent between the lead electrode by the electrode that in liquid crystal panel etc., connected and flexible printed board, make it to be electrically connected and employed thermal pressed silicon rubber sheets and manufacture method thereof during mechanical connection.

Background technology

In recent years, liquid crystal panel is used as the indicating meter of mobile telephone, portable computer, computer control unit, Kamera, digital camera, navigationsystem, portable television, ultra-thin television more and more.When making this liquid crystal panel, in order to drive liquid crystal, usually by importing anisotropic conductive tackiness agent and heat pressure adhesive with carrying between the lead electrode that drives with the flexible printed board (FPC) of LSI, realize electrical connection and mechanical connection at the transparent lead electrode of liquid crystal panel.

In this case, in order to anisotropic adhesive, to apply uniform pressure in the transferred heat, with this end in view, generally use heat pressure adhesive to be clipped between heating and pressurizing adhesion material and the FPC with film from the heating and pressurizing adhesion material.As this heat pressure adhesive thin slice, also can use fluororesin films such as polytetrafluoroethylene (PTFE), but, generally use to have low elasticity and flexibility, the silicone rubber plate that has good thermal conductivity simultaneously for can be more even stressed.

But, compare with fluororesin film, the surface of silicone rubber plate has binding property, thin slice closely is bonded among heating and pressurizing instrument or the FPC, in the significantly reduced while of operability of pressing sticking step, when peeling off thin slice also can variation, the weather resistance variation.In addition and since when heat pressure adhesive thermal pressed silicon rubber sheets directly contact with the anisotropic-electroconductive adhesive of being overflowed, therefore, it must be this anisotropic-electroconductive adhesive is had non-fusible.Employed up to now thermal pressed silicon rubber sheets is insufficient to the non-binding property of anisotropic-electroconductive adhesive, has the problem of weather resistance.

Known thermal pressed silicon rubber sheets is, for example, the disclosed material that mixed nitride boron is strengthened with woven fiber glass in silicon rubber in the Te Kaiping 5-198334 communique (patent documentation 1), in the Te Kaiping 6-36853 communique (patent documentation 2) disclosed in silicon rubber mixed nitride boron and conductive material, the material that prevents chargeding performance that has with the woven fiber glass reinforcement, in the Te Kaiping 6-289352 communique (patent documentation 3) disclosed in silicon rubber hybrid ceramic or metal etc. have good thermal conductivity material, disclosedly in the Te Kaiping 7-11010 communique (patent documentation 4) be lower than the carbon black of 0.5 weight % and improved stable on heating material by add dewatered volatile content to silicon rubber, etc.But, these materials the fusible problem of slice surfaces or, the problem aspect the non-binding property of anisotropic conductive tackiness agent all is not well solved.

For this class problem, patent documentation 5 has proposed by spreading lepidiod powder such as pouncing on talcum powder on the surface of silicone rubber plate, then the technical scheme of the thermal pressed silicon rubber sheets of the unnecessary powder of water flush away.In this technical scheme, the binding property of slice surfaces is improved, but does not but improve in the problem aspect the non-binding property of anisotropic conductive tackiness agent.

For the fusible problem that solves above-mentioned slice surfaces and to the problem of the non-fusible aspect of anisotropic conductive tackiness agent, also can prepare fluorine resin film and silicone rubber plates such as polytetrafluoroethylene (PTFE) respectively, and these two kinds of thin slices are piled up use, in the method, owing to must use two kinds of thin slices thereby cause cost to increase, owing to must use different device that two kinds of thin slices are provided, so the cost of manufacturing installation also increases thereupon.

In addition, patent documentation 6～8 provides by silicone rubber plate and compoundization of heat-resistant resin film laminating are made its fusible while that loses slice surfaces, has the silicon rubber composite sheet that high-intensity heat pressure adhesive is used.But, when using this thin slice,, thereby come from the flexibility disappearance of rubber monomer because silicon rubber is bonded together with the heat-resistant resin film.Thereby occurred when pressurization, being difficult to evenly stressed, the necessary institute's applied pressure that increases, be limited but press the intensity of sticking thing, in addition, also exist owing to the heat-resistant resin film is the comparison costliness problem that raises the cost.

For solving this class problem, patent documentation 9,10 has proposed to make it have release property by lamination silicone layer on face of thermal conductivity sheet rubber or two faces, perhaps, do not contain the rubber-like release layer that the rubber combination of weighting agent is formed by lamination at least one face of thermal conductivity sheet rubber, can provide with inexpensive method can have the good film release property, not bonding, good durability, have the scheme of the heat bonding of flexibility when evenly transmitting pressure concurrently with silicone rubber plate with anisotropic conductive.

But, only being coated with, in the laminated release layers of methods institute such as rod is coated with, dip-coating at the blade coating by routine, tube, the release layer surface cunning that flattens easily shows the peculiar binding property of silicon rubber.Because this binding property causes in the operability worsens of making thermal pressed silicon rubber sheets, simultaneously, in actual use, also exist with each position the bonding generation that causes problem takes place.In order to solve this adherent problem, can perfuse by surface up to now as flakey powder such as mica that prevents tackiness agent or talcums, but these powder exist each position generation pollution problems at thin slice.Wherein, in patent documentation 10, proposed surperficial formation concaveconvex shape and made surface roughening, do not pounced on the scheme that prevents from also can not produce the binding property problem of spreading to release layer surface adherent powder even make.But, the methods such as method, corona discharge method or sand-blast of the transfer printing embossed surface after coating have been proposed as the method for this surface roughening, but the essential extra surface roughening step that increases exists the production performance variation of silicone rubber plate and the problem that cost increases.In addition,, promptly allow to solve fusible problem, also have problem for the surperficial release property variation of anisotropic conductive tackiness agent because the method for surface roughening and degree is different.

[patent documentation 1] spy opens flat 5-198344 communique

[patent documentation 2] spy opens flat 6-36853 communique

[patent documentation 3] spy opens flat 6-289352 communique

[patent documentation 4] spy opens flat 7-11010 communique

[patent documentation 5] spy opens flat 10-219199 communique

[patent documentation 6] spy opens flat 8-174765 communique

[patent documentation 7] spy opens the 2001-18330 communique

[patent documentation 8] spy opens flat 7-214728 communique

[patent documentation 9] spy opens the 2001-232712 communique

[patent documentation 10] spy opens the 2003-236988 communique

Summary of the invention

In view of the foregoing, the object of the present invention is to provide a kind of thermal pressed silicon rubber sheets of cheapness, even this silicone rubber plate except have good surperficial release property do not pounce on spread mica and talcum etc. also can to around device feature or pressed sticking deposits yields bonding, also has good release property, do not pounce on loose not bonding with the anisotropic conductive tackiness agent, have favorable durability, also have the flexibility that can evenly transmit pressure etc. concurrently.

In addition, the invention provides the manufacture method of a kind of heat conductivity silastic-layer and the laminated thermal pressed silicon rubber sheets of release layer, this method is at the blade coating by routine, after tube is coated with, rod is coated with, dip-coating etc. is coated with, by directly vulcanizing, form concaveconvex shape on the release layer surface easily.

The inventor has carried out positive research for achieving the above object, found that, press release layer by surperficial upper strata at the thermal pressed silicon rubber sheets of prior art, wherein the loading level of the mineral filler of this release layer is few and fill silicone powder in the base material of the silicon rubber with good release property, can obtain good effect.

That is, the present invention finds that because lamination forms second silastic-layer at least one face of first silastic-layer, wherein said first silastic-layer is to be made by the cured article of the rubber composition that contains following component:

(A) mean polymerisation degree is the organopolysiloxane more than 200 or 200: 100 weight parts,

(B) dewatered volatile matter be the following carbon black of 0.5 weight % or 0.5 weight %,

(C) the BET specific surface area is 50m ²/ g or 50m ²Fine silica end, (wherein, component (B) and total combined amount (C) are 0～150 weight part) that/g is above

That (D) selects from metal, metal oxide, metal nitride, metallic carbide except that said components (C) is at least a: 0～1,600 weight parts, (wherein, component (B), (C) and total combined amount (D) are 10～1,600 weight parts)

(E) solidifying agent: solidified significant quantity

Wherein said second silastic-layer is to be made by the cured article of the rubber composition that contains following component, thereby has finished the present invention:

(F) organopolysiloxane: 100 weight parts,

(G) silicone powder: 1～200 weight part

(H) dewatered volatile matter be the following carbon black of 0.5 weight % or 0.5 weight %,

(I) the BET specific surface area is 50m ²/ g or 50m ²Fine silica end, (wherein, component (H) and total combined amount (I) are 0～50 weight part) that/g is above

(J) solidifying agent: solidified significant quantity.

Therefore, the invention provides thermal pressed silicon rubber sheets as described below and manufacture method thereof.

[1] be provided with the formed silicone rubber plate of multilayer silastic-layer of second silastic-layer different with this first silastic-layer component by at least one face of first silastic-layer, wherein above-mentioned first silastic-layer is to contain the layer that the formed rubber composition forming and hardening of following component forms:

(E) solidifying agent: solidified significant quantity

Wherein above-mentioned second silastic-layer is to contain the layer that the formed rubber composition forming and hardening of following component forms:

(F) organopolysiloxane: 100 weight parts,

(G) silicone powder: 1～200 weight part

(I) the BET specific surface area is 50 m ²/ g or 50 m ²Fine silica end, (wherein, component (H) and total combined amount (I) are 0～50 weight part) that/g is above

(J) solidifying agent: the solidified significant quantity,

[2] manufacture method of thermal pressed silicon rubber sheets, it is characterized in that: first rubber composition is shaped to sheet, before or after this forming composition is solidified, on face of above-mentioned flap or two faces, second rubber composition is shaped to sheet, described second rubber composition is different with the first rubber composition component, in composition, be dispersed with silicone rubber powder, second rubber composition is heating and curing, perhaps make up when uncured at first silicon rubber, heat first and second rubber composition simultaneously and make its curing, on the cured article laminar surface of the second rubber composition flap, form concaveconvex shape, its medullary ray average roughness Ra: 0.4 μ m≤Ra≤5.0 μ m, maximum height Rmax:Rmax≤50 μ m.

The invention effect

Thermal pressed silicon rubber sheets of the present invention, be a kind of silicone rubber plate as described below: add mineral filler or silicone resin etc. on a small quantity, described material is inhibited to the non-binding property of the anisotropic conductive tackiness agent that silicon rubber itself is had, and the material layer that non-binding property is not had the destructive silicone powder is pressed onto on the existing thermal pressed silicon rubber sheets, forms surperficial release layer; Owing to being filled with silicone powder in the material that is formed with this surface release layer, at the blade coating by routine, after tube is coated with, rod is coated with, dip-coating etc. carries out lamination, directly sulfuration, thus, can form concaveconvex shape easily on this release layer surface, surface, can not pounce on and spread mica or talcum etc., avoid the peculiar binding property problem of polysiloxane.Thereby, need not to use repeatedly fluoro-resin such as polytetrafluoroethylene (PTFE), heat pressure adhesive becomes feasible with the use in the thin slice monomer, thereby can solve because pollution problem that dusting caused or for the adherent problem of each several part.In addition, can also be to make thermal pressed silicon rubber sheets than inexpensive method.Its result also helps to reduce the cost of heat pressure adhesive operation.

Embodiment

Silicon rubber sheet rubber of the present invention is by at least one face of first silastic-layer, is provided with to form the multilayer silastic-layer that the second different silastic-layers constituted with this first silastic-layer and form.

First silastic-layer among the present invention be by comprise following component (A) and, at least a among component (B), (C), (D) and, the cured article of the rubber composition that component (E) obtains:

(C) the BET specific surface area is 50m ²/ g or 50m ²Fine silica end more than the/g,

(D) from metal, metal oxide, metal nitride, metallic carbide except that said components (C), select at least a,

(E) solidifying agent: solidified significant quantity

Wherein, above-mentioned mean polymerisation degree is that to be preferably an average group accepted way of doing sth be R for organopolysiloxane more than 200 ¹ _aSiO _(4-a)/2(a is 1.95～2.05 positive number) represented organopolysiloxane, in the formula, R ¹Expression monovalence alkyl that replace or non-replacement.R ¹Specific examples comprise alkyl such as methyl, ethyl, propyl group, cycloalkyl such as cyclopentyl, cyclohexyl, alkenyl such as vinyl, allyl group, aryl such as phenyl, tolyl, perhaps the halogenation alkyl that partly replaced of the hydrogen atom in these groups by chlorine atom, fluorine atom etc.In the present invention, R ¹Be preferably 0.001～5 mole of %, the alkenyl of preferred especially 0.01～1 mole of %.

Above-mentioned organopolysiloxane is preferably importing vinyl, phenyl, trifluoro propyl etc. by dimethyl siloxane units in formed main chain or the main chain at this organopolysiloxane.In addition, as long as molecular end is to seal with three Organosilyls or hydroxyl, trimethyl silyl, dimethyl vinyl silyl, trivinyl silyl etc. are arranged as what the example of this three Organosilyl can be enumerated.

In addition, the mean polymerisation degree of above-mentioned organopolysiloxane is more than 200 or 200, is preferably 3,000～20,000.When polymerization degree less than 200, the physical strength variation after the curing becomes fragile.In addition, the viscosity of component (A) under 25 ℃ of temperature is preferably 10Pas or more than the 10Pas.

Dewatered volatile matter as component (B) is 0.5 weight % or the following carbon black of 0.5 weight %, this not only can improve the thermotolerance and the heat conductivity of above-mentioned first silastic-layer, and when improving physical strength, also by making it have charging preventive property the silicone rubber plate conductionization.Usually, because the thermotolerance of silicon rubber is subjected to the influence of pH value, moisture or impurity in the composition, therefore must give one's full attention to selection for additive.Carbon black can improve the thermotolerance of silicon rubber, but must consider its impurity and volatile matter.The weight of sooty volatile matter is equivalent to the oxygen compound (acidic components such as carboxyl, benzoquinones, lactone, hydroxyl) of chemisorption in the surface, and owing to cause oxygenatedchemicals to be vaporized from the surface by heating, to the thermotolerance generation detrimentally affect of silicone rubber resina.Therefore, by using the following carbon black of 0.5 weight % or the volatile matter below the 0.5 weight %, particularly 0.4 weight % or 0.4 weight %, even can realize also spendable thermotolerance under 300 ℃ high temperature.

What in addition, the measuring method of volatile matter of the present invention used is the method for being put down in writing in JIS K 6221 " rubber grade carbon black test method ".Particularly, be by in crucible, adding the carbon black of specified amount, after under 950 ℃ of temperature, heating 7 minutes, measuring the reduction of volatile matter.

Carbon black can be divided into furnace black, thermally oxidized black, thermal black, Shawinigan black etc. according to its manufacture method, as the carbon black that contains 0.5 weight % or the volatile matter below the 0.5 weight %, be preferably Shawinigan black or conductive carbon black etc. (for example the spy opens flat 1-272667 communique page 3 the 36th～40 row).

The sooty specific surface area is big more, and its effect that improves thermotolerance, the reduction of the physical strength when suppressing high temperature is just obvious more, therefore, in the present invention, preferred BET specific surface area 30m ²Above, the preferred especially 50m of/g ²/ g or 50m ²More than/the g, more preferably 100m ²/ g or 100m ²The carbon black that/g is above.The preferred 500m of the higher limit of BET specific surface area wherein ²/ g or 500m ²Below/the g, more preferably 300m ²/ g or 300m ²Below/the g.

The BET specific surface area of component (C) is 50m ²/ g or 50m ²The above fine silica end of/g can be used as the reinforcement composition of silicon rubber.This powder not only can be a wetting ability but also can be hydrophobic, considers from the aspect of strengthening performance, and preferred BET specific surface area is 50～800m ²/ g, preferred especially 100～500m ²/ g.The not enough 50m of specific surface area ²During/g, can not obtain sufficient strengthening effect.

Component of the present invention (B) and component (C) all have the effect that strengthens silicon rubber.As the dewatered volatile matter of component (B) is 0.5 weight % or the following carbon black of 0.5 weight %, with BEF specific surface area as component (C) be 50m ²/ g or 50m ²/ g compares at above fine silica end, and it is bigger to improve stable on heating effect, but at room temperature littler to the effect of intensity.Can strengthen composition to these two kinds according to the employed temperature of thermal pressed silicon rubber sheets and carry out suitable adjustment.Here, total combined amount of component (B) and component (C) is that per 100 parts by weight of component (A) are used 0～150 weight part, preferred 10～120 weight parts, most preferably 20～100 weight parts.If more than 150 weight parts, will be difficult to mix, cause the moulding processability variation.

Component (D) is for being selected from least a of metal, the metal oxide except that said components (C), metal nitride, metallic carbide, and can make silicone rubber plate of the present invention have heat conductivity.The example can be enumerated metals such as silver powder, copper powder, iron powder, nickel powder, aluminium powder, metal oxides such as zinc oxide, magnesium oxide, aluminum oxide, silicon oxide, ferric oxide, metal nitrides such as boron nitride, aluminium nitride, silicon nitride, metallic carbide such as silicon carbide, norbide.

The combined amount of component (D) is that per 100 parts by weight of component (A) are used 0～1,600 weight parts, preferred especially 0～1,000 weight part.If more than 1600 weight parts, then be difficult to mix, cause the moulding processability variation.

In addition, total combined amount of component of the present invention (B) and component (C) and component (D) is that per 100 parts by weight of component (A) are used 10～1,600 weight parts, preferred 20～1,200 weight parts, preferred especially 30～1,000 weight part.When total combined amount of component (B) and component (C) and component (D) was less than 10 weight parts, thermal conductivity was low, can not obtain sufficient performance.If surpass 1600 weight parts, then be difficult to mix, knead, cause the moulding processability variation.

In addition, in the rubbery intensity of emphasizing thermal pressed silicon rubber sheets of the present invention or stable on heating situation, the mixing portion rate component (D) at the fine silica end of the carbon black of preferred ingredient (B) or component (C) is many.Specifically, the component (A) of preferred per 100 weight parts, total combined amount of component (B) and component (C) is 30～100 weight parts, preferred ingredient (D) is 0～50 weight part.In addition, in emphasizing the situation of heat conductivity, the mixing portion rate of the thermal conduction additives of preferred ingredient (D) is many with respect to component (B) or component (C).Specifically, preferably with respect to the component (A) of 100 weight parts, total combined amount of component (B) and component (C) is 10～50 weight parts, and component (D) is 50～1,000 weight part.

The solidifying agent of component (E) can be suitably to be selected from employed known solidifying agent in the curing of conventional silicon rubber.What the example of these solidifying agent can be enumerated for example has: employed ditertiary butyl peroxide in the free radical reaction, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, organo-peroxides such as dicumyl peroxide, contain in the situation of the alkenyl more than 2 or 2 in the organopolysiloxane for 1 molecule of component (A), solidifying agent as addition reaction, that can enumerate has organic hydrogen polysiloxanes that is combined in the hydrogen atom on the Siliciumatom and a platinum class catalyzer that contains more than 2 or 2 in 1 molecule, for the organopolysiloxane that contains the silanol base more than 2 or 2 in the component (A), as the condensation reaction solidifying agent, having of can enumerating contains 2 or 2 above alkoxyl groups, acetoxyl group, ketoxime, the silicoorganic compound of the hydrolization group of allyloxy etc.In the present invention, preferably be cured by free radical reaction and/or addition reaction.

The addition of these solidifying agent, it both can be the identical amount in the situation with silicon rubber, it also can be the solidified significant quantity, in the situation of free radical reaction, the component (A) of preferred per 100 weight parts is used the organo-peroxide of 0.1～10 weight part, in the situation of addition reaction, preferably with respect to the alkenyl of component (A), use the SiH base and 1～2 of organic hydrogen polysiloxanes of 0.5～5 mole amount, the platinum class catalyzer of the amount of 000ppm.

In above-mentioned first rubber composition that forms first silastic-layer, also can be in the scope of not damaging purpose of the present invention, as required, adding is as the non-reacted organopolysiloxane of other components, the organopolysiloxane that end seals with hydroxyl silyl dimethyl etc. is used for the thinner of viscosity and hardness adjusting, clay, lime carbonate, weighting agents such as diatomite, mineral dyes such as cobalt blue, tinting materials such as organic dye, zinc carbonate, manganous carbonate, red iron oxide, titanium oxide, cerium oxide etc. improve thermotolerance, the reagent of flame retardant resistance, improve the reagent of the flame retardant resistance of platinum group metal metal species catalyzer, low molecular silicone esters, the dispersion agent of silanol, silane coupling agent, bonding imparting agent such as titanium coupling agent, the tetrafluoro polyethylene particulate of the green strength of raising rubber stock etc.

Secondly, in thermal pressed silicon rubber sheets of the present invention, second silastic-layer mainly with the release property that improves the first silastic-layer surface, prevent with the anisotropic conductive tackiness agent be bonded as purpose setting.

This second silastic-layer is formed by the cured article of the rubber composition that comprises following component (F), component (G), component (J) and preferred ingredient (H) and/or component (I), wherein the loading level of the non-fusible generation interferential mineral filler of the anisotropic conductive tackiness agent that is had for silicon rubber itself or silicone resin is few, and is that lamination is filled with and does not disturb the formed surperficial release layer of non-fusible silicone powder on existing thermal pressed silicon rubber sheets:

(F) organopolysiloxane,

(G) silicone powder,

(I) the BET specific surface area is 50m ²/ g or 50m ²Fine silica end more than the/g,

(J) solidifying agent,

Wherein, the organopolysiloxane of above-mentioned (F) component is R for example ² _bSiO _(4-b)/2Represented organopolysiloxane.Wherein, R ²Expression is selected from alkyl such as methyl, ethyl, propyl group, butyl, cycloalkyl such as cyclopentyl, cyclohexyl, alkenyls such as vinyl, allyl group, propenyl, butenyl, hexenyl, aryl such as phenyl, tolyl, xylyl, arylalkyls such as benzyl, 2-phenylethyl, perhaps in these groups with the part or all of hydrogen atom of carbon atom bonded by identical or different groups such as chloromethyl that halogen atom, cyano group etc. replaced, trifluoro propyl, cyano ethyls and contain 1～10 carbon atom, the monovalence alkyl replacement of preferred 1～8 carbon atom or unsubstituted.Substituent R 2 in conjunction with Siliciumatom can be above-mentioned any basically, preferably as the vinyl of alkenyl, as other substituent methyl or phenyl.Especially, in the situation that must have solvent resistance, preferred trifluoro propyl.In addition, b is 1.9～2.4 positive number.

This organopolysiloxane most preferably main chain is the two organopolysiloxanes of straight catenate, also can be to contain part R in the molecule ²SiO _3/2(R ²With above-mentioned), SiO ₂Branch's structures such as unit.Its mean polymerisation degree is preferably 10～20, and 000, during mean polymerisation degree less than 10, the physical strength of cured article can not fully satisfy the needs when using, if surpass 20,000, the roll operation of rubber stock and calendering formation are with variation.

In thermal pressed silicon rubber sheets of the present invention,, also can except being straight catenate diorganopolysiloxanecompositions, main chain use silicone resin, as the organopolysiloxane component of said components (F) in order to improve the physical strength of second silastic-layer.As silicone resin, preferably use by R ² ₃SiO _0.5Unit (M unit) and SiO ₂Unit (Q unit), perhaps, M unit and Q unit and R ²SiO _1.5Unit (T unit) and/or R ² ₂SiO unit (D unit) (R ²The same) MQ resin, MTQ resin, MDQ resin or the MDTQ resin formed any, preferably basically with M unit and Q unit as major constituent.In addition, as required, can also use and contain (CH ₂=CH) (CH ₃) ₂SiO _0.5Unit or (CH ₂=CH) CH ₃The unitary vinyl polysiloxane that contains of SiO.Particularly, preferably use by (CH ₃) ₃SiO _0.5Unit, (CH ₂=CH) (CH ₃) ₂SiO _0.5Unit and SiO ₂The resin that the unit is formed, or by (CH ₃) ₃SiO _0.5Unit, (CH ₂=CH) (CH ₃) SiO unit and SiO ₂The resin that the unit is formed.

The content of the silicone resin in this component (F) be preferably second rubber composition total amount 20 weight % or below the 20 weight %, preferred especially 0.1～10 weight %, if surpass 20 weight %, its release property for the anisotropic conductive tackiness agent will variation.

As the silicone powder of component (G), be to be used to prevent owing to the become binding property problem that smoothly causes of the second silastic-layer surface.That is,, can form concaveconvex shape easily on the surface of second silastic-layer and make it surface roughening, thereby not spread mica or talcum etc., also can avoid the binding property problem by pouncing on by filling silicone powder.Also have, do not make the method for the second silastic-layer surface roughening, use blade coating, the simple coating laminating methods such as tube is coated with, rod is coated with, dip-coating of routine,, can realize surface roughening by the filling silicone powder by the filling silicone powder.In the situation of only considering surface roughening, also can use for example powder filler except that silicone powder such as aluminum oxide or crystalline silica, in this case, can not damage the non-binding property of the anisotropic conductive tackiness agent that polysiloxane was had originally.On the one hand, in the filling of silicone powder, can not damage non-binding property, can make the surface roughening of silicon rubber yet the anisotropic conductive tackiness agent.

Material as silicone powder for example has, and is mainly the crosslinked silicone powder of straight catenate organopolysiloxane, siloxane bond (RSiO _3/2) _nThe silicone powders of the organic poly sesquisiloxane curing powder of the three-dimensional netted crosslinking structure of (R represents the monovalence alkyl of that replace or non-replacement) expression, the silicone composite powder of the structure of silicone resin is arranged in the surface coated of polysiloxane rubber powder, the silicone powder of component of the present invention (G) can be used the powder that only contains single-material, also can use the powder that contains material more than 2 kinds or 2 kinds.

The median size of silicone powder is that 1～50 μ m is suitable, more preferably 3～30 μ m.If median size less than 1 μ m, then silastic-layer surface can cause the binding property problem near even surface, if median size greater than 50 μ m, the concave-convex surface shape becomes excessive, just can not transmit pressure equably as the pressure bonding die.Owing to the concave-convex surface shape of second silastic-layer can change along with particle diameter, material, loading level, bed thickness or the condition of molding of silicone powder, therefore, must select the silicone powder of optimum grain-diameter.In addition, in the present invention, can measure median size by the laser diffraction and scattering method.

The combined amount of silicone powder is 1～200 weight part with respect to the organopolysiloxane of the component (F) of per 100 weight parts, preferred 3～100 weight parts, preferred especially 5～50 weight parts.When less than 1 weight part, the silastic-layer surface causes adhesion problem near even surface.If surpass 200 weight parts, a little less than the intensity of second silastic-layer became in the situation of silicone rubber powder, cause demoulding weather resistance variation, in the situation of silicone powders, because the extensibility when cutting off diminishes, it is really up to the mark to become simultaneously, therefore, can not chap with first silastic-layer is movable to such an extent as to become.

Dewatered volatile matter as component (H) is thermotolerance and the heat conductivity that 0.5 weight % or the following carbon black of 0.5 weight % not only can improve above-mentioned second silastic-layer, can also when improving physical strength, make it have anti-charging property by making the second silastic-layer conductionization.The carbon black of the component (B) of the carbon black in the component of second silastic-layer (H) and first silastic-layer is the same, consider stable on heating problem, preferred use 0.5 weight % or below the 0.5 weight %, the volatile matter that preferred especially 0.4 weight % or 0.4 weight % are following, for example acetylene black or conductive carbon black are suitable (for example, the spy open flat 1-272667 communique page 3 the 36th～40 row).

Because the sooty specific surface area is big more, just can improve its thermotolerance more, the effect that inhibition physical strength at high temperature is low is just big more, therefore, in the present invention, preferably uses the BET specific surface area to be 30m ²/ g or 30m ²More than/the g, preferred especially 50m ²/ g or 50m ²More than/the g, more preferably 100m ²/ g or 100m ²The carbon black that/g is above.

BET specific surface area as component (I) is 50m ²/ g or 50m ²The above fine silica end of/g is the reinforcement composition as second silastic-layer.Its specific examples comprises wetting ability or hydrophobic fumed silica (dry type silicon-dioxide) and deposits silica (wet silicon dioxide), crystallinity silicon-dioxide, quartz etc. that it can use separately, also can use with its two or more mixing.From the property strengthened consideration, the BET surface-area of fine powder used in the present invention is necessary for 50m ²/ g or 50m ²More than/the g, use 50～800m usually ²/ g, particularly 100～500m ²Be suitable about/g.The not enough 50m of specific surface area ²During/g, can not obtain sufficient strengthening effect.

In these silicon-dioxide, can use commercially available wetting ability silicon-dioxide, for example Aerosil 130,200,300 (trade(brand)names, Japan アエロジ Le company or Degussa company make), Cabosi 1MS-5, MS-7 (trade(brand)name, Cabot company makes), Rheorosil QS-102,103 (trade(brand)names, ト Network ヤマ Co., Ltd. makes), Nipsil LP (trade(brand)name, the シリカ of Japanese firm makes), in addition, can use hydrophobic silicon-dioxide, Aerosil R-812 for example, R-812S, R-972, R-974 (trade(brand)name, Degussa company makes), Rheorosil MT-10 (trade(brand)name, ト Network ヤマ Co., Ltd. makes), Nipsil SS series (trade(brand)name, the シリカ of Japanese firm makes), and to above-claimed cpd and unrestricted.

In the present invention, in order to make the non-binding property of its physical strength that has second silastic-layer concurrently and anisotropic conductive tackiness agent, preferably use the hydrophobic silica of surface preparation and when material is kneaded, hydrophilic silica sphere is handled by adding the surface treatment agent that organosilicone compounds forms.

Above-mentioned hydrophobic silicon-dioxide, basically be by using the surface treatment agent of dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, hexamethyldisilazane or its mixture etc., perhaps use these surface treatment agents and water that these hydrophilic fine silica ends are heat-treated and obtain, use through (CH on its surface ₃) ₃SiO _1/2Base, (CH ₃) ₂SiO _2/2Base, CH ₃SiO _3/2Base, preferred (CH ₃) ₂SiO _2/2Base and CH ₃SiO _3/2The hydrophobic silicon-dioxide that base is handled is especially preferably through CH ₃SiO _3/2Base is handled, and the surface-treated hydrophobic silica contains total relatively silicon-dioxide 0.5 weight % or the above carbon of 0.5 weight % usually like this.

The example of the surface treatment agent that above-mentioned organosilicon ammonia hydride compounds is formed can be enumerated for example (CH ₃) ₃SiNHSi (CH ₃) ₃, (CH ₃) ₃SiNHSi (CH ₃) ₂NHSi (CH ₃) ₃, (CH ₃) ₂(CF ₃CH ₂CH ₂) SiNHSi (CF ₃CH ₂CH ₂) (CH ₃) ₂Deng the organic the silazane, (CH that do not contain carbon functional group's group (for example alkenyl) of six organic silazane with alkyl, aryl, substituted alkyl, eight organic three silazane etc. ₃) ₂(CH=CH ₂) SiNHSi (CH ₃) ₂NHSi (CH=CH ₂) (CH ₃) ₂, (CH ₃) ₃SiNHSi (CH ₃) (CH ₂=CH) [OSi (CH ₃) ₂] _nNHSi (CH ₃) ₃, CH ₂=CHSi[NHSi (CH ₃) ₃] ₃Deng organosilicon ammonia hydride compounds that contains alkenyls such as vinyl etc.These organosilicon ammonia hydride compounds can only use the organosilicon ammonia hydride compounds that does not contain the carbon functional group, also can use the organosilicon ammonia hydride compounds that contains alkenyl, also it can be mixed and use.Especially, by using the most frequently used hexamethyldisilazane (CH ₃) ₃SiNHSi (CH ₃) ₃, can access cheap and easy effect.

Surface treatment method when kneading as material, can be in mixing tank, will heat when kneading as adding mixture as the wetting ability silicon-dioxide of component (I) in the organopolysiloxane of said components (F), when adding organosilicon ammonia hydride compounds, add a spot of water as required, carry out heat treated, because the silanol on the such processing and the surface of silicon-dioxide has obtained processing, can have good anti-release property by the silicon rubber that the curing said composition obtains.

The combined amount of this organosilicon ammonia hydride compounds is equivalent to the fine silica end of the component (I) of 100 weight parts, is preferably 1～100 weight part, more preferably 1～50 weight part.If less than 1 weight part, the degree of treatment of silicon oxide surface is just insufficient, causes bad influence for the release property for the anisotropic conductive tackiness agent.In addition, if surpass 100 weight parts, not only can not see obvious improvement for this effect, but also can bring detrimentally affect to the physical strength of the silicon rubber after solidifying, and in actual use, the problem that the danger that ammonia caused that is produced when also existing owing to these silazane reactions increases.

In the present invention, can use the hydrophobic silica fine powder, more preferably organosilicon ammonia hydride compounds carries out surface treatment.As the treatment process in this situation, surface-treated method that can be when kneading above-mentioned wetting ability silicon-dioxide is identical, and the degree of treatment of silica sphere silanol is high more, and is just good more by the demoulding weather resistance of solidifying the resulting silicon rubber of said composition.

Component of the present invention (H) and component (I) all have the effect of strengthening silicon rubber, are 0.5 weight % or the following carbon black of 0.5 weight % as the dewatered volatile matter of component (H), though the BET specific surface area that likens to component (I) is 50m ²/ g or 50m ²The stable on heating effect of fine silica end raising more than the/g is bigger, but at room temperature littler to the effect of intensity.Can strengthen composition to these two kinds and suitably adjust according to the use temperature of thermal pressed silicon rubber sheets of the present invention.In addition, can be according to the working conditions of thermal pressed silicon rubber sheets of the present invention, to carrying out suitable adjustment as the carbon black of component (H) and total combined amount as the fine silica end of component (I), its organopolysiloxane as component (F) with respect to 100 weight parts is 0～50 weight part, preferred 1～30 weight part, preferred especially 3～20 weight parts.If surpass 50 weight parts, it is insufficient that its release property just becomes, and just easy and anisotropic conductive tackiness agent takes place bonding.

The solidifying agent of component (J) can be selected from employed known solidifying agent in the curing of conventional silicon rubber.The example of these solidifying agent is employed ditertiary butyl peroxides in the free radical reaction for example, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, organo-peroxides such as dicumyl peroxide, the situation that contains the alkenyl more than 2 or 2 in 1 molecule for the organopolysiloxane in (F) component, be organic hydrogen polysiloxanes that is connected the hydrogen atom on the Siliciumatom and the platinum class catalyzer that for example contains in 1 molecule more than 2 or 2, containing the situation of the silanol more than 2 or 2 for the organopolysiloxane in (F) component, is for example as the alkoxyl group more than 2 or 2 of containing of condensation reaction solidifying agent, acetoxyl group, ketoxime, the silicoorganic compound of the hydrolization group of propenyloxy group etc.

The add-on of these solidifying agent can be the amount identical with silicon rubber, also can be to solidify significant quantity, in the situation of free radical reaction, with respect to the component (F) of 100 weight parts, preferably use the organic peroxy compound of 0.1～10 weight part, in the situation of addition reaction, alkenyl with respect to component (F), the preferred SiH base that uses 0.4～4 mole organic hydrogen polysiloxanes, and 1～2, the platinum series catalysts of 000ppm.

In the above-mentioned second polysiloxane rubber composition that forms second silastic-layer, also can be in the scope of not damaging purpose of the present invention, as required, adding is as the non-reacted organopolysiloxane of other components in second rubber composition, viscosity such as terminal organopolysiloxane with the sealing of hydroxyl silyl dimethyl and hardness are regulated the thinner of usefulness, clay, lime carbonate, weighting agents such as diatomite, mineral dyes such as cobalt blue, tinting materials such as organic dye, zinc carbonate, manganous carbonate, red iron oxide, titanium oxide, cerium oxide etc. improve thermotolerance, the reagent of flame retardant resistance, the reagent of the flame retardant resistance of raising platinum class catalyzer etc., low molecular silicone esters, the dispersion agent of silanol, silane coupling agent, bonding imparting agent such as titanium coupling agent, tetrafluoro polyethylene particulate of the green strength of raising elastomeric material etc. or metal, metal oxide, metal nitride, heat conductivities such as metallic carbide improve reagent etc.Wherein, the mineral filler that contains the fine silica end of described component (H) carbon black and component (I) is preferably added on a small quantity, this is based on producing non-binding property between it and the anisotropic conductive tackiness agent, the easily demoulding, preferred mineral filler add-on is 20 weight % of the second rubber composition total amount or below the 20 weight %, preferred especially 0.1～15 weight %.

And, can use planetary-type mixer, kneading machine, two Rolled machine, three Rolled machines, banbury mixers to mix above-mentioned each component, also this solidifying agent can be added directly before using solidifying agent, to prepare above-mentioned first rubber composition, second rubber composition.

Wherein, condition of cure in the time of can suitably selecting the curing of above-mentioned first rubber composition, second rubber composition, and the condition optimization that is heating and curing particularly heated 30 seconds～60 minutes particularly 1 minute～30 minutes at 60～200 ℃ under 80～150 ℃ the temperature.

The JIS K 6253 Zou Shi sclerometers of second silastic-layer after the preferred consolidation, the hardness of hardness test A type is more than 20 or 20, preferred especially 30～95.If hardness less than 20 is pressed when gluing, each is pressed sticking parts just to become and is bonded together easily.

In thermal pressed silicon rubber sheets of the present invention, the surface of (second silastic-layer or it and first silastic-layer) is provided with concaveconvex shape in its both sides, pass through surface roughening, do not pounce on and spread as the mica of anti-adhesive agent or talcum etc., the peculiar binding property of silicon rubber is disappeared, thus can avoid operational issue when the manufacturing of silicone rubber plate or actual the use time for the adhesion problem of each parts.It is 0.4～5.0 μ m that the concaveconvex shape degree on two surfaces of silicone rubber plate is preferably center line average roughness Ra, and 0.5～3.0 μ m particularly, maximum height Rmax are preferably 50 μ m or below the 50 μ m, preferred especially 30 μ m or below the 30 μ m.When Ra less than 0.4 μ m, avoid fusible effect just insufficient by concaveconvex shapeization, if Ra is bigger than 5.0 μ m, Rmax is bigger than 50 μ m, it is just inhomogeneous to transmit pressure when pressure is sticking, so not preferred.

The thickness of preferred above-mentioned second silastic-layer of thermal pressed silicon rubber sheets of the present invention is 1～50 μ m, the total thickness that is pressed with the silastic-layer thin slice of second silastic-layer at face of first silastic-layer or two surface layers is 0.1～10mm, the thickness of preferred especially second silastic-layer is 2～30 μ m, and the total thickness that is pressed with the silastic-layer thin slice of second silastic-layer at face of above-mentioned first silastic-layer or two surface layers is 0.1～10mm.The thickness less than 1 μ m of second silastic-layer can not find sufficient release property, if surpass 50 μ m then the heat conductivity variation.In addition, when the not enough 0.1mm of the total thickness of silicone rubber plate,, then can not evenly transmit pressure, if surpass 10mm, heat conductivity variation owing to can not fully cooperate with being pressed sticking body.

The forming method of the silicon rubber of heat pressure adhesive of the present invention can be a method as described below, but is not limited to following method.

(1) after reheat solidifies to the carrier thin film that is processed as center line average roughness Ra:0.4 μ m≤Ra≤5.0 μ m, maximum height Rmax:Rmax≤50 μ m by embossing by calendering or extrusion molding with first rubber composition, by blade coating, tube is coated with, methods such as rod is coated with, dip-coating will be dissolved in the liquid state in the toluene equal solvent the second rubber composition coated and molded in the above, directly in air, remove the method for desolvating and being heating and curing then.At this moment, in the lower situation of the viscosity of second polysiloxane composition, also can it be dissolved in the toluene equal solvent and direct coated and molded.

(2) first rubber composition is dissolved in the toluene equal solvent makes its liquid stateization, with its coated and molded remove again on the carrier thin film of above-mentioned identical embossing processing desolvate be heating and curing after, by blade coating, tube is coated with, methods such as rod is coated with, dip-coating will be dissolved in the liquid stateization in the toluene equal solvent the second rubber composition coated and molded in the above, directly in air, remove the method for desolvating and being heating and curing then.At this moment, in the lower situation of the viscosity of second polysiloxane composition, also can it be dissolved in the toluene equal solvent and direct coated and molded.

(3) first rubber composition is dissolved in the toluene equal solvent makes its liquid stateization, with its coated and molded on the carrier thin film of above-mentioned identical embossing processing, keep its uncured state after removing solvent composition, by blade coating, tube is coated with, methods such as rod is coated with, dip-coating will be dissolved in the liquid stateization in the toluene equal solvent the second rubber composition coated and molded in the above, directly in air, remove then desolvate after, two-layer method is heating and curing.Wherein, in the lower situation of the viscosity of second polysiloxane composition, also can it be dissolved in the toluene equal solvent and direct coated and molded.

In the present invention, in order to strengthen the bonding of first silastic-layer and second silastic-layer, can use suitable methods such as prime treatment.In addition, second silastic-layer also can be set on two faces of first silastic-layer form 3-tier architecture, in this case, the material of 2 layers second silastic-layer can be different, also can be identical.

Can use glass transition temperature is the cloth of the resin formation more than 200 ℃, and perhaps the strengthening material of woven fiber glass formation is strengthened thermal pressed silicon rubber sheets of the present invention.

Thermal pressed silicon rubber sheets of the present invention is preferably 0.2 weight % or below the 0.2 weight % at the volatile matter of heating after 3 hours under 150 ℃ the temperature, more preferably 0.1 weight % or below the 0.1 weight %.If volatile matter surpasses 0.2 weight %, volatile component will condense upon on the end of electrode, causes conducting bad.For this reason, preferably thermal treatment silicone rubber plate at high temperature preferably in drying machine or continuous furnace, carries out heat treated under 150 ℃ of temperature.

Below, in conjunction with the embodiments and comparative example the present invention is carried out specific description, but the present invention is not limited to specific embodiment described below.And, below in the specific embodiment, specific surface area is the value representation measured by BET method (N2 gas adsorption method), median size is the value representation measured by the laser diffraction and scattering method, volatile matter is by under 150 ℃ of temperature, heated 3 hours, the value of quality of getting back to the minimizing of measuring after the room temperature then is represented.

[embodiment 1]

Use that kneading machine is formed with the methyl vinyl siloxane unit by the dimethyl siloxane units of 99.85 moles of % and 0.15 mole of % of 100 weight parts, mean polymerisation degree is 8,000 methylvinyl-polysiloxane, alumina powder as 400 weight parts of the weighting agent with good heat conductivity: aluminum oxide AL-45 (clear and electrician (Co., Ltd.) makes), the specific surface area of 30 weight parts is 200m ²The fine silica end of/g: アエロジ Le 200 (Japanese アエロジ Le (Co., Ltd.) manufacturing) and the represented α of 5 weight part following formulas (1), the alpha, omega-dihydroxy methyl polysiloxane, mix equably, and under 150 ℃ of temperature heat treated 2 hours.

After the cooling, use two Rolled machines in this silicon rubber rubber compound of 100 weight parts, mixing the specific surface area that adds 0.5 weight part is 140m ²The ceria oxide powder of/g, 1.5 weight parts are as the organo-peroxide of solidifying agent: C-23 (SHIN-ETSU HANTOTAI's chemical industry (Co., Ltd.) manufacturing), use the calendering formation machine its compressing tablet to be become the thickness of 0.30mm then, it is transferred to the medullary ray surface roughness Ra is that the thickness of face embossing processing of 0.7 μ m is on the PET film of 125 μ m, be placed on then in 160 ℃ the process furnace and it solidified in 5 minutes, make first silastic-layer of thermal pressed silicon rubber sheets of the present invention.

To two ends of 85 weight part molecular chains by the vinyl-dimethyl base silyl-capped, mean polymerisation degree is 180 dimethyl polysiloxane, two ends of the molecular chain of 10 weight parts by the vinyl-dimethyl base silyl-capped, mean polymerisation degree is 510 dimethyl polysiloxane, and 5 weight part be 8 by the dimethyl siloxane units of 90.25 moles of % and the formed mean polymerisation degree of ethylene methacrylic radical siloxane of 9.75 moles of %, in 000 the methylvinyl-polysiloxane, add the about 300m of BET specific surface area of 5 weight parts ²The wetting ability silicon-dioxide of/g (アエロジ Le 300: trade(brand)name, Japan's アエロジ Le (Co., Ltd.) is made), and then add the hexamethyldisilazane of 1 weight part and the water of 0.5 weight part, in 1 hour time, after in planetary-type mixer, mixing under the room temperature, 60 ℃ of heat treated 4 hours reduce temperature then to normal temperature.

Then, add that 30 weight parts have silicone rubber powder that the median size that straight catenate dimethyl organopolysiloxane is cross-linked to form is 5 μ m and the specific surface area of 0.5 weight part is 140m ²The ceria oxide powder of/g, at room temperature mix 1 hour after, in three Rolled machines, further mix.

And then, mix and add Platinic chloride successively with respect to the platinum weight of the dimethyl polysiloxane 50ppm except that silicone powder, with respect to ethynylcyclohexanol, the represented methylhydrogenpolysi,oxane of last 8 weight part following formulas (2) of the reaction suppressor of 0.2 weight part of the dimethyl polysiloxane except that silicone powder of 100 weight parts

Make second rubber composition of even composition.Said composition was heating and curing 5 minutes under 150 ℃ of temperature, and then under 200 ℃ of temperature after the after fixing 4 hours, recording its A type hardness tester by the scleroscopic hardness test of JIS K 6253 Zou Shi is 40.

Above-mentioned second rubber composition is dissolved in the toluene, it is adjusted to the concentration of 40 weight %, on the first polysilicone rubber layer, its coated and molded is become the thickness of 15 μ m by blade coating, then with it directly by removing toluene in the process furnace of 50 ℃ of temperature in 5 minutes, then by making its crosslinking curing in the process furnace of 150 ℃ of temperature in 5 minutes.Then, peel off the silicone rubber plate of these 2 layers of structures from the PET film, after fixing is 4 hours under 200 ℃ of temperature, the thickness that makes second silastic-layer is 15 μ m, and the total thickness of the silicone rubber plate that first silastic-layer and second silastic-layer combine is the thermal pressed silicon rubber sheets of the present invention of 0.315mm.

The surfaceness of the silicone rubber plate of these 2 layers of structures is, the first silastic-layer Ra is that 0.74 μ m, Rmax are 5.5 μ m, and the second silastic-layer Ra is that 0.9 μ m, Rmax are 7.2 μ m.In addition, 3 hours volatile matter of heating is 0.12 weight % under 150 ℃ of temperature.

[embodiment 2]

Use that two rollers are formed to the methyl vinyl siloxane unit by the dimethyl siloxane units of 99.85 moles of % and 0.15 mole of % of 100 weight parts, mean polymerisation degree is 8, in 000 the methylvinyl-polysiloxane, the median size of mixing 50 weight parts is that 23nm, volatile matter are that the BET specific surface area of 0.10 weight % is 130m ²The acetylene black of/g, the BET specific surface area of 5 weight parts is 120m ²The hydrophobic silica of/g (アエロジ Le R-972: trade(brand)name, Degussa company make) and the BET specific surface area of 0.5 weight part are 140m ²The ceria oxide powder of/g is with its mixing homogenizing of kneading.

Adding is with respect to this silicone rubber compound of 100 weight parts, the represented methylhydrogenpolysi,oxane of following formula (3) as the ethynylcyclohexanol and 1.2 weight parts of reaction suppressor of the aqueous isopropanol of the Platinic chloride of 0.1 weight part (platinum content is 2 weight %), 0.1 weight part:

It is mixing fully to knead with two rollers, prepares the rubber composition that forms first silastic-layer.

Use the calendering formation machine this rubber composition compressing tablet to be become the thickness of 0.25mm, it is transferred to the medullary ray surface roughness Ra is that the thickness of the single face embossing processing of 0.7 μ m is on polyethylene terephthalate (PET) film of 125 μ m, be placed on then in 160 ℃ the process furnace and it solidified in 5 minutes, make first silastic-layer of thermal pressed silicon rubber sheets of the present invention.

The composition of second silastic-layer and forming method are identical with embodiment 1, the thickness that makes second silastic-layer is 15 μ m, and the total thickness of the silicone rubber plate that first silastic-layer and second silastic-layer combine is the silicone rubber plate of the laminar structure of identical after fixing with embodiment 1 of 0.265mm.

The surfaceness of the silicone rubber plate of these 2 layers of structures is, the first polysiloxane rubber layer Ra is that 0.74 μ m, Rmax are 5.5 μ m, and the second polysiloxane rubber layer Ra is that 0.9 μ m, Rmax are 7.2 μ m.In addition, 3 hours volatile matter of heating is 0.08 weight % under 150 ℃ of temperature.

[embodiment 3]

Make first silastic-layer that thickness is 0.2mm according to same procedure with embodiment 1.

Except the median size of using organic poly sesquisiloxane to solidify fine powder is the silicone powders of 10 μ m, the method that other is all identical with embodiment 1 prepares second rubber composition.The said composition that under 150 ℃ of temperature, is heating and curing 5 minutes, after fixing is after 4 hours under 200 ℃ of temperature again, and recording its A type hardness tester by JIS K 6253 Zou Shi sclerometers is 55.

The composition of second silastic-layer and forming method are identical with embodiment 1, the thickness that makes second silastic-layer is 10 μ m, the total thickness of the silicone rubber plate that first silastic-layer and second silastic-layer combine be 0.21mm and with embodiment 1 silicone rubber plate of identical laminar structure through after fixing.

The surfaceness of the silicone rubber plate of these 2 layers of structures is, the first silicon rubber Ra is that 0.8 μ m, Rmax are 5.8 μ m, and the second silicon rubber Ra is that 1.2 μ m, Rmax are 9.3 μ m.In addition, 3 hours volatile matter of heating is 0.10 weight % under 150 ℃ of temperature.

[embodiment 4]

Is that the BET specific surface area of 0.10 weight % is 130m except using median size as 23nm, volatile matter ²It is 300m that the acetylene black of/g replaces the BET specific surface area ²Outside the wetting ability silicon-dioxide of/g, other is all identical with embodiment 1, prepares second rubber composition.The said composition that under 150 ℃ of temperature, is heating and curing 5 minutes, after fixing is after 4 hours under 200 ℃ of temperature again, and recording its A type hardness tester by JIS K 6253 Zou Shi sclerometers is 43.

The composition of second silastic-layer and forming method are identical with embodiment 1, the thickness that makes second silastic-layer is 15 μ m, the total thickness of the silicone rubber plate that first silastic-layer and second silastic-layer combine be 0.215mm and with embodiment 1 the silicon rubber thin slice of the laminar structure of identical after fixing.

The surfaceness of the silicon rubber thin slice of these 2 layers of structures is, the first silastic-layer Ra is that 0.8 μ m, Rmax are 5.8 μ m, and the second silastic-layer Ra is that 1.5 μ m, Rmax are 12.3 μ m.In addition, 3 hours volatile matter of heating is 0.10 weight % under 150 ℃ of temperature.

[embodiment 5]

Second rubber composition identical with embodiment 1 is dissolved in the toluene, with its concentration adjustment to 18 weight %, is the coating of 15 μ m by dip coating at two faces formation thickness of first silastic-layer of being peeled off from the PET film, subsequently, removed toluene in 5 minutes by it directly being put into 50 ℃ of process furnace, then put it in 150 ℃ of process furnace and to make its crosslinking curing in 5 minutes.Then, after fixing is 4 hours under 200 ℃ of temperature, the thickness that makes second silastic-layer is 15 μ m, and the total thickness of the silastic-layer that first silastic-layer and second silastic-layer combine is the thermal pressed silicon rubber sheets of the 3-tier architecture of the present invention of 0.330mm.

The surfaceness of the silicone rubber plate of this 3-tier architecture is, a lateral Ra is that 1.9 μ m, Rmax are 18.5 μ m, and the Ra of another side is that 2.3 μ m, Rmax are 20.1 μ m.In addition, 3 hours volatile matter of heating is 0.11 weight % under 150 ℃ of temperature.

[comparative example 1]

Except not adding the silicone powder, all the other are all identical with embodiment 1 method, prepare second rubber composition.The said composition that under 150 ℃ of temperature, is heating and curing 5 minutes, after fixing is after 4 hours under 200 ℃ of temperature again, and recording its A type hardness tester by JIS K 6253 Zou Shi sclerometers is 44.

The composition of second silastic-layer, forming method and thickness are identical with embodiment 1, make the silicon rubber thin slice of the laminar structure of the after fixing identical with embodiment 1.

The surfaceness of the silicone rubber plate of these 2 layers of structures is, the first silastic-layer Ra is that 0.8 μ m, Rmax are 5.8 μ m, and the second silastic-layer Ra is that 0.2 μ m, Rmax are 1.3 μ m.In addition, 3 hours volatile matter of heating is 0.10 weight % under 150 ℃ of temperature.

[comparative example 2]

Except the median size of adding 50 weight parts is that the crystallinity SiO 2 powder (crystallinity silica A-1, dragon gloomy (strain)) of 12 μ m is produced, trade(brand)name replaces the silicone powder, all the method with embodiment 1 is identical for other, prepares second rubber composition.The said composition that under 150 ℃ of temperature, is heating and curing 5 minutes, after fixing is after 4 hours under 200 ℃ of temperature again, and recording its A type hardness tester by JIS K 6253 Zou Shi sclerometers is 48.

The surfaceness of the silicone rubber plate of these 2 layers of structures is, the first silastic-layer Ra is that 0.8 μ m, Rmax are 5.8 μ m, and the second silastic-layer Ra is that 1.4 μ m, Rmax are 13.1 μ m.In addition, 3 hours volatile matter of heating is 0.09 weight % under 150 ℃ of temperature.

[comparative example 3]

Making thickness according to the same procedure with embodiment 1 is that first silastic-layer of 0.2mm is pressed with the double-deck silicone rubber plate through after fixing that thickness is second silastic-layer of 15 μ m on a face upper strata of this layer.

Then, carry out sandblasting by surface, make its surface have concaveconvex shape and surface roughening, by washing except that after the shakeout powder to second silastic-layer, drying is 30 minutes under 150 ℃ of temperature, obtains two faces all by the double-deck silicon rubber thin slice of surface roughening.

The surfaceness of the silicone rubber plate of these 2 layers of structures is, the first silastic-layer Ra is that 0.8 μ m, Rmax are 5.8 μ m, and the second silastic-layer Ra is that 0.9 μ m, Rmax are 6.5 μ m.In addition, 3 hours volatile matter of heating is 0.10 weight % under 150 ℃ of temperature.

The evaluation of manufacturing step

In embodiment 1～5 and comparative example 1～3, the number of the forming step of second silastic-layer compares.

Evaluation during the shipment operation

The product warehouse-out form of the silicone rubber plate that heat pressure adhesive is used is to be crimped onto the form in the volume core cylindraceous mostly.If there is binding property in the sheet rubber surface when this curling operation, just be bonded together between sheet and the sheet when curling, be difficult to reduction, for situation, just can not load and transport outbound with this form with big machinery device intractable.Now, for relatively, with artificial form the heat pressure adhesive of manufacturing in embodiment 1～5 and the comparative example 1～3 is crimped onto in the volume core cylindraceous with the silicon rubber thin slice and compares.

Press sticking test evaluation

When heat pressure adhesive, the heat pressure adhesive thin slice directly contacts with the anisotropic conductive tackiness agent that overflows sometimes.Wherein, in order to observe non-binding property for this anisotropic conductive tackiness agent, thermal pressed silicon rubber sheets with manufacturing in embodiment 1～5 and the comparative example 1～3 is arranged in the sticking machine of pressure as described below: below this sheet, thickness is set directly.Be the anisotropic conductive film of 22 μ m, thereunder clamping thickness is the pressurizing tool that the polyimide film of 100 μ m uses the temperature be heated to 240 ℃ then, presses down sticking 20 seconds in the extruding of 4 Mpa.In the situation of 2 synusia structures, be provided with as follows during the heat pressure adhesive silicone rubber plate: first silastic-layer is arranged on a side of heating and pressurizing instrument, and the second silicone rubber layer is arranged on a side of anisotropic conductive tackiness agent.Whenever once press stickingly, just use new anisotropic conductive film instead, and it is sticking still to use original silicone rubber plate to press repeatedly, measure until the anisotropic conductive tackiness agent and be adhered to number of times in the thermal pressed silicon rubber sheets.

In addition, in order to observe except to the weather resistance the non-binding property of anisotropic conductive tackiness agent, in embodiment 1～5 and comparative example 1～3 below the thermal pressed silicon rubber sheets of manufacturing, using 2, to be provided with spacing be that the FPC of the copper electrode of 50 μ m is provided with clamping thickness is arranged is the anisotropic conductive membrane of 22 μ m, then it is arranged on and presses in the sticking machine, use is heated to the pressurizing tool of 340 ℃ temperature, presses down sticking 20 seconds in the extruding of 4Mpa.In this test,, press that its structure is the structure that does not overflow from the gap of 2 FPC according to the anisotropic conductive tackiness agent when sticking in order to estimate bonding between anisotropic conductive tackiness agent and the heat pressure adhesive sheet according to the method described above in addition.In the situation of 2 synusia structures, thermal pressed silicon rubber sheets is that assembling is set like this: first silastic-layer is arranged on pressurizing tool one side, second silastic-layer is arranged on FPC one side.Press repeatedly sticking, measure sheet rubber to the adherent state of FPC and under uniform pressure until the number of times that can not be heating and curing to the anisotropic conductive tackiness agent.This number of times is to confirm by the conduction of the copper electrode of FPC up and down.

The result is as shown in table 1.As can be known, there is not the distinctive binding property problem of polysiloxane in the thermal pressed silicon rubber sheets of embodiments of the invention 1～5, has favorable durability for the good non-binding property of having of anisotropic conductive tackiness agent, rubber self from table.And, can form concaveconvex shape on its surface simply with existing coating method by in second silastic-layer, filling silicone powder.

Shown in comparative example 1, do not carry out lamination if do not add silicone powder in the blade coating mode, its surface becomes smoothly, shows the distinctive binding property of polysiloxane, causes when the manufacturing shipment of silicone rubber plate is dispatched from the factory, and goes wrong in pressing sticking step.

Shown in comparative example 2, if fill crystalline silica except that silicone powder, can use conventional blade coating concavo-convex in the formation of sheet rubber surface, the non-tackiness agent of anisotropic conductive tackiness agent is become insufficient.

Shown in comparative example 3, when not adding silicone powder, undertaken also can forming concaveconvex shape on the surface after the lamination by sandblast by blade coating, still, cause its manufacturing step to increase, the problem that cost rises.

[table 1]

Sample	The forming step number of second silastic-layer	Whether manually it is crimped onto in the volume core cylindraceous	The number of occurrence when the anisotropic conductive tackiness agent is bonding	Under uniform pressure until the number of times of the anisotropic conductive tackiness agent that can not be heating and curing	Tacky state to the FPC of silicone rubber plate
Sample	The forming step number of second silastic-layer				Tacky state to the FPC of silicone rubber plate	Embodiment 1	1 (blade coating)	?????○	More than 100 or 100	?????????68	No problem
Embodiment 2	1 (blade coating)	?????○	More than 100 or 100	?????????88	No problem	Embodiment 1	1 (blade coating)	?????○	More than 100 or 100	?????????68	No problem
Embodiment 2	1 (blade coating)	?????○	More than 100 or 100	?????????88	No problem	Embodiment 3	1 (blade coating)	?????○	More than 100 or 100	?????????58	No problem
Embodiment 4	1 (blade coating)	?????○	More than 100 or 100	?????????61	No problem	Embodiment 3	1 (blade coating)	?????○	More than 100 or 100	?????????58	No problem
Embodiment 4	1 (blade coating)	?????○	More than 100 or 100	?????????61	No problem	Embodiment 5	1 (dip-coating)	?????○	More than 100 or 100	?????????63	No problem
Comparative example 1	1 (blade coating)	?????×	More than 100 or 100	?????????65	Strongly bonded	Embodiment 5	1 (dip-coating)	?????○	More than 100 or 100	?????????63	No problem
Comparative example 1	1 (blade coating)	?????×	More than 100 or 100	?????????65	Strongly bonded	Comparative example 2	1 (blade coating)	?????○	??23	?????????55	No problem
Comparative example 3	2 (blade coating+sandblasts)	?????○	??65	?????????51	No problem	Comparative example 2	1 (blade coating)	?????○	??23	?????????55	No problem

Claims

1. thermal pressed silicon rubber sheets, it is the silicone rubber plate that is formed by the multilayer silastic-layer, wherein, second silastic-layer different with this first silastic-layer component is set at least one face of first silastic-layer, it is characterized in that above-mentioned first silastic-layer is the layer that the rubber composition forming and hardening that will contain following component forms:

(wherein, component (B) and total combined amount (C) are 0～150 weight part)

That (D) selects from metal, metal oxide, metal nitride, metallic carbide except that said components (C) is at least a: 0～1,600 weight parts,

(wherein, component (B), (C) and total combined amount (D) are 10～1,600 weight parts)

(E) solidifying agent: the solidified significant quantity,

Wherein, described second silastic-layer is the layer that the rubber composition forming and hardening that will contain following component forms:

(F) organopolysiloxane: 100 weight parts,

(G) silicone powder: 1～200 weight part

(wherein, component (H) and total combined amount (I) are 0～50 weight part)

(J) solidifying agent: solidified significant quantity.

2. thermal pressed silicon rubber sheets as claimed in claim 1, wherein, the silicone powder of described component (G) is selected from: the silicone rubber powder that straight catenate organopolysiloxane is cross-linked to form, the silicone powders with the three-dimensional netted crosslinked structure that forms of siloxane bond, at the polysiloxane composite powder of the surface coated silicone resin of spherical silicone rubber powder.

3. the thermal pressed silicon rubber sheets described in claim 1 or 2, wherein, the median size of the silicone powder of said components (G) is 1～50 μ m.

4. as each described thermal pressed silicon rubber sheets in the claim 1～3, wherein, the content that comprises the mineral filler of component (H) in the composition that forms above-mentioned second silastic-layer, (I) is 20 weight % of total composition or below the 20 weight %.

5. as each described thermal pressed silicon rubber sheets in the claim 1～4, wherein, forming and removing the outer silicone resin content of component (G) silicone powder in the composition of above-mentioned second silastic-layer is 20 weight % of total composition or below the 20 weight %.

6. as each described thermal pressed silicon rubber sheets in the claim 1～5, wherein, above-mentioned second silastic-layer carries out JIS K 6253 Shore durometer hardness tests after solidifying, and the A type hardness tester is more than 20 or 20.

7. as each described thermal pressed silicon rubber sheets in the claim 1～6, wherein, heat pressure adhesive is with the surfaceness on two surfaces of silicon rubber: center line average roughness Ra is 0.4 μ m≤Ra≤5.0 μ m, and maximum height Rmax is Rmax≤50 μ m.

8. as each described thermal pressed silicon rubber sheets in the claim 1～7, wherein, the thickness of above-mentioned second silastic-layer is 1～50 μ m, lamination second silastic-layer on face of first silastic-layer or two faces and the total thickness of the silicone rubber plate that forms is 0.1～10mm.

9. as each described thermal pressed silicon rubber sheets in the claim 1～7, wherein, be 0.2 weight % or below the 0.2 weight % at 3 hours volatile matter of heating under 150 ℃ of temperature.

10. method of making thermal pressed silicon rubber sheets, it is characterized in that, first rubber composition is shaped to sheet, before or after making this forming composition curing, on face of above-mentioned flap or two faces, second rubber composition is shaped to sheet, described second rubber composition is different with the first rubber composition component and be dispersed in the composition by silicone rubber powder and form, second rubber composition is heating and curing, perhaps when first rubber composition is uncured, heat first and second rubber composition simultaneously and make its curing, on the cured article laminar surface of the second rubber composition flap, form concaveconvex shape, the average roughness Ra of its medullary ray is 0.4 μ m≤Ra≤5.0 μ m, and maximum height Rmax is Rmax≤50 μ m.

11. manufacture method as claimed in claim 10, first rubber composition that wherein will contain following component is shaped to sheet:

(wherein, component (B) and total combined amount (C) are 0～150 weight part)

(E) solidifying agent: the solidified significant quantity,

Before or after this forming composition was solidified, on face of above-mentioned flap or two faces, second rubber composition that will contain following component was shaped to sheet:

(F) organopolysiloxane: 100 weight parts,

(G) silicone powder: 1～200 weight part

(wherein, component (H) and total combined amount (I) are 0～50 weight part)

(J) solidifying agent: the solidified significant quantity,

Second rubber composition that is heating and curing perhaps when first rubber composition is uncured, heats first and second rubber composition simultaneously and makes its curing, forms the multilayer silastic-layer.