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    • 专利摘要:
    PURPOSE: To provide a thermally conductive composite sheet being excellent in thermal conductivity and also in reworking properties and suitable particularly for a radiating structure that is used as an interposition between a heat generating electronic component and a radiating component such as a heat sink or a circuit board for radiation/cooling of the heating electronic component and the like. CONSTITUTION: This thermally conductive composite sheet comprises (a) a heat-softening thermally conductive sheet layer containing a silicone resin and a thermally conductive filler and (b) a thermally conductive silicone rubber sheet layer containing the thermally conductive filler.
    公开号:KR20040023520A
    申请号:KR1020030060673
    申请日:2003-09-01
    公开日:2004-03-18
    发明作者:요시따까 아오끼；즈또무 요네야마；구니히꼬 미따
    申请人:신에쓰 가가꾸 고교 가부시끼가이샤；
    IPC主号:
    专利说明:

    Thermally Conductive Composite Sheets and Manufacturing Method Thereof {Thermal-Conductive Composite Sheets and Process for Preparing the Same}
    [1] The present invention relates in particular to a thermally conductive composite sheet suitable for a heat dissipation structure that is interposed between a heat generating electronic component and a heat dissipating component such as a heat sink and a circuit board for heat dissipation of a heat generating electronic component, and a manufacturing method thereof. .
    [2] In recent years, the circuit design of electronic devices such as televisions, radios, computers, medical devices, office equipment, communication devices, and the like has increased in complexity as the device continues to be miniaturized. For example, integrated circuits for electronic devices and the like that contain a substantial amount of hundreds of thousands of transistors have been manufactured. While the complexity of the design has increased, the miniaturization of electronic components has been made to enable the assembly of many more components in a smaller area and the dimensions of the devices are becoming smaller and smaller.
    [3] These electronic components, especially IC packages such as CPUs mounted on printed wiring boards, are degraded as the temperature rises due to heat generation during use, causing problems such as failures and malfunctions. BACKGROUND ART Conventionally, grease, silicone rubber sheet, and the like having good thermal conductivity are interposed between an IC package and a heat sink. However, with the miniaturization and high performance of electronic components, the amount of heat generated increases, and therefore, development of a member having better heat dissipation performance is required.
    [4] Conventional thermal conductive grease has the advantage of being able to cope with and closely adhere to these deposited surfaces without being influenced by the uneven shape of the surface of electronic components such as CPU, heat sink, etc., and low interfacial thermal resistance. Oil is bleed / separated due to contamination of parts or long-term use, or viscosity rises over time, so it adheres too tightly to the surface to be deposited. At the time of removal, electronic components such as the CPU also fell together.
    [5] In addition, the thermally conductive silicone rubber sheet has the advantage that it can be easily mounted or has good reworkability, but the content of the thermally conductive filler is limited in terms of processability of the manufacturing process, and the adhesion and correspondence with the surface to be adhered are insufficient. There was a drawback that the heat dissipation performance was not sufficiently exhibited because the interface thermal resistance at the time of mounting was large. In order to solve the said drawback, JP-A-2000-509209 and JP-A-2000-327917 have described the heat radiation sheet which has a thermosoftening layer. In such a case, however, the increase in the interface thermal resistance can be prevented by allowing the resin component after thermal softening to cope with and adhere to the adhered surface to prevent voids. However, the content of the thermally conductive filler is limited as in the prior art, and the resin itself is the interface. It is a cause of thermal resistance or, in some cases, when used at a high temperature for a long time as in the case of the thermally conductive grease, it is too tightly adhered to an electronic component or the like, resulting in poor reworkability.
    [6] Disclosure of Invention An object of the present invention is to provide a thermally conductive composite sheet and a method for producing the same, which are used for heat dissipation of a heat generating electronic component, and which has not only good thermal conductivity but also excellent reworkability.
    [7] In order to achieve the above object,
    [8] A thermally conductive composite sheet comprising (a) a thermosoftening thermal conductive sheet layer containing a silicone resin and a thermally conductive filler, and (b) a thermally conductive silicone rubber sheet layer containing a thermally conductive filler, and a method for producing the same. .
    [9] <Embodiment of the invention>
    [10] Hereinafter, the present invention will be described in detail.
    [11] [(a) Thermosoftening Thermally Conductive Sheet Layer]
    [12] In the thermally conductive composite sheet of the present invention, the layer (a), the thermosoftening thermal conductive sheet layer, is basically formed of a composition containing a silicone resin that becomes a matrix and a thermally conductive filler dispersed in the matrix. In addition, the layer (a) is a layer on the side where the composite sheet according to the present invention comes into contact with a heat generating electronic component or the like, and at least the contact surface of the layer (a) has a low viscosity and hot rolling due to heat generation during operation of the heat generating electronic component or the like. (A) the surface of the layer is fluidized to cope with and adhere to the surface to be deposited to prevent voids and to increase the interfacial thermal resistance, and a thermally conductive filler is formulated at a high ratio to provide good thermal conductivity. The layer also has the function of ensuring the effect and improving the heat dissipation characteristics.
    [13] <Silicone resin component>
    [14] As said silicone resin used by this invention, the composition containing the said silicone resin and thermally conductive filler which comprises (a) layer is substantially solid at normal temperature, and is 40 degreeC or more normally and reaches the highest by heat generation of a heat generating electronic component. It may be that the contact surface of the at least (a) layer with the exothermic electronic component is fluidized by low viscosity, hot softening or melting in a temperature range of 40 to 100 ° C., in particular 40 to 90 ° C. or less. The matrix-type silicone resin becomes an important factor in the thermosoftening property of this (a) layer.
    [15] Here, the low-viscosity, hot-softening or melting temperature is used as the composition, and does not exclude the case where the silicone resin itself has a melting point of less than 40 ° C. However, in the said temperature range, a considerable part including other than the said contact surface part of (a) layer should not flow out by melting of the silicone resin which is matrix form.
    [16] In addition, the silicone resin needs to be of a high molecular weight sufficient to be able to maintain a highly charged and dispersed thermally conductive filler in the layer (a). Moreover, it is necessary for the thermally conductive silicone rubber layer of (a) layer and said (b) layer to be chosen adhesively, and both layers do not cause interface peeling.
    [17] The silicone resin constituting the matrix phase of layer (a) may satisfy the above conditions, and is not particularly limited, but the composition may be substantially solid (non-flowable) at room temperature, in particular by combination with a thermally conductive filler. Polymers containing RSiO 2/2 units (hereinafter referred to as T units) and / or SiO 2 units (hereinafter referred to as Q units), as needed, and these and R 2 SiO units (hereinafter referred to as D units) The copolymer with etc. are illustrated, and the silicone oil and silicone raw rubber containing D unit can also be added. Of these, a combination of a silicone resin containing a T unit and a D unit, a silicone resin containing a T unit, and a silicone oil or silicone raw rubber having a viscosity at 100C of 100 Pa · s or more is preferable. The silicone resin may be terminally sealed in R 3 SiO 1/2 units (M units).
    [18] Here, R is a C1-10, preferably unsubstituted or substituted C1-6 monovalent hydrocarbon group, specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, aryl groups, benzyl groups, such as alkyl groups such as tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group and decyl group, phenyl group, tolyl group, xylyl group and naphthyl group Aralkyl groups such as phenylethyl group and phenylpropyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and octenyl group and hydrogen atoms of these groups A part or all substituted by halogen atoms, such as fluorine, bromine, chlorine, and a cyano group, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group, etc. are mentioned. Among these, especially methyl, phenyl, Carbonyl group is preferred.
    [19] In addition, the silicone resin will be described in detail. The silicone resin includes T units and / or Q units, and M units and T units, or M units and Q units are designed. However, in order to be excellent in the toughness at the time of solidification (to improve brittleness and to prevent breakage during handling), it is effective to introduce a T unit, and the use of the D unit is preferable. Here, as a substituent (R) of a T unit, a methyl group and a phenyl group are preferable, and as a substituent (R) of a D unit, a methyl group, a phenyl group, and a vinyl group are preferable. In addition, the composition ratio of the T unit and the D unit is preferably 10:90 to 90:10, particularly 20:80 to 80:20.
    [20] In addition, even in the case of resins synthesized from M units and T units, or M units and Q units, which are commonly used, high viscosity oils containing T units and mainly including D units (the terminal is M units) (more than 100 Pa · s) ) Or by mixing the raw rubber compound, it is possible to prevent the brittleness and pumping out (the formation of bubbles or separation of the base siloxane by separation of the filler and the base siloxane) in the event of a thermal shock. Therefore, when using the silicone resin which contains T unit and does not contain D unit, it is preferable to add high viscosity oil, a raw rubber-like compound, etc. which have D unit as a main component to this silicone resin.
    [21] Therefore, when the silicone resin having a softening point contains a T unit and does not contain a D unit, for this reason, the addition of a high viscosity oil or raw rubber containing the D unit as a main component results in a material having excellent handleability. In this case, the addition amount of the high-viscosity oil or the raw rubber-like compound mainly containing D units is 1 to 100 parts by weight, in particular 2 to 10 parts by weight, based on 100 parts by weight of the silicone resin having a softening point or melting point higher than room temperature. desirable. If it is less than 1 part by weight, the pumping-out phenomenon is likely to occur, and if it is more than 100 parts by weight, the thermal resistance may increase and the heat dissipation performance may be reduced.
    [22] As mentioned above, since silicone resin produces | generates a critical viscosity fall, it is preferable to use the thing of comparatively low molecular weight. As a molecular weight of this low melting silicone resin, it is preferable that it is 500-10,000, especially 1,000-6,000.
    [23] In addition, the silicone resin preferably imparts flexibility and adhesion (required from the necessity of temporarily stopping the heat dissipation sheet to the electronic component or the heat sink) to the thermally conductive material used in the present invention, and a polymer having a single viscosity may be used, but the viscosity is high. In the case where two or more different polymers are used in combination, a sheet having excellent balance between flexibility and adhesiveness is obtained, which is advantageous, and therefore two or more types having different viscosities can be used.
    [24] Specifically, the silicone resin which has a bifunctional structural unit (D body) and a trifunctional structural unit (T body) as a specific composition is mentioned as follows, for example.
    [25] D 1 m T p D 2 n
    [26] Wherein D 1 is a dimethylsiloxane unit (ie, (CH 3 ) 2 SiO), T is a phenylsiloxane unit (ie (C 6 H 5 ) SiO 3/2 ), and D 2 is a methylvinylsiloxane unit (ie (CH 3 ) (CH 2 = CH) SiO), and the range of (m + n) / p (molar ratio) = 0.25 to 4.0 with respect to the composition ratio, and also (m + n) / m (molar ratio) = 1.0 to 4.0 Mine
    [27] Moreover, the silicone resin which has a monofunctional structural unit (M body), a bifunctional structural unit (D body), and a trifunctional structural unit (T body) in a specific composition is mentioned, for example.
    [28] M 1 D 1 m T p D 2 n
    [29] In the formula, M represents a trimethylsiloxane unit (that is, (CH 3 ) 3 SiO 1/2 ), D 1 , T and D 2 are as described above and (m + n) / p (molar ratio) with respect to the composition ratio = 0.25 to 4.0, (m + n) / m (molar ratio) = 1.0 to 4.0, and 1 / (m + n) (molar ratio) = 0.001 to 0.1.
    [30] Moreover, the silicone resin which has a monofunctional structural unit (M body), a bifunctional structural unit (D body), and a tetrafunctional structural unit (Q body) in a specific composition is mentioned, for example.
    [31] M 1 D 1 m Q q D 2 n
    [32] Wherein, Q denotes a SiO 4/2, M, D 1 and D 2 are as defined above, (m + n) / q (molar ratio) = 0.25 to 4.0, according to the composition ratio (m + n) / m (Molar ratio) = 1.0-4.0, and 1 / (m + n) (molar ratio) = 0.001-0.1.
    [33] These can be used individually by 1 type or in combination of 2 or more types.
    [34] <Thermally conductive filler>
    [35] As said thermally conductive filler, the well-known material generally used as a thermally conductive filler for this type of use can be used without a restriction | limiting, For example, Metals, such as copper, silver, aluminum; Metal oxides such as alumina, silica, magnesium oxide and zinc oxide; Metal nitrides such as aluminum nitride, silicon nitride, and boron nitride; Artificial diamond can be used.
    [36] The thermally conductive filler preferably has an average particle diameter in the range of 0.1 to 100 µm, and more preferably 0.1 to 25 µm in that both characteristics of fluidity and thermal conductivity are compatible. When the average particle diameter is too small, the viscosity at the time of manufacturing the said composition which comprises (a) layer becomes high and workability is inferior. If the average particle diameter is too large, the working viscosity decreases, but in the case of actually used as a heat dissipation member, the gap between the electronic component and the heat dissipation component is not squeezed to below the particle diameter (for example, 100 μm or less), and the thermal resistance is high, resulting in sufficient heat dissipation performance. It becomes difficult to express.
    [37] The shape of the particles of the thermally conductive filler is not particularly limited, but spherical shape is preferred. In addition, a thermally conductive filler may be used individually by 1 type or in combination of 2 or more types. In order to improve thermal conductivity, the formulation close to the fine packing using two or more kinds of particles having different average particle diameters is preferable. The amount of this thermally conductive filler is 70 to 97 weight% normally with respect to the whole said composition which comprises (a) layer, Preferably it is 85 to 95 weight%. If the amount is too small, the thermal conductivity of the thermally conductive composite sheet of the present invention is insufficient, and if too large, the thermal softening property is insufficient.
    [38] <Other additives>
    [39] In the composition constituting the layer (a), additives or fillers used for synthetic rubber, for example, may be used as necessary.
    [40] Specifically, as a shape retainer, EPT polymer etc .; Olefin pressure-sensitive adhesives and the like as the adhesion improving agent; Silicone oil, fluorine-modified silicone surfactant, etc. as a releasing agent; Carbon black, titanium dioxide, red iron oxide, and the like as colorants; As a flame retardant imparting agent, metal oxides, such as a platinum catalyst, iron oxide, titanium oxide, cerium oxide, or a metal hydroxide; Process oils, process oils, reactive silanes or siloxanes, reactive titanate catalysts, reactive aluminum catalysts, and the like; To improve workability and processability, solvents such as toluene, xylene, hexane, heptane, acetone and methyl ethyl ketone can be optionally added and used.
    [41] [(b) Thermally Conductive Silicone Rubber Sheet Layer]
    [42] The thermally conductive silicone rubber sheet layer, which is the (b) layer of the thermally conductive composite sheet of the present invention, is a punching material for aiding the shape stability of the (a) thermosoftening thermally conductive sheet layer, and has a relatively high hardness and adhesion to the (a) layer. Since this is excellent, reworkability is provided to the composite sheet of this invention.
    [43] The type of heat conductive silicone rubber sheet layer is not particularly limited as long as it contains a heat conductive filler. However, it is preferable that the hardness of this heat conductive silicone rubber sheet layer is 5-100 in Asuka C hardness, More preferably, it is 10-50 in Asuka C hardness. Here, Asuka C hardness is hardness measured using the spring type hardness tester Asuka C type according to SRIS 0101 (Nisbon Rubber Association standard) and JIS S 6050. When the said Asuka C hardness is too small, it is too soft, it is difficult to maintain the shape of a heat conductive composite sheet, its reinforcement is inadequate, and productivity is also very bad. On the contrary, when too big | large, adhesiveness with the electronic component of the (a) layer integrated with too hard will fall too much, or a correspondence will worsen.
    [44] Next, the curable silicone rubber composition which is a raw material of the thermally conductive silicone rubber sheet layer of the layer (b) will be described.
    [45] <Addition Reaction Curing Type Silicone Rubber Composition>
    [46] The addition-reaction-curable silicone rubber composition is basically an organopolysiloxane having two or more alkenyl groups in one molecule (A) and a polyorganohydrogen having two or more hydrogen atoms bonded to silicon atoms in one molecule (B). Siloxane, and (C) a platinum-based catalyst.
    [47] If the organopolysiloxane of the component (A) is liquid, its molecular structure is not limited, and examples thereof include linear, branched, and straight chains having some branches, preferably straight and partially branched. It is a strand. This organopolysiloxane is also a homopolymer having these molecular structures, a copolymer comprising these molecular structures, or a mixture of these polymers.
    [48] Examples of the alkenyl group include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, and the like, but a vinyl group is preferable in view of ease of synthesis and cost. The alkenyl group may be at the molecular chain terminal and / or in the side chain, and it is preferable that at least one alkenyl group is bonded to the silicon atom at the molecular chain terminal, but it is more preferable to exist only at both ends of the molecular chain, especially in view of flexibility. Do.
    [49] Examples of groups other than the alkenyl group bonded to the silicon atom include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and octadecyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; Aralkyl groups, such as a benzyl group, a phenethyl group, and 2-phenylpropyl group; Halogenated alkyl groups such as chloromethyl group, 3,3,3-trifluoropropyl group, and 3-chloropropyl group, and the like, and the like. Among these, in view of ease of synthesis and cost, at least 90 mol% of the total groups occupy a methyl group. It is preferable.
    [50] It is preferable that it is the range of 10-100,000 mPa * s, and, as for the viscosity in 25 degreeC of this (A) component, it is more preferable that it is the range which is 100-50,000 mPa * s. When the said viscosity is too low, the shape retention property of (b) layer will worsen, and when too high, the progress of the composition obtained will worsen.
    [51] As a specific example of (A) component, For example, molecular chain both terminal trimethylsiloxy group blocking dimethylsiloxane and methylvinylsiloxane copolymer, molecular chain both terminal trimethylsiloxy group blocking methylvinyl polysiloxane, molecular chain both terminal trimethylsiloxy group blocking dimethylsiloxane Methyl vinyl siloxane, methylphenyl siloxane copolymer, molecular chain both terminal dimethylvinyl siloxy group blocking dimethyl polysiloxane, molecular chain both terminal dimethylvinyl siloxy group blocking Methyl vinyl polysiloxane, molecular chain both terminal dimethylvinyl siloxane group blocking dimethylsiloxane, methyl vinyl siloxane Copolymerization, molecular chain both terminal dimethylvinylsiloxy group blocking dimethylsiloxane, methylvinylsiloxane, methylphenylsiloxane copolymer, molecular chain both terminal trivinylsiloxy group blocking dimethylpolysiloxane, etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.
    [52] The polyorganohydrogensiloxane of the component (B) acts as a crosslinking agent, and if it is a liquid, its molecular structure is not limited, and examples thereof include linear, branched, and straight chains having some branches. Is linear, and is linear with some branches. This organopolysiloxane is also a homopolymer having these molecular structures, a copolymer comprising these molecular structures or a mixture of these polymers. As for the compounding quantity of (B) component, the quantity which becomes 0.6-5.0 pieces of hydrogen atoms (SiH) couple | bonded with the silicon atom with respect to one alkenyl group contained in (A) component becomes like this, More preferably, it becomes 0.8-4.0 pieces Amount. If the blending amount is too small, sufficient network structure cannot be obtained, and the required hardness is not obtained after curing, and if too large, foaming by dehydrogenation becomes a problem or insufficient flexibility of the thermally conductive silicone rubber sheet layer obtained.
    [53] Specific examples of the component (B) include, for example, molecular chain both terminal trimethylsiloxy group blocking methylhydrogenpolysiloxane, molecular chain both terminal trimethylsiloxy group blocking dimethylsiloxane and methylhydrogensiloxane copolymer, molecular chain both terminal trimethylsiloxy group blocking dimethyl Siloxane, methylhydrogensiloxane, methylphenylsiloxane copolymer, molecular chain both terminal dimethylhydrogensiloxy group blocking dimethylpolysiloxane, molecular chain both terminal dimethylhydrogensiloxy group blocking dimethylpolysiloxane, methylhydrogensiloxane copolymer, molecular chain both terminal dimethyl Hydrogensiloxy group blocking dimethylsiloxane methylmethylsiloxane copolymer, Molecular chain both terminal dimethylhydrogensiloxy group blocking methylphenyl polysiloxane can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
    [54] The platinum-based catalyst of component (C) is a catalyst for promoting the curing of the composition, and for example, chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum, a carbonyl complex of platinum, and the like. Can be mentioned. In the present composition, the content of the platinum-based catalyst is not particularly limited, and may be an effective amount as a catalyst, but is usually an amount such that the platinum metal in the present component is 0.01 to 1,000 ppm by weight relative to component (A), preferably 0.1 to 500 ppm. When there is too little content of this component, the silicone rubber composition obtained may not fully harden on the other hand, On the other hand, even if it uses in large quantities, the hardening rate of the silicone rubber composition obtained may not improve and it may become economically disadvantageous.
    [55] <Condensation Curing Type Silicone Rubber Composition>
    [56] Condensation-curable silicone rubber compositions basically contain (1) organopolysiloxanes having two or more silanol groups or silicon atom-bonded hydrolyzable groups in one molecule, and (2) hardeners containing three or more silicon atom-bonded hydrolysable groups in one molecule. Silane or a partial hydrolysis condensate thereof, and (3) optionally a condensation reaction catalyst.
    [57] The organopolysiloxane of the component (1) preferably has a viscosity at 25 ° C in the range of 10 to 100,000 mPa · s. Moreover, as said hydrolysable group which this organopolysiloxane has, it is acyloxy groups, such as an acetoxy group, an octanoyloxy group, a benzoyloxy group; Ketoxim group, such as a dimethyl ketoxim group, a methyl ethyl ketoxim group, and a diethyl ketoxim group; Alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group; Alkoxyalkoxy groups such as methoxyethoxy group, ethoxyethoxy group, and methoxypropoxy group; Alkenyloxy groups such as vinyloxy group, isopropenyloxy group and 1-ethyl-2-methylvinyloxy group; Amino groups such as dimethylamino group, diethylamino group, butylamino group and cyclohexylamino group; Aminoxy group, such as a dimethyl amino group group and a diethyl amino group group; Amide groups such as N-methylacetamide group, N-ethylacetamide group, and N-methylbenzamide group.
    [58] Specific examples of the component (1) include, for example, molecular chain both terminal silanol group-blocked polydimethylsiloxane, molecular chain both terminal silanol group-blocked dimethylsiloxane and methylphenylsiloxane copolymer, molecular chain both terminal trimethoxysiloxy group-blocked polydimethylsiloxane, Molecular chain both terminal trimethoxysiloxy group blocking dimethylsiloxane and methylphenylsiloxane copolymer, molecular chain both terminal methyldimethoxysiloxy group blocking polydimethylsiloxane, molecular chain both terminal triethoxysiloxy group blocking polydimethylsiloxane, molecular chain both terminal 2-trimethoxy siloxyethyl group blocking polydimethylsiloxane etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.
    [59] As a specific example of the hardening | curing agent of (2) component, for example, ethyl silicate, propyl silicate, methyl trimethoxysilane, methyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, and methyl tris (methoxyethoxy) Silane, vinyltris (methoxyethoxy) silane, methyltripropenoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, methyltri (methylethylketoxime) silane, vinyltri (methylethylketoxime) silane , Phenyl tri (methyl ethyl ketoxime) silane, phenyl tri (methyl ethyl ketoxime) silane, propyl tree (methyl ethyl ketoxime) silane, tetra (methyl ethyl ketoxime) silane, 3,3,3-trifluoropropyl Tri (methylethylketoxime) silane, 3-chloropropyltri (methylethylketoxime) silane, methyltri (dimethylketoxime) silane, methyltri (diethylketoxime) silane, methyltri (dimethylethylketoxime) silane , Tri (cyclohexaoxime) silane and the like and partial hydrolyzates thereof There may be mentioned condensation. These can be used individually by 1 type or in combination of 2 or more types.
    [60] It is preferable that it is 0.01-20 weight part with respect to 100 weight part of components (1) normally, and, as for the compounding quantity of (2) component, it is especially preferable that it is 0.1-10 weight part. If the content is less than the lower limit of the above range, the storage stability of the composition to be obtained tends to be lowered or the adhesiveness is lowered. On the other hand, if the amount exceeds the upper limit of the above range, curing of the resulting composition tends to be significantly slowed. .
    [61] The catalyst for condensation reaction of the component (3) is an optional component, and for example, organic titanic acid esters such as tetrabutyl titanate and tetraisopropyl titanate; Organic titanium chelate compounds such as titanium diisopropoxybis (ethylacetoacetate) and diisopropoxybis (ethylacetoacetate); Organoaluminum compounds such as aluminum tris (acetylacetonate) and aluminum tris (etheracetoacetate); Organic zirconium compounds such as zirconium tetra (acetylacetonate) and zirconium tetrabutylate; Organic tin compounds such as dibutyltin dioctoate, dibutyltin dilaurate and dibutyltin di (2-ethylhexanoate); Metal salts of organic carboxylic acids such as naphthenic acid tin, tin oleate, tin butyrate, cobalt naphthenate and zinc stearate; Amine compounds and salts thereof, such as hexylamine and dodecyl phosphate; Quaternary ammonium salts such as benzyltriethylammonium acetate; Lower fatty acid salts of alkali metals such as potassium acetate and lithium nitrate; Dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; Guanidyl group containing organosilicon compound etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.
    [62] In the case of compounding the component (3), the compounding amount is not particularly limited and may be an effective amount as a catalyst, but is preferably 0.01 to 20 parts by weight, and particularly preferably 0.1 to 10 parts by weight based on 100 parts by weight of the component (1). . When using this catalyst, if the content of this catalyst is an amount less than the lower limit of the said range, the composition obtained may not be hardened enough depending on the kind of crosslinking agent, and if it exceeds the upper limit of the said range, the storage stability of the composition obtained This may fall.
    [63] <Radical reaction curable silicone rubber composition>
    [64] The radical reaction curable silicone rubber composition basically contains an organopolysiloxane and an organic peroxide, and the organopolysiloxane is not particularly limited but preferably has two or more alkenyl groups in one molecule. As said alkenyl group, Especially preferably, it is a vinyl group. As a group couple | bonded with another silicon atom, the said alkyl group and an aryl group are preferable, Especially preferably, they are a methyl group and a phenyl group.
    [65] As a specific example of such organopolysiloxane, for example, molecular chain both terminal dimethylvinylsiloxy group blocking polydimethylsiloxane, molecular chain both terminal methylphenylvinylsiloxy group blocking polydimethylsiloxane, molecular chain both terminal dimethylvinylsiloxy group blocking dimethylsiloxane and methylphenylsiloxane Copolymer, molecular chain both terminal dimethylvinylsiloxy group blocking dimethylsiloxane, methylvinylsiloxane copolymer, molecular chain both terminal trimethylsiloxy group blocking dimethylsiloxane, methylvinylsiloxane copolymer, molecular chain both terminal dimethylvinylsiloxy group blocking polymethyl ( 3,3,3-trifluoropropyl) siloxane, molecular chain both terminal silanol group blocking dimethylsiloxane, methylvinylsiloxane copolymer, molecular chain both terminal silanol group blocking dimethylsiloxane, methylvinylsiloxane, methylphenylsiloxane copolymer, etc. are mentioned. Can be. These can also be used individually by 1 type or in combination of 2 or more types.
    [66] Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-butyl peroxide and t-butylperbenzoate. Etc. can be mentioned. These can be used individually by 1 type or in combination of 2 or more types. It is preferable that the addition amount of this organic peroxide is the amount within the range of 0.1-5 weight part with respect to 100 weight part of said organopolysiloxanes.
    [67] <Thermally conductive filler>
    [68] As the thermally conductive filler added and blended with respect to the respective curable silicone rubber compositions, the same ones as those described for the composition for layer (a) can be basically used, but from the viewpoint of affinity with the layer (a), the above (a) It is preferable to make it the same as what was used for the layer composition. The amount of this thermally conductive filler is 60 to 95 weight% normally with respect to the whole curable silicone rubber composition of the said (b) layer, Preferably it is 70 to 90 weight%. If the amount is too small, the thermal conductivity of the thermally conductive composite sheet decreases, resulting in insufficient thermal conductivity. If the amount is too large, the flexibility of the thermally conductive composite sheet decreases, and the thermal conductivity at the time of mounting becomes large, resulting in insufficient thermal conductivity.
    [69] <Other subsidiary materials and additives>
    [70] In order to further improve the shape stability of the layer (b), a glass cross, graphite sheet, aluminum foil, or the like is integrally formed on the outer surface of the layer (b) when the composite sheet is used according to the purpose by means of thermocompression bonding or bonding. Can be laid. Moreover, the said glass cross etc. can also be arrange | positioned integrally in the intermediate part of (b) layer.
    [71] Moreover, the curable silicone rubber composition which forms (b) layer can be added and mix | blended as well as a well-known additive or filler normally used for curable silicone rubber composition as arbitrary components similarly to the case of (a) layer composition as needed. Specific examples include control agents selected from acetylene compounds such as 1-ethynyl-1-cyclohexanol, various nitrogen compounds, organophosphorus compounds, oxime compounds, organic chloro compounds and the like for the purpose of inhibiting catalytic activity; Silicone oil, fluorine-modified silicone surfactant, etc. as a releasing agent; Carbon black, titanium dioxide, red iron oxide, and the like as colorants; Examples of the flame retardant imparting agent include metal oxides and metal hydroxides such as platinum catalyst, iron oxide, titanium oxide, cerium oxide, and the like; Reactive silane, siloxane, etc. can also be added as a workability improving agent.
    [72] [Production of Thermally Conductive Composite Sheet]
    [73] The method of manufacturing the thermally conductive composite sheet containing the (a) heat softenable thermally conductive sheet layer and (b) heat conductive silicone rubber sheet layer of the present invention will be specifically described below.
    [74] <Heat conductive silicone rubber sheet>
    [75] When using the heat conductive silicone rubber sheet shape | molded previously, the following method is mentioned, for example.
    [76] For example, an uncured addition reaction curable liquid silicone rubber composition containing a thermally conductive filler is introduced into a mold, and after the mold is fastened, it is 49.0 kPa (0.5 kgf / cm 2 ) to 4903.5 kPa (50 kgf / A thermally conductive silicone rubber sheet obtained by applying a pressure of cm 2 ), heated to 100 to 180 ° C., left to stand for 5 to 30 minutes, and molding and curing the liquid silicone rubber composition is used.
    [77] <Thermal softening thermally conductive sheet with a polymer film which carried out the release process>
    [78] When molding a thermosoftening thermally conductive sheet, it is useful to use a release-treated polymer film as an auxiliary material for shape maintenance. Examples of the polymer film subjected to the release treatment include a polyethylene terephthalate film coated with a fluorine release agent, a polypropylene film coated with a fluorine release agent, a polyethylene terephthalate film coated with a silicone release agent, a polypropylene film coated with a silicone release agent, and the like. have. After the formation of the thermally conductive composite sheet, the polymer film is peeled off and removed during use and mounting of the sheet.
    [79] When using the thermosoftening thermal conductive sheet with a polymer film which carried out the mold release process previously shape | molded, the following method is mentioned, for example.
    [80] Tape-type release-treated polymer film was supplied to a coating apparatus, and a liquid thermally conductive filler-containing silicone resin composition which was diluted by mixing a solvent such as toluene and improving processability was subjected to a knife coater at a coating rate condition of 0.5 to 3.0 m / min. After apply | coating to the polymer film which carried out the mold release process by constant thickness, the mold release-treated thermosoftenable heat conductive sheet with a polymer film obtained by volatilizing and removing toluene etc. through the 50 degreeC-20 degreeC heating furnace is used.
    [81] <Mold molding method-1>
    [82] A thermally conductive silicone rubber sheet is placed on the mold surface, a thermally conductive filler-containing silicone resin composition is placed thereon, fastened using a separate mold with a polymer film subjected to a release treatment, and then pressure and heat are applied by a heat press. It is a method of shape | molding a heat conductive composite sheet, adding and heat-softening the said composition.
    [83] As the molding conditions, the matrix component of the composition may be fluidized, and may be a moldable condition, and is not particularly limited. It is preferable that temperature conditions are 100 degreeC-200 degreeC, More preferably, they are 120 degreeC-180 degreeC. It is preferable to pressurize the pressure condition to 49.0-1961.4 kPa (0.5-20 kgf / cm <2> ) of surface pressures normally, in order to avoid foaming.
    [84] <Mold molding method-2>
    [85] A thermosoftening thermal conductive sheet with a polymer film subjected to release treatment on a mold surface was placed, and an uncured addition reaction curable liquid silicone rubber composition containing, for example, a thermally conductive filler was placed thereon, and the mold was fastened. By applying pressure and heat to form a thermally conductive composite sheet while curing the liquid silicone rubber composition.
    [86] The molding conditions may be the usual conditions employed when the curable silicone rubber composition is cured by press molding and molded, and is not particularly limited. It is preferable that temperature conditions are 50 degreeC-200 degreeC, More preferably, they are 60 degreeC-180 degreeC. It is preferable to pressurize pressure conditions to surface pressure of 490.4-4903.5 kPa (5-50 kgf / cm <2> ) normally in order to avoid bubble drying.
    [87] <Injection Molding Method-1>
    [88] A thermally conductive silicone rubber sheet is installed on the mold surface of the injection molding machine, and a separate mold to which a release-treated polymer film is attached is fastened. Next, after heat-softening a thermally conductive filler containing silicone resin composition in the heated barrel, it injects from a nozzle through the injection sprue of a metal mold | die, it fills in a mold, and pressurizes. A metal mold | die is opened after cooling, and the molded thermal conductive composite sheet is taken out.
    [89] As the molding conditions, the matrix components of the composition may be fluidized and molded, and are not particularly limited. It is preferable that barrel temperature conditions are 50 degreeC-150 degreeC, More preferably, they are 70 degreeC-130 degreeC. The pressure condition is preferably pressurized at a surface pressure of 49.04 kPa (0.5 kgf / cm 2 ) to 4903.5 kPa (50 kgf / cm 2 ) in order to avoid air bubbles.
    [90] <Injection Molding Method-2>
    [91] On the heated mold surface of an injection molding machine, the mold release is performed by installing the thermosoftening thermal conductive sheet with a polymer film which carried out the release process. Next, for example, an uncured addition reaction curable liquid silicone rubber composition containing a thermally conductive filler is introduced into the raw material supply pump, injected from the metered discharge pump through the injection port of the mold, and filled into the mold and cured by applying pressure. . After hardening, it is a method of taking out a molded thermally conductive composite sheet by opening a metal mold | die.
    [92] Molding conditions may be the usual conditions when curing and molding the curable silicone rubber composition by injection molding, and are not particularly limited. It is preferable that mold heating temperature conditions are 50 degreeC-200 degreeC, More preferably, they are 60 degreeC-180 degreeC. The pressure condition is preferably pressurized at a surface pressure of 49.04 kPa (0.5 kgf / cm 2 ) to 4903.5 kPa (50 kgf / cm 2 ) in order to avoid air bubbles.
    [93] <Coating Molding Method-1>
    [94] After supplying a tape-type thermally conductive silicone rubber sheet to the coating apparatus and applying a liquid thermally conductive filler-containing silicone resin composition, which was diluted with a solvent to improve processability, on a thermally conductive silicone rubber sheet by a knife coater or the like. A method of forming a thermally conductive composite sheet by volatilizing and removing a solvent through a heating furnace.
    [95] Molding conditions may be conditions under which the used solvent can fully volatilize and remove, and is not specifically limited. It is preferable that coating speed conditions are 0.5 m / min-10 m / min, More preferably, they are 1 m / min-5 m / min. Heating furnace The heating conditions depend on the kind of solvent, but in order to avoid the generation of bubbles, the heating conditions are preferably 50 ° C to 200 ° C, more preferably 60 ° C to 180 ° C. Moreover, it is necessary to make the polymer film which carried out the mold release process adhere to the surface of (a) layer in order to maintain the low viscosity, heat softening, or meltability of (a) layer surface.
    [96] <Coating Molding Method-2>
    [97] A polymer film obtained by supplying a thermosoftening thermal conductive sheet with a polymer film subjected to mold release treatment to a coating apparatus, and releasing the uncured addition reaction curable liquid silicone rubber composition containing a thermally conductive filler, for example, by a knife coater or the like. It is a method of forming a thermally conductive composite sheet by applying a predetermined thickness on an adhesive softening thermally conductive sheet and curing it through a heating furnace.
    [98] Molding conditions may be conditions at the time of hardening | curing curable silicone rubber composition by coating molding and shaping | molding, and are not specifically limited. It is preferable that coating speed conditions are 0.5 m / min-10 m / min, More preferably, they are 1 m / min-5 m / min. Heating conditions The heating conditions are preferably 50 ° C to 200 ° C, more preferably 60 ° C to 180 ° C, in order to avoid generation of bubbles.
    [99] Thermocompression Molding Method
    [100] A tape type thermosoftening thermal conductive silicone rubber sheet and a tape type softening thermal conductive sheet with a polymer film subjected to mold release treatment are simultaneously supplied to a heating roll, followed by thermocompression molding with a heating roll to form a thermally conductive composite sheet.
    [101] Molding conditions are not particularly limited as long as the matrix component in the softenable thermally conductive sheet is thermosoftened and fluidized and can be molded. It is preferable that heat roll temperature conditions are 100 degreeC-200 degreeC, More preferably, it is 120 degreeC-180 degreeC. The pressure conditions are preferably pressurized to a surface pressure of 49.0 to 1961.4 kPa (0.5 to 20 kgf / cm 2 ) in order to avoid bubbles from entering.
    [102] Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, the number in Table 1 shows a weight part.
    [103] First, the composition component of the said composition for each (a), (b) layer used in order to form the thermally conductive composite sheet which concerns on this invention, and the manufacturing method of the composition are as follows.
    [104] <Composition component for thermosoftening thermal conductive sheet layer>
    [105] ㆍ Component (F) Matrix Component
    [106] F-1: polysiloxane represented by the following composition
    [107] D 1 25 T 55 D 2 20
    [108] Wherein D 1 is a dimethylsiloxane unit (ie, (CH 3 ) 2 SiO), T is a phenylsiloxane unit (ie (C 6 H 5 ) SiO 3/2 ), and D 2 is a methylvinylsiloxane unit (ie (CH 3 ) (CH 2 = CH) SiO).
    [109] ㆍ Component (G) Polyolefin (for comparison)
    [110] G-1: DYRAYEN 30 (brand name, manufactured by Mitsubishi Chemical Corporation)
    [111] G-2: diamond 208 (trade name, manufactured by Mitsubishi Chemical Corporation)
    [112] ㆍ Component (H) shape retainer (for comparison)
    [113] H-1: EPT-PX-055 (trade name, manufactured by Mitsui Chemicals, Inc.)
    [114] Component (I) Adhesion Enhancer (Comparative)
    [115] I-1: Lucant HC 300O X (trade name, manufactured by Mitsui Chemical Industries, Ltd.)
    [116] ㆍ Component (D) Thermal Conductive Filler
    [117] D-1: aluminum powder with an average particle diameter of 7.4 mu m
    [118] D-2: Alumina Powder with an Average Particle Size of 5.3 µm
    [119] D-3: Zinc oxide powder with an average particle diameter of 1.0 micrometer
    [120] ㆍ Component (E) Processability Enhancer
    [121] E-1: C 10 H 21 Si (OCH 3 ) 3
    [122] <Production of Composition for Thermosoftening Thermal Conductive Sheet Layer>
    [123] Using a 5L gate mixer (trade name: 5 liter planetary mixer, manufactured by Inoue Seisakusho Co., Ltd.), each component was mixed at 120 ° C for 1 hour using the composition of Table 1 below, and a target composition, K-1 (for comparison) ), K-2 and K-3.
    [124] <Composition component for thermally conductive silicone rubber sheet layer>
    [125] ㆍ Component (A) Polyorganosiloxane Containing Alkenyl Group
    [126] A-1: Polydimethylsiloxane whose both ends are sealed with the dimethylvinylsiloxy group, and the viscosity in 25 degreeC is 600 mPa * s.
    [127] Component (B) Polyorganohydrogensiloxane containing silicon atom-bonded hydrogen atoms
    [128] B-1: Polymethylhydrogensiloxane represented by the following general formula (1)
    [129]
    [130] ㆍ Component (C) Platinum Catalyst
    [131] C-1: Toluene solution of platinum-divinyltetramethyldisiloxane complex (concentration: 1% by weight as platinum metal)
    [132] ㆍ Component (D) Thermal Conductive Filler
    [133] D-1: aluminum powder with an average particle diameter of 7.4 mu m
    [134] D-2: Alumina Powder with an Average Particle Size of 5.3 µm
    [135] D-3: Zinc oxide powder with an average particle diameter of 1.0 micrometer
    [136] ㆍ Component (E) Processability Enhancer
    [137] E-1: C 10 H 21 Si (OCH 3 ) 3
    [138] Component (J) Catalytic Activity Control Agent
    [139] J-1: 50 wt% toluene solution of 1-ethynyl-1-cyclohexanol
    [140] <Production of Composition for Thermally Conductive Silicone Rubber Sheet Layer>
    [141] Using a 5L gate mixer (trade name: 5 liter planetary mixer, manufactured by Inoue Seisakusho Co., Ltd.), each component other than component (B) and component (C) and component (J) was added to the composition shown in Table 1 below. After mixing for 1 hour at room temperature, after cooling to room temperature, component (B) and component (C) and component (J) are added, and mixed at room temperature for 30 minutes to prepare the desired compositions L-1 and L-2. Got it.
    [142]
    [143] [Examples 1 to 8 and Comparative Examples 1 to 6]
    [144] The combination of the compositions for thermosoftening thermally conductive sheet layers (K-1, K-2, K-3) and compositions for thermally conductive silicone rubber sheet layers (L-1, L-2) described in Tables 2 and 3 below are used. And the thermally conductive composite sheet was manufactured according to the manufacturing method (1)-(7) of the thermally conductive composite sheet shown in following Table 2 and Table 3.
    [145] In addition, (1)-(7) mean as follows, and each manufacturing method is as above-mentioned; ① Mold molding method-1, ② Mold molding method-2, ③ Injection molding method-1, ④ Injection molding method-2, ⑤ Coating molding method-1, ⑥ Coating molding method-2, ⑦ Thermocompression molding method.
    [146] [Assessment Methods]
    [147] About each of the obtained thermally conductive composite sheets, the following characteristics were tested and measured. The results are shown in Tables 2 and 3.
    [148] Thickness, heat resistance
    [149] A sample for measuring thermal resistance was prepared by sandwiching each thermally conductive composite sheet (peeled and removed a release-treated polymer film) between two standard aluminum plates. Substantially the thickness of each thermally conductive composite sheet is obtained by using a micrometer (manufactured by Mitsutoyo Co., Ltd., model M820-25 VA) and measuring the thickness of this sample and subtracting the thickness of a standard aluminum sheet having a known thickness. It was.
    [150] In addition, about each said sample, the heat resistance (unit: ° C-cm <2> / w) of each thermal conductive composite sheet was measured using the heat resistance measuring device (The Horometrics company make, micro flash).
    [151] Reworkability
    [152] Each sample after the heat resistance measurement was sandwiched by a double clip (pressure: 196 kpa (2 kgf / cm 2 )), and the peelability between the aluminum plate and the thermally conductive composite sheet after 96 hours in an oven at 150 ° C. was measured. The evaluation was as follows.
    [153] Evaluation A: It peels easily.
    [154] Evaluation B: It is difficult to peel off.
    [155] Heat cycle test
    [156] Insert each thermally conductive composite sheet cut at 25 mm angle (peeled and removed mold release polymer film) between two transparent glass plates (thickness 1 mm, 50 mm x 75 mm), and then double-left Both sides were sandwiched (pressure: 196 kPa (2 kgf / cm 2 )) to obtain a sample. The sample was put into a cycle tester at -30 ° C to 100 ° C, and the number of cracks generated in the sample after 500 cycles (one cycle: 30 minutes) was visually observed and evaluated as follows.
    [157] Evaluation A: 0 to 5 cracks
    [158] Evaluation B: 6 or more cracks
    [159] Interlayer Peelability
    [160] About each thermally conductive composite sheet cut | disconnected by 25 mm <2> , when (b) holding a thermally conductive silicone rubber sheet layer with a finger | tip etc., and peeling and removing the polymer film which carried out the release process of (a) layer with a finger, (a ) The presence or absence of interlaminar peeling between the thermosoftening thermally conductive sheet layer and (b) the thermally conductive silicone rubber sheet layer was evaluated as follows.
    [161] Evaluation A: No delamination occurred at all (0%)
    [162] Evaluation B: Delamination occurs somewhat (1 to 10%)
    [163] Evaluation C: Delamination is likely to occur (11 to 100%)
    [164]
    [165]
    [166] (7) (7) means that the composite sheet was manufactured using composition (K-1) which used polyolefin as a matrix instead of silicone resin according to the said manufacturing method (7).
    [167] [evaluation]
    [168] In Comparative Example 1 and Comparative Example 2, the matrix of the thermosoftening thermal conductive sheet layer is a polyolefin, and in Comparative Example 1, which is a composite sheet with (b) the thermally conductive silicone rubber sheet layer, the thermal resistance is relatively high and the amount is It can be seen that the layer is likely to peel off at the interface. In addition, the thing of the comparative example 2 of the monolayer which is not a composite with layer (b) was not favorable in the result of reworkability and a heat cycle test.
    [169] In addition, the comparative example 3 and the comparative example 4 were sheets of (a) layer only, and also were not favorable in the result of reworkability and a thermal cycle test.
    [170] Next, Comparative Example 5 and Comparative Example 6 were sheets of (b) layer alone, and the results of reworkability and thermal cycle tests were good, but the thermal resistance was high. This shows that even if it contains a thermally conductive filler, adhesiveness with an aluminum plate is inferior to layer (b) alone, and interface heat resistance becomes high.
    [171] The thermally conductive composite sheet of the present invention has not only good thermal conductivity but also excellent reworkability, interposed between heat generating electronic components and heat dissipating components such as heat sinks and circuit boards for heat dissipation and cooling of heat generating electronic components. It is suitable for the heat dissipation structure used for mounting.
    权利要求:
    Claims (5)
    [1" claim-type="Currently amended] A thermally conductive composite sheet comprising (a) a thermosoftening thermal conductive sheet layer containing a silicone resin and a thermally conductive filler, and (b) a thermally conductive silicone rubber sheet layer containing a thermally conductive filler.
    [2" claim-type="Currently amended] The manufacturing method of the composite sheet of Claim 1 shape | molded the composition containing a silicone resin and a thermally conductive filler in layer shape on the silicone rubber sheet layer of Claim 1.
    [3" claim-type="Currently amended] A method for producing a composite sheet according to claim 1, wherein the liquid curable silicone rubber composition containing a thermally conductive filler is molded in a layered form on the thermally conductive sheet layer according to claim 1 for curing.
    [4" claim-type="Currently amended] The method according to claim 3, wherein the liquid curable silicone rubber composition is an addition reaction curable type.
    [5" claim-type="Currently amended] The method for producing the composite sheet according to claim 1, wherein the thermally conductive sheet layer according to claim 1 and the silicone rubber sheet layer are thermally compressed.
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    同族专利:
    公开号 | 公开日
    TWI278392B|2007-04-11|
    JP2004090516A|2004-03-25|
    US20040043229A1|2004-03-04|
    CN1324700C|2007-07-04|
    CN1495245A|2004-05-12|
    KR100674072B1|2007-01-26|
    TW200404843A|2004-04-01|
    JP3920746B2|2007-05-30|
    US7279224B2|2007-10-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-09-02|Priority to JP2002256564A
    2002-09-02|Priority to JPJP-P-2002-00256564
    2003-09-01|Application filed by 신에쓰 가가꾸 고교 가부시끼가이샤
    2004-03-18|Publication of KR20040023520A
    2007-01-26|Application granted
    2007-01-26|Publication of KR100674072B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2002256564A|JP3920746B2|2002-09-02|2002-09-02|Thermally conductive composite sheet and method for producing the same|
    JPJP-P-2002-00256564|2002-09-02|
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