TW201132691A - Thermal conductive sheet - Google Patents

Abstract

A thermal conductive sheet of the invention is a thermal conductive sheet containing plate-shaped boron nitride particles. The content ratio of the boron nitride particles is above 35 volume%. The thermal conductivity of the orthogonal direction for the thermal conductive sheet relative to the thickness direction is above 4W/m. K.

Description

201132691 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a thermally conductive sheet, and more particularly to a thermally conductive sheet that can be used in power electronics. [Prior Art] In recent years, power electronics technology for converting and controlling electric power by semiconductor elements has been used in a hybrid device, a light emitting diode (LED) device, and an electromagnetic induction heating device. In power electronics, in order to convert a large current into heat or the like, a material disposed in the vicinity of a semiconductor element is required to have high heat dissipation (high thermal conductivity). For example, a heat conductive sheet containing a plate-like boron nitride powder and an acrylate copolymer resin is proposed (for example, see JP-A No. 2-28 No.). In the heat conduction sheet of the Japanese Patent Publication No. 2-28-280496, the powder is nitrided in such a manner that the direction of the nitriding is aligned in the direction of the thickness of the sheet orthogonal to the thickness of the nitrided powder. Thereby, the thermal conductivity in the thickness direction of the thermally conductive material is improved. [Explanation] To: = = : There is a case where high thermal conductivity is required depending on the use and purpose and the thickness * 曰 I. In the case of the long-axis direction of the boron powder in the conductive sheet, the thermal conductivity of the surface is not sufficient in the direction of the surface. ® This soft I heat-conducting piece is also required to be excellent in terms of operability. J53628.doc 201132691 The object of the present invention is to provide a heat conductive sheet excellent in thermal conductivity in the softness and surface direction. . The heat conductive film according to the present invention is characterized in that it contains plate-like nitride shed particles, and the ratio of the boron nitride particles 3 is 35 vol% or more, and the thermal conductive sheet is oriented to 4 W/v and the thickness direction. The thermal conductivity in the orthogonal direction is 4 W/m*K or more. Further, in the sheet of the present invention, it is preferred that the boron nitride particles have an average particle diameter of 2 Å as measured by the first scattering method. 2. The hot-material sheet towel of the present invention is preferably used in the f-resistance test of the cylindrical mandrel method according to ns κ test by the following test, which is not evaluated by the following test. A fracture was observed on the above-mentioned hot material W material. Test conditions

Test apparatus: Model I Mandrel · Diameter 1 〇 mm Bending angle: 90 degrees or more Thickness of the above-mentioned heat conductive sheet: 0.3 mm Further, it is preferable that the heat conductive sheet of the present invention further contains a resin component in the resin component The dynamic viscosity measured according to JIS K 7233 (bubble viscosity meter method): (temperature Wt, solvent: butyl carbitol, solid content concentration · 40% by mass) is 〇22"〇4~2 〇(4) 〇4 m2/s is excellent in thermal conductivity and thermal conductivity in the plane direction orthogonal to the thickness direction in the heat conductive sheet of the present invention. 153628.doc 201132691 Excellent in thermal conductivity, and excellent in workability and surface orientation The heat conductive sheet of the present invention contains a boron nitride particle. The heat conductive sheet contains a nitrided egg N particle as a necessity, and further, for example. The resin component is formed in a plate shape (or a scaly shape), and is dispersed in a direction in which a thermally conductive sheet is aligned in a specific direction (described later). The length of the boron nitride particles in the longitudinal direction ( The average of the maximum length in the direction orthogonal to the thickness direction of the sheet is, for example, preferably (b) (4), preferably 3 to 9 〇 (4). Further, the average length of the long-side direction of the nitriding butterfly particles is preferably 5 _, preferably Above the teacher, it is preferably 2 or more, more preferably 3 or more, and most preferably 40 (10) or more, and is usually, for example, 100 μΓΠ or less, preferably 90 μηη or less. Further, the thickness of the boron nitride particles (plate The average of the length in the thickness direction, that is, the length in the side direction of the particles is, for example, 〇J 2 to 2, preferably 〇1 to 1 5 μηι. Further, the aspect ratio (longitudinal length/thickness) of the condensed butterfly particles is, for example, 2 to 1 0000, preferably 10 to 5000. Further, the average particle diameter of the boron nitride particles measured by a light scattering method is, for example, 5 μη or more, preferably 1 μm or more, more preferably 1 or more. Preferably, it is 30 μmη or more, and most preferably 4 〇μηη or more is usually (10) (four) or less. Further, the average particle diameter measured by the light scattering method is a volume average particle diameter measured by a dynamic light scattering type particle size distribution measuring apparatus. .doc 201132691 If the boron nitride particles are used When the average particle diameter measured by the scattering method does not satisfy the above range, the thermally conductive sheet becomes brittle and the workability is lowered. Further, the bulk density (JIS κ 5101, apparent density) of the boron nitride particles is, for example, 0.3 to 1.5 g. Further, the product of the boron nitride particles may be a commercially available product or a processed product obtained by processing the boron nitride particles. For example, a commercially available product of boron nitride particles may, for example, be mentioned. : "PT" series (such as "PT_U0") manufactured by Momentive Performance Materials japan, and "SHOBNUHP" series (such as "SHOBNUHP-1") manufactured by Showa Denko. The resin component is a dispersion medium (matrix) in which boron nitride particles are dispersed, that is, a dispersion of boron nitride particles, and examples thereof include a resin component such as a thermosetting resin component and a thermoplastic resin component. Examples of the thermosetting resin component include an epoxy resin, a thermosetting polyimide, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, a diallyl phthalate resin, and a polycondensation. A silicone resin, a thermosetting amine resin, or the like. Examples of the thermoplastic resin component include polyolefin (for example, polyethylene, polypropylene, ethylene-propylene copolymer, etc.), acrylic resin (for example, polymethyl methacrylate), polyvinyl acetate, and ethylene-vinyl acetate. Ester copolymer, polyethylene, polystyrene, polyacrylonitrile, polyamine (nylon (registered trademark)), polycarbonate, polyacetal, polyethylene terephthalate, polystyrene, poly Phenylene sulfide, polyhard, polyhard, polyetheretherketone, polyallyl barrier, thermoplastic polyimine, thermoplastic amine ester resin, polyamine bismaleimide, polyamidimide, Polyether quinone imine, bismaleimide three tillage tree 153628.doc 5 201132691 Lipid, polydecyl pentylene, fluororesin, liquid crystal polymer, dilute hydrocarbon-ethylene alcohol copolymer, ionomer, poly Illustrative, acrylonitrile, ethylene styrene copolymer, acrylonitrile butadiene styrene copolymer, acrylonitrile styrene copolymer, and the like. These resin components may be used alone or in combination of two or more. In the resin component, 'as a thermosetting resin component' is preferably an epoxy resin, and it is preferably a thermoplastic resin component, and a polythene hydrocarbon is preferable. The epoxy resin is in any state of liquid state, semi-solid state and solid state at normal temperature. Specifically, examples of the epoxy resin include bisphenol type epoxy resins (for example, bisphenol A type epoxy resin, (four) F type epoxy resin, indophenol § type epoxy resin, and hydrogenated double age A type epoxy. Resin, dimer acid modified double age epoxy resin, etc.), (4) varnish type epoxy resin (such as benzene varnish type epoxy resin, A (four) paint type epoxy resin, biphenyl type epoxy resin type Epoxy resin, first-type epoxy resin (for example, bisaryl g-type epoxy resin), triphenyl-based epoxy resin (for example, tri-vinyl phenyl-resin resin), etc. ; Oxygen tree 曰, for example, trisepoxypropyl isocyanurate, bismuth (diglycidyl succinyl / rat urinary sputum i 曰), ethyl carbendazole epoxy resin, etc., such as fat A family of lacquers, a resin-based epoxy resin (for example, a bicyclic ring-type epoxy resin, etc.), a glycidyl (tetra) epoxy methacrylic amine-based epoxy resin, etc. Two or more types may be used alone or in combination. The semi-solid epoxy resin may be used alone, and it is more preferable to use the semi-solid & - J cattle is more specific and t4 epoxy tree wax. As such an epoxy resin, the semi-solid type epoxy resin is listed. 153628.doc 201132691 Also, preferred are liquid epoxy resin and solid state ring The combination of the oxygen resin is more preferably a combination of a liquid aromatic epoxy resin and an aromatic solid epoxy resin. Examples of such a combination include a liquid bisphenol type epoxy resin and a solid triphenyl group. Combination of epoxy resin, liquid bismuth epoxy resin and solid bisphenol epoxy resin. If it is a semi-solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin, it can improve thermal conductivity. The step followability of the sheet (hereinafter, the epoxy equivalent of the epoxy resin is, for example, 1 〇〇 to 1 〇〇〇 iv, preferably just ～700 g/eqiv., softening temperature (ring and ball method), for example It is _ below (specifically 20~8〇. (:), preferably 耽 below (specifically 35~7 generation). Also, epoxy resin is 80. (: The melt viscosity is, for example, ι〇~2〇 , preferably 5〇~1〇_秦", when two or more kinds of epoxy resins are used in combination, In the case where two or more kinds of epoxy resins are used in combination, for example, an epoxy resin which is solid at normal temperature and an epoxy resin which is liquid at normal temperature can be used in combination. In the case of the above epoxy resin, the first epoxy resin having a softening temperature of, for example, less than 45 C, preferably not more than hunger, and a second epoxy resin having a softening temperature of, for example, a valence or more, preferably 55 t or more, may be used. In this case, the dynamic viscosity of the resin component (mixture) can be set to a desired range (in accordance with JIS KK, described later). The epoxy resin can be prepared, for example, by using a curing agent and a curing accelerator to prepare an epoxy resin composition. The hardener is a latent hardener (epoxy hardener) which hardens an epoxy resin by heating, for example, a sputum compound, an amine compound 153628.doc 201132691, a melamine compound, an gland compound, an object, An acid anhydride compound, a guanamine compound, a ruthenium compound or the like. Further, in addition to the above, a phenol compound polysulfide compound or the like can be also mentioned. For example, 2-phenylimidazole and 2·indolyl 2phenyl-4-mercapto-5-hydroxymethylimidazole are exemplified. The compound can be exemplified as an amine compound, for example, a polyamine such as __-amine, propylenediamine, diethylenetriamine or triethylenetetramine. Or an amine, a neck, etc., such as m-phenylenediamine-amine-based monomethane, diamine-based, stupid mill, and the like. Examples of the acid anhydride compound include: ^ * * - net-type monocarboxylic anhydride, maleic acid liver, tetrakis phthalic anhydride, hexa-n-benzoic acid, stearyl anhydride, methyl-resistant As the acid anhydride, the company has a tetracarboxylic acid dianhydride, a dodecenyl succinic anhydride, a dioxosuccinic acid, and an anthraquinone anhydride. The mercapto anhydride and the gas, as the guanamine compound, for example, an isomeric diamine or a polyamine can be used as the ruthenium compound, for example, a ruthenium adipic acid or the like. Examples of the compound of the (IV) compound include a methyl group, a 2-ethyl-ethyl-m-methyl-salt, an ethyl-salt, an isopropyl miso, a 24-dimethylimidazoline, a phenylimidazoline, and a _ , shouting, decamethyl imiline, heptadecyl (tetra) lin, 2 - keto-4 - fluorenyl salicin and so on. These hardeners may be used alone or in combination of two or more. Tris-2, 4, 6_ 2 As the curing agent, an imidazole compound is preferred. Examples of the hardening accelerator include, for example, triethylenediamine 153628.doc -9. 201132691 tertiary amine compounds such as aminomethyl-rezyme, such as triphenyl scale, tetraphenyl quaternary tetraphenyl acid salt, and tetra Orthobutyl scales _. ,. _Diethyldisulfide salt An scaly compound, such as a quaternary salt compound, for example, an organometallic salt, such as a derivative thereof. These hardening accelerators may be used alone or in combination of two or more. The blending ratio of the hardener in the epoxy resin composition is, for example, 0 5 to 5 parts by mass, preferably 1 part by mass, based on 100 parts by mass of the epoxy resin, and the ratio of the hardening accelerator is, for example, G1~ 1 g parts by mass, preferably 〜5 parts by mass. The above-mentioned curing agent and/or curing accelerator may be used as a solvent solution and/or a solvent dispersion which is dissolved and/or dispersed by a solvent, if necessary. The solvent may, for example, be an anthracene or a methyl ethyl group. For example, an organic solvent such as acetonide such as N,N-dimethylformamide or the like may be used. Further, as the solvent, for example, water, for example, an aqueous solvent such as an alcohol such as methanol, ethanol, propanol or isopropanol may be mentioned. The solvent is preferably an organic solvent, and more preferably a ketone. The polythene hydrocarbon is preferably a polyethylene or ethylene-propylene copolymer. The 乍 is a polyethylene, and examples thereof include low density polyethylene and high density polyethylene. Examples of the ethylene propylene-baked copolymer' include, for example, ethylene and propylene copolymers, block copolymers, and graft copolymers. These polyolefins may be used alone or in combination of two or more. Further, the weight average molecular weight and/or the number average molecular weight of the polycondensate are 153628.doc

-10 201132691 For example, 1000~10000. Further, the polyolefin may be used singly or in combination of plural kinds. Among the resin components, a thermosetting resin component is preferable, and an epoxy resin is more preferable. Further, the resin component was subjected to a dynamic viscosity test according to JIS κ 7233 (bubble viscosity meter method) (temperature: 25 it ± 0.5. (:, solvent: butyl carbitol, resin component (solid content) concentration: 40 mass %) The measured dynamic viscosity is, for example, 0.22Χ10·4~2.00x10-4 m2/s, preferably 〇3χΐ〇-4~ι 9χΐ〇-4, more preferably 0.4X10·4~l.8xl0-4 m2 Further, the dynamic viscosity may be set to, for example, 0.22×10·4 〜1.〇〇xl〇-4 m2/s, preferably 〇3χΐ〇·4 〇4 m2/s, more preferably 〇 .4xl〇·4~〇.8xi〇-4m2/s. When the dynamic viscosity of the resin component exceeds the above range, excellent flexibility and step followability (described later) may not be imparted to the thermally conductive sheet. On the other hand, when the dynamic viscosity of the resin component does not satisfy the above range, the boron nitride particles may not be aligned in a specific direction. Further, in the dynamic viscosity test according to JIS K 7233 (bubble viscosity meter method), The rate of rise of the bubble in the resin component sample is compared with the rate of rise of the bubble in the standard sample (the known dynamic viscosity is known) The dynamic viscosity of the standard sample having the same speed is the dynamic viscosity of the resin component, and the dynamic viscosity of the resin component is measured. Further, in the heat conductive sheet, the volume ratio of the boron nitride particles is based on the solid content, that is, the resin component is contained. In the case of the thermoplastic resin component, the volume fraction of the boron nitride particles to the total volume of the thermoplastic resin component and the nitride side particles is 35 vol% or more, preferably 6% by volume or more, more preferably 153628.doc 201132691 is preferably 75 vol. % or more, for example, it is preferably 95% by volume or less, preferably 9% by volume or less. When the content ratio of the volume basis of the boron nitride particles does not satisfy the above range, the boron nitride particles cannot be made specific to the thermally conductive sheet. On the other hand, when the content ratio of the volume basis of the boron nitride particles exceeds the above range, the thermally conductive sheet becomes brittle, and the workability and the step followability (described later) are lowered. The total amount of each component (boron nitride particles and resin component) of the heat conductive sheet (total amount of solid components) 1 part by mass, boron nitride The blending ratio of the mass basis is, for example, 4 to 95 parts by mass, preferably 65 to 9 parts by mass, based on 1 part by mass of the total amount of each component forming the thermally conductive sheet, and the mass of the resin component. The blending ratio is, for example, 5 to 6 parts by mass, preferably 10 to 35 parts by mass. Further, the blending ratio of the boron nitride particles to the mass basis of the resin-forming 100-mass damage is, for example, (6) to 丨9〇〇. The mass portion is preferably 185 to 900 parts by mass. When the two types of epoxy resins (the second epoxy resin and the second epoxy resin) are used in combination, the quality of the first epoxy resin relative to the second epoxy resin The ratio (the mass of the i-th epoxy resin / the mass of the second epoxy resin) can be appropriately set according to the softening temperature of each epoxy resin (the i-th epoxy resin and the second epoxy resin), for example, 1/99. ~99/1, preferably ι0/9〇~9〇/1〇. Further, in addition to the above respective components (polymers), the resin component may further contain, for example, a polymer precursor (for example, a low molecular weight polymer containing a polymerizable polymer, etc.) and/or a monomer. One of the thermally conductive sheets of the invention is a standing hip 153628.doc • 12· 5. 201132691 One of the thermally conductive sheets of the present invention will be described with reference to Figs. 1 and 2 for the production of the method of the present embodiment. In this method, the above components are first formulated by the above-mentioned blending ratio and stirred and mixed, whereby a mixture is prepared. In the mixing and mixing, in order to efficiently mix the components, for example, a solvent may be blended with each of the above components, or a resin component (preferably a thermoplastic resin component) may be fused, for example, by heating. The solvent is the same as the above-mentioned organic solvent. Further, when the curing agent and/or the curing accelerator are prepared as a solvent solution and/or a solvent dispersion, the solvent may be directly supplied to the solvent solution and/or the solvent dispersion without adding a solvent during the (4) mixing. Mix the mixed solvent. Alternatively, a solvent may be further added as a mixed solvent when stirring and mixing. When the solvent is used for (4) mixing, the solvent is removed after (4) mixing. In order to remove the solvent, for example, it is left at room temperature for 48 hours, or for example, heated at 2 to 2 hours for 0.5 to 3 hours, or for example, under the decompression of the heart, heated at 20 to 60 ° C. · 5 to 3 hours. When the resin component (preferably a thermoplastic resin component) is melted by heating, the heating temperature is, for example, near or above the softening temperature of the resin component, specifically 40 to 15 ° C, preferably 70 to 14 (TC. Then 'in this method, the mixture obtained by hydrazine is hot pressed. The steroid is not as shown in Fig. 2(a), and the mixture is subjected to hot pressing through, for example, two release films 4 as needed. The pressed sheet is obtained. The condition of hot pressing is 153628.doc 201132691, for example, 50 to 15 ° C, preferably 60 to 140 t, and the pressure is, for example, 〜1 〇〇 MPa, preferably 5 to 50 MPa 'time. For example, it is 1 to 1 minute, preferably 1 to 30 minutes. More preferably, the mixture is subjected to vacuum hot pressing. The vacuum degree of vacuum hot pressing is, for example, 1 to 100 Pa, preferably 5 to 5 Å Pa. The temperature, the pressure, and the time are the same as the temperature, the house force, and the time of the heat. When the temperature, pressure, and/or time of the hot press are outside the above range, there is a void ratio p (which will be described later) in which the thermally conductive sheet cannot be twisted. The case of adjusting to a desired value. The thickness of the pressed sheet 1A obtained by hot pressing, for example 504 〇〇〇, preferably 10 〇 to 8 〇〇 μιη. Then, in the method, as shown in Fig. 2(b), the pressed sheet is divided into a plurality of (for example, four), thereby obtaining Split sheet #1B (dividing step). In the division of the pressed sheet 1A, the pressed sheet is cut in a plurality of directions in a manner of being divided into a plurality in the thickness direction. Further, the pressed sheet is pressed. 1A is cut so as to have the same shape when the divided sheets are projected in the thickness direction. In the D Hai method, as shown in FIG. 2(c), each divided sheet 1B is laminated in the thickness direction to obtain Laminated sheet 1C (layering step). "After 'in *Haifang*', as shown in Fig. 2(a), the laminated sheet ic is subjected to hot pressing (preferably vacuum hot pressing) (hot pressing step) The conditions of the hot pressing are the same as those of the above-mentioned mixture. The thickness of the material 1 C is, for example, 1 mm or less, less than 4 〇·8 mm, 诵赍. Usually, for example, 0.05 mm or more, preferably (U m 153628 .doc 201132691 Then, in the thermally conductive sheet 1, in order to make the boron nitride particles 2 effective in a specific direction in the resin 3 The above-described dividing step (Fig. 2(b)), the laminating step (Fig. 2(c)), and the hot pressing step are repeated, and the number of repetitions of the series of steps is not particularly limited, and may be based on boron nitride particles. The filling state is appropriately set, for example, ~~! times, preferably 2 to 7 times. Thereby, the thermally conductive sheet 1 can be obtained. The thickness of the obtained thermally conductive sheet 1 is, for example, 丨mm or less, preferably 〇. In the case of 8 mm or less, it is usually 〇〇5 mm or more, preferably 〇"", and the volume ratio of the boron nitride particles in the thermally conductive sheet 1 (solid content, that is, boron nitride particles). The volume percentage of the total volume of the resin component and the boron nitride particles is 35 volume D / ❶ or more (preferably 60 vol% or more, more preferably 75 vol% or more), usually % volume, as described above. Below % (preferably 90 volume ❶ /. the following). When the content ratio of the boron nitride particles does not satisfy the above range, there is a method in which the boron nitride particles are blended in a specific direction in the thermally conductive sheet. Further, when the resin component 3 is a thermosetting resin component, the uncured (or semi-cured (B-stage)) thermally conductive sheet 1 is subjected to the hot pressing step (Fig. 2 (a)). Thermal hardening, and the heat-conductive sheet 1 after hardening is produced. The heat conductive sheet is used. When the heat is hardened, the above-mentioned hot press or dryer can be used. It is preferred to use a dryer. The temperature hardening conditions are, for example, 60 to 250 ° C, preferably 80 to 200 eC. When a hot press is used, the pressure is, for example, 100 MPa or less, preferably 5 MPa or less. 153628.doc •15· 201132691 Further, in the thermally conductive sheet 1 thus obtained, as shown in FIG. 1 and a partial enlarged view thereof, the long-side direction LD of the boron nitride particles 2 is along with the thermally conductive sheet 1 The thickness direction TD intersects (orthogonally) in the plane direction Sd to be aligned. Further, the arithmetic mean of the angle between the longitudinal direction LD of the boron nitride particles 2 and the surface direction SD of the thermally conductive sheet 1 (the alignment angle α of the boron nitride particles 2 with respect to the thermally conductive sheet 1) is, for example, 25 degrees. In the following, it is preferably 20 degrees or less, and is usually 0 degrees or more. Further, the alignment angle α of the boron nitride particles 2 with respect to the thermally conductive sheet 1 is calculated as follows: by a cross-section polisher (cp, Cross) Secti〇n Polisher) cuts the thermally conductive sheet 1 in the thickness direction, and takes a photograph of the cross section which is observed by using a scanning electron microscope (SEm) at a magnification in which the field of view of 200 or more boron nitride particles 2 can be observed. The inclination angle α of the longitudinal direction ld of the boron nitride particles 2 with respect to the plane direction SD of the thermally conductive sheet 1 (the direction orthogonal to the thickness direction TD) was obtained from the obtained SEM photograph, and was calculated as the average value. Thereby, the thermal conductivity of the surface direction SD of the thermally conductive sheet 1 is 4 w/mK or more, preferably 5 W/mK or more, more preferably 10 w/m, K or more, and particularly preferably 15 W/mK. The above is particularly preferably 25 w/mK or more, and is usually 2 〇〇W/m*K or less. In addition, when the resin component 3 is a thermosetting resin component, the thermal conductivity of the surface of the thermally conductive sheet 1 is substantially the same before and after the thermosetting. If the thermal conductivity does not satisfy the above range, the thermal conductivity of the surface direction SD may be insufficient, and it may not be used for the heat dissipation application of the thermal conductivity of the surface direction SD of 153628.doc 201132691. Further, the thermal conductivity of the surface direction SD of the thermally conductive sheet 1 was measured by a pulse heating method. The pulse heating method was a "FLA-447 type" (manufactured by NETZSCH Co., Ltd.) using a xenon flash analyzer. Further, the thermal conductivity of the thickness direction TD of the thermally conductive sheet 1 is, for example, 〇·5 to 15 W/m, and K, preferably i~i〇 w/m.K. Further, the thermal conductivity of the thickness direction TD of the thermally conductive sheet 1 is measured by a pulse heating method, a laser flash method or a TWA (Temperature Wave Analysis) method. In the pulse heating method, "TC-9000" (manufactured by ULVAC-RIKO Co., Ltd.) was used in the same manner as the above-mentioned laser flash method. "Ai-phase mobile" (manufactured by ai-Phase Co., Ltd.) was used. Thereby, the ratio of the thermal conductivity of the surface direction SD of the thermally conductive sheet 相对 to the thermal conductivity of the thickness direction TD of the thermally conductive sheet 1 (the thermal conductivity of the surface direction SD / the thermal conductivity of the thickness direction TD) For example, it is ι 5 or more, preferably 3 or more, more preferably 4 or more 'usually 2 〇 or less. Further, in the thermally conductive sheet 1, although not illustrated in the drawings, a void (gap) may be formed, for example. The ratio of the voids in the thermally conductive sheet 1, that is, the void ratio p, can be obtained by boron nitride. The content ratio of the particles 2 (volume basis), and further the hot pressing of the mixture of the boron nitride particles 2 and the resin component 3 (Fig. 2 The temperature, pressure, and/or time of a)) are adjusted to be 'specifically' adjusted by setting the temperature, pressure, and/or time of the hot pressing (Fig. 2(a)) to the above range. The porosity p in the thermally conductive sheet is, for example, 3 vol% or less, preferably 153628.doc 201132691 is 1 vol% or less. The void ratio P is measured by, for example, first cutting the thermally conductive sheet i in the thickness direction by a cross-section polisher (CP), and the resulting cross section is scanned by a scanning electron microscope (SEM). The image was obtained by observation in multiples, and the void portion and the other portions were binarized according to the obtained image, and then the area ratio of the void portion to the entire cross-sectional area of the thermally conductive sheet 1 was calculated. In the thermally conductive sheet 1, the void ratio P2 after curing is, for example, 100% or less, preferably 5% by weight or less, relative to the void ratio P1 before curing. In the measurement of the porosity P (P1), when the resin component 3 is a thermosetting resin component, the thermally conductive sheet 1 before thermal curing can be used. When the porosity P of the thermally conductive sheet 1 is within the above range, the step followability (described later) of the thermally conductive sheet 1 can be improved. Further, in the bending resistance test of the cylindrical conductive mandrel according to the cylindrical mandrel method of JIS K 5600-5-1, the thermal conductivity sheet 1 was evaluated by the following test conditions, for example, no fracture was observed. Test condition test device: Model I Mandrel: diameter 10 mm Bending angle: 90 degrees or more Thermal conductive sheet 1 thickness: 0.3 mm Further, 'the stereoscopic diagram of the model I test device is shown in Fig. 9 and Fig. 10, below The test device of model I will be described. In Fig. 9 and Fig. 10, the type I test apparatus is different: the first flat plate 153628.doc 201132691 11, the second flat plate 12 arranged in parallel with the first flat plate 11, and the first flat plate u and the second flat plate 12 The mandrel (rotating pumping) 丨3 is set to rotate relative to each other. The first flat plate 11 is formed in a substantially rectangular flat plate shape. Further, a stopper portion 14 is provided at one end portion (free end portion) of the first flat plate. The stopper portion 14 is formed on the surface of the second flat plate 12 so as to extend along one end portion of the second flat plate 12. The second flat plate 12 is formed in a substantially rectangular flat plate shape, and one side thereof is adjacent to one side of the first flat plate (one side of the other end portion (base end portion) on the side opposite to the end portion on which the stopper portion 14 is provided) The way to configure. The mandrel 13 is formed to extend along the sides of the second plate 丨丨 and the second plate 12 adjacent to each other. In the test apparatus 1 of this type I, as shown in Fig. 9, the surface of the first flat plate 11 and the surface of the second flat plate 12 were formed in the same plane before the start of the bending resistance test. Further, when the bending resistance test is performed, the thermally conductive sheet 1 is placed on the surface of the first flat plate 11 and the surface of the second flat plate 12. Further, the thermally conductive sheet 1 is placed such that one side thereof abuts against the stopper portion 14. Then, as shown in FIG. 10, the first flat plate 11 and the second flat plate 12 are relatively rotated, and the free end portions of the first flat plate 11 and the free end portions of the second flat plate 12 are rotated only around the mandrel 13 as shown in FIG. Specific angle. Specifically, the first flat plate 11 and the second flat plate 12 are rotated such that the surface of the free end portion thereof approaches (opposes). Thereby, the thermally conductive sheet bundle follows the rotation of the second sheet u and the second sheet 12, and the surface is curved around the mandrel 13. Preferably, in the above-mentioned test conditions, the thermal conductive sheet 1 is not observed to have a fracture even if the bending angle of the 153628.doc -19-201132691 is set to 180 degrees. When the fracture was observed on the thermally conductive sheet 1 in the test conducted at the above bending angle, there was no difference in flexibility. I. Conductive Steep Sheets 丄 Excellent = In the bending resistance test, when the resin component 3 is a thermosetting tree, the heat conductive sheet before heat hardening can be used. In the second embodiment, when the conductive sheet 1 was evaluated at three points in accordance with JIS κ 7171_year by the following test conditions, for example, no break was observed.眺木眺祭 test conditions s type test: size 20mmxl5mm distance between fulcrums: 5 mm test speed: 20mm / min (pressure speed under the head) bending angle: 120 degrees evaluation method: visual observation by the above test conditions The test piece at the time of the test caused the central part to have cracks such as cracks. Further, in the three-point "curve test", when the resin component 3 is a thermosetting resin component, a heat conductive sheet before heat curing can be used. Therefore, the thermal conductive sheet was excellent in step followability because no fracture was observed in the above-described triaxial test. In addition, the step followability refers to a characteristic that follows when the thermally conductive sheet bundle is placed on a setting object having a step difference so as to be closely adhered along the step. Further, for example, a mark such as a character or a symbol can be attached to the heat conductive sheet! That is, the thermal conductive sheet i is excellent in label adhesion. The so-called mark attachment 153628.doc 5 -20· 201132691 Ί ± , ^ characteristics. The mark in which the above-mentioned mark is surely attached to the thermally conductive sheet 1 is +, and can be attached (coated, fixed or fixed) to the thermally conductive sheet by printing, engraving or the like. The ’ is printed, for example, inkjet printing, letterpress printing, gravure printing, laser printing, and the like. When the marking is carried out by inkjet printing, letterpress printing or gravure printing, for example, an ink fixing layer for improving the fixing property of the marking can be provided on the surface (printing side) of the thermally conductive sheet 1. When the mark is printed by laser printing, for example, a toner fixing layer for fixing the same particle 5 can be provided on the surface (printing side) of the heat conductive sheet 1. As the engraving, for example, laser marking, engraving, and the like can be cited. Further, the volume resistance R of the thermally conductive sheet 1 is, for example, lxi〇w, preferably lxl〇12 Q.cm or more, and is usually 1χ1〇2. the following. The volume resistance R of the thermally conductive sheet 1 was measured in accordance with JIS K 6911 (General Test Method for Thermosetting Plastics, 2006 Edition). When the volume resistance r of the thermally conductive sheet 1 does not satisfy the above range, there is a case where the short circuit between the electronic components described later cannot be prevented. Further, in the thermally conductive sheet crucible, when the resin component 3 is a thermosetting resin component, the volume resistive R is a value of the thermally conductive sheet 1 after curing. Further, the dielectric breakdown voltage of the thermally conductive sheet 1 measured in accordance with JIS C 2110 (2010 edition) is, for example, 10 kV/mm or more. When the dielectric breakdown voltage of the thermally conductive sheet 1 does not satisfy 10 kV/mm, there is no guarantee of excellent resistance.

153628.doc •21 201132691 Insulation destructive (resistance to tracking). In addition, the above-mentioned dielectric breakdown voltage is measured in accordance with JIS C 2110-2 (2010 edition) "Testing method of strength of solid electrical insulating material - insulation breakdown - Part 2 · Test for applying DC voltage". Specifically, the voltage at which the dielectric breakdown is generated on the thermally conductive sheet 1 is measured as the dielectric breakdown voltage by a short-time (rapid boost) test with a step-up speed of 100 V V s. Further, the dielectric breakdown voltage of the thermally conductive sheet 1 is preferably 15 kV/mm or more, and is usually 100 kV/mm or less. When the resin component 3 is a thermosetting resin component, the dielectric breakdown voltage of the thermally conductive sheet 1 is substantially the same before and after the thermal curing of the thermally conductive sheet 1. Further, the glass transition point of the thermally conductive sheet 1 is, for example, 125 or more, preferably 13 (TC or more, more preferably 140 ° C or more, and particularly preferably 15 (rc or more, more preferably 170 ° C or more, Furthermore, it is more preferably 190 ° C or higher, and still more preferably 210 ° C or higher, and usually 3 ° C or lower. When the glass transition point is at least the above lower limit, excellent heat resistance of the thermally conductive sheet can be ensured. The deformation at a high temperature is reduced, and the peeling is suppressed. That is, when the thermal conductive sheet is bonded to various devices, the temperature rises when the temperature of the device exceeds the glass transition point of the thermally conductive sheet, and the thermally conductive sheet is present. The material 1 is peeled off from various devices due to a change in the linear expansion coefficient. However, in the heat conductive sheet material, since the glass transition point is equal to or higher than the above upper limit, even if the temperature of the device rises, the heat conductive sheet can be prevented from exceeding. The glass transition point of 1 can reduce the deformation of the thermally conductive sheet 1 153628.doc -22- 201132691 and inhibit the peeling β. The glass transition point is measured by dynamic viscoelasticity at a frequency of 10 Hz. Place Further, the thermal conductive sheet 1 is 5 Å. The mass reduction temperature is, for example, 25 〇 or more, preferably 300. (: Above, usually 45 〇) Below °C. When the temperature is reduced above the above lower limit in the right 5th, the decomposition can be suppressed even when exposed to high temperatures, and the heat generated by various devices can be efficiently conducted. Further, the 5% mass reduction temperature can be heated by heat. The mass analysis (heating rate: 10 ° C / min, in a nitrogen atmosphere) was measured in accordance with JIS κ 7120. Further, the thermal conductive sheet 1 was not peeled off from the adherend, for example, in the following initial adhesion test (1). That is, the heat conductive sheet 1 and the adherend are temporarily fixed. Initial adhesion test (1): The heat conductive sheet is heat-pressed and bonded to the bonded body in the horizontal direction to be temporarily fixed and placed. After 1 minute, the adherend is inverted upside down. Examples of the adherend include a substrate including stainless steel (for example, SuS304), or a plurality of 1C (integrated circuit) wafers, capacitors, and coils. , resistor, etc. In a notebook computer package substrate, the electronic components are usually separated from each other on the upper surface (the surface) in the surface direction (the direction of the package substrate for the notebook computer). In the case of the pressure bonding, for example, the surface of the thermally conductive sheet 1 is rotated by pressing the thermal conductive sheet 1 with a sponge comprising a resin such as a polyoxymethylene resin, and the surface of the thermally conductive sheet 1 is rotated 153628.doc • 23· 201132691. When the resin component 3 is a thermosetting resin component (for example, an epoxy resin), the temperature is, for example, 80. (:: In addition, the temperature of the thermocompression bonding is a thermoplastic resin component in the resin component 3 ( For example, in the case of polyethylene, for example, a temperature of 10 to 3 is added to the softening point or melting point of the thermoplastic resin component (the temperature of TC is preferably 15 to 25 t at the softening point or melting point of the thermoplastic resin component, more preferably Adding a temperature of 2〇»c to the softening point or melting point of the thermoplastic resin component, specifically 12〇β (: (ie, the softening point or melting point of the thermoplastic resin component is 100 ° C, adding 20 ° to the l〇〇oc C temperature). When the thermally conductive sheet 1 is detached from the adherend in the initial adhesion test (1), that is, when the thermally conductive sheet 丨 and the adherend are temporarily held, the thermally conductive sheet may not be reliably provided. The material is temporarily fixed to the bonded body. In the case where the resin component 3 is a thermosetting resin component, the thermally conductive sheet 1 to be subjected to the initial adhesion test (1) and the initial adhesion test described later is an uncured heat conductive sheet 丨, which is initially In the adhesion test (1) and the initial adhesion test (2), the heat-conductive sheet is brought into a B-stage state. In the case where the resin component 3 is a thermoplastic resin component, the thermally conductive sheet 1 to be subjected to the initial adhesion test (1) and the initial adhesion test (2) (described later) is a solid heat conductive sheet 1 by initial In the adhesion test (丨) and the initial pressure bond test (2), the heat conductive sheet 1 was softened. 153628.doc -24· 5 201132691 Preferably, the 'thermally conductive sheet 不 does not fall off from the bonded body in the two tests of the initial adhesion test (1) and the following initial adhesion test (2). That is, the heat conductive sheet 1 and the adherend are temporarily fixed. Initial adhesion test (2): The heat conductive sheet 1 is temporarily fixed by heat-compression bonding on the bonded body in the horizontal direction, and after being placed for 1 minute, the bonded body is placed in the vertical direction ( Configure in the up and down direction). The temperature at the time of the heat bonding of the initial adhesion test (2) was the same as the temperature at the time of the heat bonding of the initial adhesion test (1). Further, in the thermally conductive sheet 1, the flexibility and the thermal conductivity in the plane direction SD are excellent. Therefore, the thermally conductive sheet which is excellent in workability and excellent in thermal conductivity in the surface direction SD can be used for various heat dissipation applications, and specifically, can be used as a heat conductive sheet used in power electronics technology, and more specifically δ For example, it can be used as a heat conductive sheet applied to an LED heat sink substrate or a battery heat sink. Further, since the above-mentioned thermally conductive sheet has excellent thermal conductivity in the plane direction SD and the volume resister is within a specific range, electrical insulation is also excellent. Therefore, by coating the electronic component with the thermal conductive sheet 右, the electronic component can be protected, and the heat of the electronic component can be thermally efficiently conducted, and the short circuit between the electronic components can be prevented. In addition, the electronic component to be coated on the thermally conductive sheet is not particularly limited, and examples thereof include a 1 (: integrated circuit) wafer, a device, a coil, a resistor, a light-emitting diode, and the like. The elements are usually disposed on the substrate 153628.doc •25-201132691 and are disposed at intervals in the plane direction (plane direction of the substrate). Further, the above-mentioned thermally conductive sheet 1 is excellent in thermal conductivity in the plane direction SD and insulated. Since the breakdown voltage is within a specific range, the dielectric breakdown resistance (scratch resistance) is also excellent. Therefore, if the thermal conductive sheet 1 is used to cover electronic components used in power electronics and/or package substrates packaged therewith Therefore, the insulation breakdown of the thermally conductive sheet 1 can be prevented, and the heat of the electronic component and/or the package substrate can be dissipated along the surface direction SD by the thermally conductive sheet. As an electronic component used in power electronics For example, an IC (integrated circuit) wafer (particularly, a narrow electrode terminal portion in a 1C wafer), a thyristor (rectifier), a motor component, a transformer, and a delivery can be cited. A component, a capacitor, a coil, a resistor, a light emitting diode, etc. Further, on the package substrate, the electronic component is packaged on the surface (one surface) in the package substrate, and the electronic component is in the surface direction (the package substrate) The heat conductive sheet i covering the electronic component and/or the package substrate can be prevented from being deteriorated by high frequency noise generated by the electronic component and/or the package substrate. In the above-described thermally conductive sheet 1, the thermal conductivity in the surface direction SD is excellent, and the glass transition point is in a specific range, so that the heat resistance is also excellent. Therefore, the deformation at high temperature can be reduced and the peeling can be suppressed. A heat conductive sheet which is excellent in handleability and excellent in thermal conductivity in the surface direction can be used for various heat dissipation applications. Specifically, it can be called a bamboo φ Dan bottle. J is used as a power electronics technology. 153628.doc 5 -26- 201132691 Thermally conductive sheet, more detailed

Also Tian Tianyang. For example, it can be used as a heat conductive sheet applied to a heat dissipation substrate for a j^D and a heat dissipation material for a battery. Further, in the above thermally conductive sheet 1,

τ The field is excellent in thermal conductivity in the softness and the surface direction SD, and the 5% mass is reduced, and the clothing is in a specific range. Therefore, the heat resistance is also excellent. That is, according to the thermally conductive sheet 1, for example, it is exposed to 200. 〇; the above-mentioned high temperature can also suppress decomposition, and is used as a heat conductive sheet which is excellent in handleability and excellent in surface thermal conductivity, and is used for various heat dissipation applications, specifically, it can be used for generating high temperature of 200~boots. The heat conductive sheet # used in the power electronics technology is, for example, a heat conductive sheet which can be applied to a Sic wafer, an LED heat sink substrate, or a heat sink for a battery. Further, the thermal conductive sheet 1 is excellent in thermal conductivity in the plane direction SD, and in the initial adhesion test (1), for example, does not fall off from the adherend, and therefore the heating pressure is applied to the specific temperature of the adherend. The adhesion (initial adhesion) is also excellent. Therefore, when the thermally conductive sheet 1 is heat-pressed on the adherend, the thermally conductive sheet 1 can be surely fixed (temporarily fixed) to the adherend. Therefore, the thermally conductive sheet is temporarily fixed to the adherend in the B-stage state, and then the thermally conductive sheet 1 is thermally cured by heating, whereby the thermally conductive sheet 1 can be surely bonded to the thermally conductive sheet 1 The heat of the adherend can be efficiently thermally conducted along the surface direction SD of the thermally conductive sheet 1 by the thermally conductive sheet 1 on the adhesive body. 153628.doc -27- 201132691 Further, as the adherend, there is no particular limitation on the sub-components (ic crystal #, capacitor ', the above-mentioned electroluminescent diode, etc., wires, resistors, etc.) In addition, on the other hand, the 'hot material W material' is temporarily fixed on the bonded body, and if necessary, it is temporarily peeled off for position adjustment, and it is necessary to re-attach (secondary processing). The conductive sheet 1 is in the B-stage state, and the secondary workability:: = The conductive sheet 1 can be prevented from remaining on the surface of the jointed body when peeled off and can be easily performed: secondary processing. Further, even if the hot material sheet is left on the surface of the adherend, if the material 1 is unhardened (before curing), the residue can be easily wiped (removed). Further, in the above-described enthalpy (Fig. 2 (4)) step, for example, the mixture and the laminated sheet 1C may be rolled by a plurality of calender rolls or the like. When the resin component 3 is a thermosetting resin component, it is possible to obtain a thermally conductive sheet in the form of an uncured thermally conductive sheet 1 as described above without performing thermal curing. In other words, the heat conductive sheet of the present invention is not particularly limited as long as the resin component is a thermosetting resin, and the time is not particularly limited. For example, as described above, the step of laminating (Fig. 2(c)) may be employed. Or after the specific hot pressing step (Fig. 2(a), hot pressing of the mixture, and hot pressing without heat hardening) after a certain period of time, specifically, when applied to power electronics technology, or from the application After a certain period of time, heat hardening is performed. EXAMPLES The following examples and comparative examples are disclosed, and the present invention is more specifically 153628.doc -28 - 8 201132691, but the present invention is not limited by the examples and comparative examples. Example 1 According to the formulation of Table 1, the components (boron nitride particles and epoxy resin composition) were blended and stirred, and placed at room temperature (23 it) under the i-night sputum (solvent solvent) The dispersant of the hardener is volatilized to prepare a semi-solid. ' σ Then, the resulting mixture was held by two release films treated with polyoxyxylene, for the vacuum heating of the press at 8 ° C, in the environment of Pa (vacuum environment), Pressing with a load of 5 tons (2 〇Mpa) for 2 minutes borrowed to obtain a pressed sheet having a thickness of 0.3 mm (refer to Fig. 2 (a)). Then, when the resulting pressed sheet was projected in the thickness direction of the pressed sheet The cut piece is cut into a plurality of pieces to obtain a divided sheet (see FIG. 2(b))'. Then, the divided sheet is laminated in the thickness direction to obtain a laminated sheet (see FIG. 2(c)). The obtained laminated sheet was hot-pressed by the same conditions as above by the same vacuum heating press as described above (refer to Fig. 2 (a)). Then, the above-mentioned series of cutting, laminating and hot pressing were repeated four times. Operation (refer to Fig. 2) 'to obtain a thermal conductive sheet having a thickness of ο. mm. ^ After that, the obtained thermally conductive sheet was placed in a dryer at 〇5 〇. The underarm was heated for 120 minutes, thereby performing thermal hardening. Example 2~8, 1〇~1 6 and Comparative Example 1, 2 According to Table 1 to Table 3, the prescription and Conditions were prepared in the same manner as in Example!, whereby thermally conductive sheets having thicknesses of 〇·3 mm of Examples 2 to 8, ι to 16 and Comparative Examples 1 and 2 were obtained, respectively. 153628.doc • 29· 201132691 Example 9 According to the formulation of Table 2, each component (boron nitride particles and polyethylene) was blended and stirred to prepare a mixture. That is, when the ingredients were mixed, the mixture was heated to 130 ° C. The polyethylene was melted. Then, the obtained mixture was held by two release films treated with polyfluorene oxide for the vacuum press at 12 Torr. Under the environment of 1 〇pa (vacuum environment) Next, it was heat-pressed at a load of 1 ton (4 MPa) for 2 minutes, thereby obtaining a pressed sheet having a thickness of 0 to 3 mm (refer to Fig. 2 (a)). Then, the resulting pressed sheet was pressed to the thickness of the pressed sheet. When the direction is projected, the film is cut into a plurality of pieces, thereby obtaining a divided sheet (see FIG. 2(b)), and then the divided sheets are laminated in the thickness direction to obtain a laminated sheet (see FIG. 2(c)). Then, the obtained laminated sheet is passed through the same vacuum heating press as described above. Hot pressing is performed under the same conditions as above (refer to Fig. 2 (a)). Then, one of the above-described series of cutting, laminating, and pressurizing operations (refer to Fig. 2) is repeated four times to thereby obtain heat conduction of a thickness of 〇3 mm. (Evaluation) (1) Thermal conductivity The thermal conductivity of the thermally conductive sheet obtained from each of the examples and the comparative examples was measured. That is, by using a scrambled flash analyzer "LFA-447 type" (NETZSCH) The thermal conductivity of the surface direction (SD) was measured by a pulse heating method manufactured by the company. Further, the thermal conductivity in the thickness direction (TD) was measured by the twA method using "ai-Phase mobile" (manufactured by Ai-Phase Co., Ltd.). 153628.doc 5 201132691 The results are shown in Tables 1 to 3 (Examples 1 to 16, Comparative Examples 1 and 2) and Fig. 8 (Examples 1 to 4 and Comparative Examples 1 and 2). (2) Observation of the cross section by an electron microscope The thermally conductive sheets of Examples 1, 3, and 5, and Comparative Examples 1 and 2 were cut in the thickness direction by a cross-section polisher, and the cut surface thereof was examined by an electron microscope (SEM). ) to observe. These image processing diagrams are shown in Fig. 3 to Fig. 7, respectively. (3) Bending resistance (flexibility) The heat conductive sheets of the respective examples and the comparative examples were subjected to a bending resistance test according to JIS κ 5600-5-1 bending resistance (cylindrical mandrel method). Specifically, first, for the thermally conductive sheets of Examples 1 to 8, 1 to 16 and Comparative Examples 1 and 2, a laminated sheet having a thickness of 〇3 mm before curing was prepared as a sample, and subjected to a bending resistance test. . Further, with respect to the thermally conductive sheet of Example 9, the obtained thermally conductive sheet having a thickness of 〇 3 mm was directly subjected to the bending resistance test. Then, the bending resistance (softness) of each of the heat conductive sheets was evaluated by the following test conditions. Test condition test device: Model I Mandrel: 10 mm in diameter and each unheated heat conductive sheet was bent at a bending angle exceeding the twist and below i8 twist, and fracture (damage) occurred according to the heat conductive sheet. The angle 'is evaluated in the following manner. The results are shown in Tables 1 to 3. 153628.doc •31 · 201132691 ◎ ·· 180 degrees, no break even if bent. 〇: If the temperature is above 90 degrees, it will not reach 18 degrees. If it is bent, it will break. △ : 10 degrees or more is less than 90 degrees, and if it is bent, it is broken. X ·· exceeds 0 degrees by less than 10 degrees, and if it bends, it breaks. (4) Void ratio (ρ) The void ratio (Ρ 1 ) of the thermally conductive sheet before thermal curing of each of the examples and the comparative examples was measured by the following measurement method. Method for measuring void ratio: First, the thermally conductive sheet was cut in the thickness direction by a cross-section polisher (cp), and the cross-section thus obtained was observed by scanning electron microscopy (SEM) at 200 times. image. Then, the void portion and the other portions were subjected to binarization processing based on the obtained image, and then the area ratio of the void portion to the entire cross-sectional area of the thermally conductive sheet was calculated. The results are shown in Tables 1 to 3. (5) Step followability (three-point bending test) The heat conductive sheets before thermal hardening of the respective examples and comparative examples were subjected to the following test conditions in accordance with JIS K 7171 (2〇1〇). The point bending test was used to evaluate the step followability based on the following evaluation criteria. The results are shown in Tables 1 to 3. Test conditions Test piece: size 20 mm><15 mm Distance between fulcrums: 5 mm Test speed: 2 〇mm/min (pressure speed under the indenter) Bending angle: 120 degrees 153628.doc _ ^2 - (1) 201132691 (Evaluation criteria) ◎: No break was observed at all. 〇: Little break was observed. χ: A fracture was clearly observed. (6) Print mark visibility (print mark adhesion: mark adhesion by inkjet printing or laser printing) The heat conductive sheets of Examples 1 to 16 were printed by inkjet printing and laser printing. Print the mark 'and observe the mark. As a result, any of the thermally conductive sheets of Examples 1 to 16 was able to visually recognize the marks obtained by both the ink jet printing and the laser printing, and confirmed that the printed mark adhesion was good. (7) Volume resistance The volume resistance (R) of the thermally conductive sheets of the respective Examples and Comparative Examples was measured. Namely, the volume resistivity (R) of the thermally conductive sheet was measured in accordance with JIS κ 6911 (General Test Method for Thermosetting Plastics, 2006 Edition). The results are not in Tables 1 to 3. (8) Insulation breakdown test (jis C 2110 (2010 edition)) The insulation breakdown voltage was measured in accordance with JIS C 2110 (2010 edition) for the thermally conductive sheets obtained in the respective examples and comparative examples. That is, the 'insulation breakdown voltage is based on JIS C 2110-2 (2010 edition), "Solid Electrical Insulation Material - Test Method for Strength of Insulation Failure - Part 2: Test for Applying DC Voltage", by the step-up speed A short time (rapid boost) test of 1000 v/s was performed. 153628.doc -33- 201132691 The results are shown in Tables 1 to 3. (9) Glass transition point The glass transition point was measured for the thermally conductive sheets obtained in the respective examples and comparative examples. Namely, the thermally conductive sheet was analyzed by a dynamic viscoelasticity measuring apparatus (model: DMS6100, manufactured by SEICO Electronics Industrial Co., Ltd.) at a temperature rising rate of ^ / min and a frequency of 10 Hz. Based on the data obtained, the glass transition point was obtained in the form of the peak of tanS. The results are not in Tables 1 to 3. (10) Mass reduction measurement The thermal conductivity sheet obtained from each of the examples and the comparative examples was measured in accordance with JIS K 7120 by thermal mass analysis using a thermal mass spectrometer (heating rate of 10 〇/min, under a nitrogen atmosphere). 5% of the mass reduces the temperature. The results are not in Tables 1 to 3. (11) Initial adhesion test A. Initial adhesion test for notebook computer package substrates For the uncured heat conductive sheets of the respective examples and comparative examples, a notebook computer for packaging a plurality of electronic components was implemented. The initial adhesion tests (1) and (2) of the package substrate were used. That is, the thermal conductive sheet is placed on the surface of the package substrate for notebook computer (the side on which the electronic component is packaged) at 80 in a sponge roll containing a polyoxyl resin. (: (Examples 1 to 8 and Examples 10 to 16) or 120 °C (Example 9), heat-pressure-bonded and temporarily fixed, and after standing for 1 minute, the pen 153628.doc -34·201132691 was recorded. The package substrate for a computer is placed in the vertical direction (initial adhesion test (2)). Then, the package substrate for the notebook computer is directed to the lower side with the heat conductive sheet (ie, after being temporarily fixed) The state of the state is reversed and reversed (the initial adhesion test). In the above initial adhesion test (1) and initial adhesion test (2), the thermally conductive sheet was evaluated according to the following criteria. The results are shown in Tables 1 to 3. [Standards] 〇·There was a loss of the thermally conductive sheet from the package substrate of the notebook computer. X: It was confirmed that the thermally conductive sheet was detached from the package substrate for the notebook computer. B. Initial Adhesion Test for Stainless Steel Substrate For the uncured heat conductive sheets of the respective examples and the comparative examples, the initial adhesion to the stainless steel substrate (manufactured by Sus3 4) was carried out in the same manner as described above. (1) and (2), and in the above initial adhesion test (1) and initial adhesion test (7), the thermally conductive sheet was evaluated according to the following criteria. The results are shown in Tables 1 to 3. Benchmark> (10) The heat conductive sheet does not fall off from the non-ferrous steel substrate. It is confirmed that the heat conductive sheet is detached from the stainless steel substrate. (12) The alignment angle of the boron nitride particles (α) 153628.doc -35- 201132691 The heat conductive sheet is cut along the thickness direction by a cross-section polisher (cp), and the resulting cross section is photographed by a scanning electron microscope (SEM) at 100 to 2000 times, according to the obtained SEM photograph (refer to 3 to 7), the inclination angle (α) of the longitudinal direction (LD) of the boron nitride particles with respect to the plane direction (SD) of the thermally conductive sheet is obtained, and the boron nitride particles are calculated as the average value thereof. The angle of alignment (c〇. The results are shown in Table 1 to Table 3. (13) Dynamic viscosity of resin component Each example and each comparative example were measured by the dynamic viscosity test according to JIS K 7233 (bubble viscosity meter method). The dynamic viscosity of the resin component used in the process. The resin component and the standard product are dissolved in a solvent (butyl carbitol) at a temperature of 25 ± 0.5 C at a solid concentration of 4 〇 mass / , to prepare a resin component sample and a standard sample, respectively. According to its dynamic viscosity, it is divided into A5~Al, A~Z, and Z1~Z10, and the corresponding dynamic viscosity is in the range of 0.005χ10·4 m2/s~1066x10·4 m2/s. Comparing the rising speed of the bubble in the resin component sample with the rising speed of the bubble in the standard sample (the known dynamic viscosity is known), and determining the dynamic viscosity of the standard sample having the same rising speed as the dynamic viscosity of the resin component, thereby The dynamic viscosity of each resin component was measured. The results are shown in Tables 1 to 3. Table 1 153628.doc -36· 8 201132691 Table 1 Campan you 1 Example 1 Example 2 Average 'Ion ium, Example 3 Example 4 Example 5 Example 6 Nitride shed particles / g * A / Γ · 3#接〇/1Ί·Β PT-110** 45 3.83 [40] [38.81 5.75 [50] [48.81 12.22 [68] [66.91 23 [80] [79.21 • 12.22 [68] fAA Q1 Sister is very /0J / [volume%]*. UHP-1 «2 9 - - - 12.22 [68] Γ66.9Ί ”ooy| Each epoxy resin A®3 _ (ample energy) 3 3 3 3 3 _ /VSl epoxy resin B*4 ( Liquid) - - - - - 1.5 Thermosetting Epoxy Resin Epoxy Resin C*5 (Gold Bear) - - - - - 1.5 Square Polymeric Resin Composition Epoxy Resin 〇86 (Gold Bear) - - - - Hardener (solid content ε) 3 (0.15) 3 (0.15) 3 (015) 3 (0.15) 3 (0.15) 3 (0.15) Hardener s8 (solid component e number) - - - - Thermoplastic resin Ethylene - - - - - Article temperature (°c) 80 80 80 80 80 80 Number of hot presses (times) *D 5 5 5 5 5 5 Pieces of load (MPa) / (tons) 20/5 20/5 20/ 5 20/5 20/5 20/5 Thermal conductivity direction (SD) 4.5 6.0 30.0 32.5 17.0 30.0 Thickness direction (TD) 1.3 3.3 5.0 5.5 5.8 5.0 Ratio (SD/TD) 3.5 1.8 6.0 5.9 2.9 6.0 Softness / Flexibility test JISK 5600-5-1 ◎ ◎ ◎ ◎ 〇 ◎ void ratio (% by volume) 0 0 5 12 6 4 Step follower/three-point distortion test JISK 7171 (2008) 〇〇〇〇〇〇 Volume resistance (Ocm) JISK 6911 (2006) 5.5χ1014 3.4χ1014 2.1Χ1014 1.3χ1014 1.7χ1014 2.2:<1014 Thermal Conductive Sheet Insulation Breakdown Voltage (kV/_) JISC 2110(2010) 48 51 38 21 40 39 Review Glass Transfer Point rc) 139 140 139 138 140 130 Price 5 % weight reduction temperature JIS K 7210 318 327 333 381 341 344 VS notebook computer test (1) 封装 initial adhesion test substrate test (2) 〇〇〇〇〇〇 test VS stainless test (1) 〇 〇〇〇〇〇Steel substrate test (2) 〇〇〇〇〇〇 nitriding collar particle alignment angle (6) (degrees) 18 18 15 13 20 15 Polymer dynamic viscosity corresponding standard A2 ~ D Α 2 ~ D Α 2 ~ D Α2~D A2-D A2~D Polymer degree JIS K 7233 (bubble viscosity meter method) Dynamic viscosity fxlO^mVs) 0·22~ 1.00 0.22- 1.00 0.22- 1.00 0.22- 1.00 0.22 〜 1.00 0.22- 1.00 g*A : Dispensing quality [Zhao product%]*8 : Percentage of total relative to heat-conducting sheet (excluding hardener) [% by volume]*C : Number of times relative to total volume of heat-conductive sheet *D : Laminated sheet The number of hot pressing times -37- 153628.doc 201132691 Table 2 Table 2 Example Average Particle Size (um) Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Formulation of each component Formulation of nitriding shed particles / g * A / [% by volume] * 8 / [馑Product %^ PT-110*1 45 12.22 [68] [66.9] 12.22 [68] [66.91 3.83 [60] Γ60] 13.42 [70] Γ69] 3.83 [40] Γ37.71 13.42 [70] UHP-1*2 9 - - - - Polymer thermosetting resin Epoxy resin month a composition Epoxy resin A15» ίFeng solid state) - - - - 3 3 氡 resin 8〃4 ί liquid form) 3 - - - - Epoxy Resin (solid) - 3 - - - - Epoxy ί solid) - - - 3 - - Hardener ί Solid component g number) 3 (0.15) 3 (0.15) - 3 (0.15) 6 (0.3) 3 (0.15 ) Hardener & ί solid component g number) - - - - - - Thermoplastic resin polyethylene 589 - - 1 - Manufacturing conditions Hot pressing temperature (°c) 80 80 120 80 80 60 times (times)*D 5 5 5 5 5 5 Load (MPa) / («S〇20/5 20/5 4/1 20/5 20/5 20/5 Evaluation of thermal conductivity sheet thermal conductivity (W/mK) Surface orientation (SD) 30.0 30.0 20 24.5 4.1 10.5 Thickness direction (TD) 5.0 5.0 2.0 2.1 1.1 2.2 Ratio (SD/TD) 6.0 6.0 10.0 11.7 3.7 4.8 Softness/bending resistance test JIS K 5600-5-1 〇Δ X 〇◎ 陈 陈 rate (% by volume) 2 13 1 10 0 29 Step follower/three-point test JISK 7171 (2008) 〇 XXX ◎ ◎ Accident resistance (Ocm) JISK691U2006) 2.4χ 1014 l.lx 10丨4 4.1x 1014 1.3χ 1014 6.4χ 1014 0.6χ 1014 Insulation damage (kV/mm) JIS C 2110(2010) 37 18 40 24 48 10 Glass Transfer Point (°c) 168 107 •24 217 145 138 5% Weight Reduction Temperature JIS K 7210 357 325 430 370 310 352 Initial Adhesion Test VS Notebook PC Package Test (1) 〇〇〇〇〇〇 Test (2) 〇〇〇〇〇〇VS stainless steel substrate test (1) 〇〇〇〇〇〇 test (2) 〇〇〇〇〇〇 boron nitride particles... alignment angle (〇0(廑) 16 16 15 16 20 17 Dynamic viscosity of polymer polymer JIS K 7233 (bubble viscosity meter method) Corresponding standard A5 Z . ΙΜ3 Α2~D A2-D Dynamic viscosity (xlO^mVs') 0.005 5.00 - 1.00- 1.55 0.22 〜 1.00 0.22^ 1.00 g*A : blending quality [% of accumulation] *8 : relative to the total volume of the thermally conductive sheet (except hardener) Fraction [% by volume]*C: number of times relative to the total volume of the thermally conductive sheet *D: number of hot pressing of the laminated sheet 153628.doc • 38 - 8 201132691 Table 3 Table 3 Example · Example Average particle size Example 13 Example 14 Example 15 Example 16 Comparative Example 1 Comparative Example 2 Formulation of each component Boron nitride particles / g * A / [% by volume] * 8 / [% by volume] * C PT- 110 Magic 45 13.42 P〇] [691 13.42 [70] 『691 13.42 [70] Γ691 13.42 [70] [691 1.44 [20] ΓΙ9.31 2.46 ρο] 『291 UH P-1*2 9 - - Polymer heat Curable resin epoxy resin A*3 ί丰固熊) 3 3 3 - 3 3 Epoxy resin Β%4 (liquid) - - - 1 - - Epoxy resin combination epoxy resin (: milk (solid) • - - - - - 氡 氡 resin 〇 _ (solid) - - - 2 - hardener ~ (solid number of turns) 3 (0.15) 3 (0.15) 3 (0.15) - 3 (0.15) 3 (0.15) _ Hardener (also ε of solid content) - - - 3 (0.15) - - Thermoplastic resin polyethylene 859 - - - - - Manufacturing conditions Hot pressing temperature (°C) 70 80 80 80 80 80 Times (times)*D 5 5 5 5 5 5 (MPa)/(ton) 20/5 20/5 40/10 20/5 20/5 20/5 Evaluation of thermally conductive sheets & Thermal conductivity (W/mK) Surface orientation (SDI 11.2 32.5 50.7 30 1.5 1.1 Thickness Direction (TD) 3.0 5.5 7.3 2.0 5.7 0.6 Ratio (SD/TD) 3.7 5.9 6.9 15.0 0.3 1.8 Flexibility/back resistance test JISK 5600-5-1 〇◎ 〇◎ XX Void ratio (body fine °/〇) 26 8 3 4 0 0 Step follower/three-point bending test JIS K 7171 (2008) ◎ ◎ 〇 ◎ 〇 0 Volume resistance (Ω·αη) JISK 6911 (2006) 0.8χ1014 2.5M014 5.3><1014 2χ1〇 '4 8.2χ1014 79χ10,4 Dielectric breakdown voltage (kV/mm) JIS 0 2110(2010) 12 30 43 45 53 50 Glass transfer point rc) 138 139 139 216 139 138 5% weight reduction 3 ^JISK7210 348 355 350 362 280 285 Initial Adhesion Test VS Notebook PC Package Test (1) 〇〇〇〇〇〇 Test (2) 〇0 〇〇〇〇VS Stainless Steel Substrate Test (1) 〇〇〇〇〇〇 Test (2) 〇 〇〇〇〇〇Boronium nitride particle alignment angle >1 change (〇0 (degrees) 15 15 13 12 31 34 Dynamic viscosity of polymer polymer ns K 7233 (bubble viscosity meter method) Corresponding Standards A2~D A2~D A2~D Α2~D A2-D Α2~D Dynamic Viscosity (xurV/s) 0.22- 1.00 0.22 ~ 1.00 0.22~ 1.00 0.22 ~ 1.00 0.22~ 1.00 0.22~ 1.00 g*A : Formulation mass [% by volume]*8: Percentage relative to the total volume of the heat conductive sheet (excluding the hardener) [% by volume] 1^: The number of times with respect to the total volume of the heat conductive sheet *D ··Laminated sheet The number of hot presses - 39 - 153628.doc 201132691 The numerical values of the respective components in Tables 1 to 3 indicate the g number unless otherwise specified. Furthermore, in the barrier of boron nitride particles in Tables 1 to 3, the value of the upper stage is the blending mass (g) of the boron nitride particles, and the value of the middle section is the side of the nitride side of the thermally conductive sheet relative to the hardening. The volume fraction of the total volume of the solid component outside the agent (ie, the solid content of the boron nitride particles and the epoxy resin or polyethylene) (volume ° / 〇) 'The value of the lower segment is the boron nitride particle relative to the thermally conductive sheet The volume fraction (volume/〇) of the total volume of the solid component (i.e., the solid content of the boron nitride particles and the epoxy resin and the hardener). In addition, in each component of Tables 1 to 3, the details of the components attached to the symbols of ※ are described below. PT-110. Trade name, plate-shaped nitride shed particles, average particle size (light scattering method) 45μηι, manufactured by Japan Momentive Advanced Materials Co., Ltd. UHP-02 : trade name: SH0BN UHIM, plate-shaped boron nitride particles, average particle Diameter (light scattering method) 9 μιη, manufactured by Showa Denko Co., Ltd. 8*3 : OGSOL EG (trade name), bisaryl fluorene epoxy resin, semi-solid, epoxy equivalent 294 g/eqiv·, softening temperature (Universal Law) 47. 〇, melt viscosity (80. 〇 1360 mPa.s, Osaka Gas Chemicals (Osaka Gas Chemicals) company made epoxy resin 3: JER828 (trade name), bisphenol A epoxy resin, liquid, epoxy equivalent 184~ 194 g/eqiv., softening temperature (global method) less than 25 ° C, melt viscosity (80 ° C) 70 mPa.s, Japan epoxy resin (Japan Epoxy Resins) company made epoxy resin 0^5: JER1002 ( Trade name), bisphenol A epoxy resin, solid-40· 153628.doc 8 201132691 state, epoxy equivalent 600-700 g/eqiv., softening temperature (ring and ball method) 78 ° C, smelting viscosity (80 °) C) 10000 mPa, s or more (above the measurement limit), epoxy resin port manufactured by Japan Epoxy Resin Co., Ltd. *6 : EPPN-501HY (trade name), triphenylmethane type epoxy resin, solid state, epoxy equivalent 163~ 175 g/eqiv•, softening temperature (global method) 57 to 63 ° C, manufactured by Nippon Kayaku Co., Ltd. *7 : 5 mass % methyl ethyl ketone solution of Curezol 2PZ (trade name, manufactured by Shikoku Chemicals Co., Ltd.) Hardener*8 : 5 mass % mercapto ethyl ketone of Curezol 2P4MHZ-PW (trade name, manufactured by Shikoku Chemicals Co., Ltd.) Dispersion polyethylene*9: low-density polyethylene, mass average molecular weight (Mw) 4000, number average molecular weight (Mn) 17 〇〇, manufactured by Aldrich Co., Ltd., the above description is provided as an exemplified embodiment of the present invention, It is merely illustrative and not limiting. It should be understood by those skilled in the art that the modifications of the present invention are also included in the scope of the claims described below. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a thermally conductive sheet of the present invention. Fig. 2 is a perspective view for explaining a method of manufacturing the thermally conductive sheet shown in Fig. 2, and (a) shows a step of hot pressing a mixture or a laminated sheet, (b) The step of dividing the pressed sheet into a plurality of sheets, and (c) showing the step of forming the laminated sheets. 153628.doc -41 - 201132691 FIG. 3 is a graph showing the thickness of the thermally conductive sheet after hardening of the example. Fig. 4 is an image processing diagram showing an SEM photograph of a cross section along the thickness direction of the thermally conductive sheet after curing in Example 3. Fig. 4 is a view showing an image of an SEM photograph of a cross section in the thickness direction of the thermally conductive sheet after curing in Example 3. An image processing chart of the SEM photograph of the cross section along the thickness direction of the thermally conductive sheet after hardening of Example 5. Fig. 6 shows the thickness direction of the thermally conductive sheet after curing of Comparative Example 1. Fig. 7 is an image processing diagram showing an SEM photograph of a cross section along the thickness direction of the thermally conductive sheet after curing in Comparative Example 2. Fig. 8 is a graph showing the relationship between the ratio of the boron nitride particles in Examples 1 to 4, Comparative Examples 2 and 2 and the thermal conductivity of the thermally conductive sheet. Fig. 9 is a perspective view showing a test device (before the bending resistance test) of the model I of the bending resistance test. Fig. 10 is a perspective view showing a test device (in the middle of the bending resistance test) of the model I of the bending resistance test. [Main component symbol description] 1 Thermal conductive sheet 1A Pressed sheet 1B Split sheet 1C Laminate sheet 2 Nitrided butterfly particles 3 Resin component 4 Release film 153628.doc .42 8 201132691 10 Model I test device 11 1 plate 12 2nd plate 13 Mandrel 14 Stop LD Long-side direction SD Face direction TD Thickness direction a Alignment angle 153628.doc ·43·

Claims (1)

201132691 VII. Patent application scope: It contains a plate-like nitriding butterfly-type thermal conductive sheet, which is characterized in that: particles, and the content ratio of boron nitride particles is 35 vol% or more, the phase of the above thermally conductive sheet The conductivity is above mK. The heat in the direction of the parent in the direction of the dimension 2. The thermal conductive sheet of claim 1 has an average particle diameter determined by the light scattering method, wherein the boron nitride particles are 20 μm or more. 3. The thermally conductive sheet according to claim 1, wherein in the bending resistance test according to the cylindrical mandrel method according to JIS K 5600-5-1, the above-mentioned test condition # 4 shells of the above thermally conductive sheet When the fracture was not observed on the above thermally conductive sheet: Test condition Test apparatus: Model i Mandrel: diameter 10 mm Bending angle: 90 degrees or more Thickness of the above thermally conductive sheet: 〇·3 mm 〇4 · As § The thermally conductive sheet of the item 1 further contains a resin component, and the resin component is subjected to an kinetic viscosity test according to JIS κ 7233 (bubble viscosity meter method) (temperature: 25 it ± 0.5. (:, solvent: The dynamic viscosity measured by butyl carbitol and a solid content concentration of 40% by mass is 〇.22><10·4 to 2·0〇χ10·4 m2/s. 153628.doc