TW201231487A - Liquid-crystalline resin composition, heat dissipation material and precursor of the same - Google Patents

Abstract

A liquid-crystalline resin composition comprises: a liquid-crystalline epoxy resin represented by the following Formula (1), a curing agent, and a composite particle including an aluminum nitride particle having a first covering layer which comprises alpha aluminum oxide and covers at least a part of a surface region of the aluminum nitride particle and a second covering layer which comprises an organic compound and covers a surface region of the aluminum nitride particle other than the surface region covered by the first covering layer. In the formula, X represents a single bond or a connecting group represented by the following chemical formulae. Y represents an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, or the like. n represents an integer from 0 to 4.

Description

201231487 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a liquid crystalline resin composition and a heat dissipating material thermal material. [Prior Art] In recent years, as electronic devices have become smaller and higher in performance, the heat dissipation property of the insulating material constituting the electronic device has been increasing. Further, in the insulating material, an organic material is used in view of easiness of insulation withstand voltage. In the liquid crystal resin which is a monomer having a liquid crystal group having a high alignment property, it is effective, for example, in the above-mentioned Japanese Patent Publication No. Hei. Further, in order to improve the heat dissipation property of the organic material, a method of adding a high thermal conductivity and insulating material is generally employed. As the insulating material, there is aluminum nitride. However, aluminum nitride-based water reacts to produce ammonia while being produced on the surface of aluminum nitride, and the thermal conductivity is greatly reduced. Therefore, a method of improving the water resistance by coating the surface of aluminum nitride with no matter is widely used. As an example of surface-coating with an inorganic material, a method of making α-alumina is known. However, in the method of making the aluminum nitride surface of α-alumina, there is a possibility that the water resistance of the α-alumina is drastically lowered. In the related art, in the case of the precursor of the α-alumina and the heat generation of the α-alumina, it is required to use a high-density or high-heat-transfer carrier to form a high-heat-transfer carrier. The rate is high, and it is easy to form an aluminum hydroxide machine or an organic thermal conductivity in the atmosphere, which is formed in the cracking of the material. For example, in the special cracking countermeasure, 201231487, by using an inert gas in the heat-treated ambient gas, Reduce the cracking of the dip. As a method of surface-coating with an organic material, for example, JP-A-2004-115369 discloses a method of surface treatment of a nitriding of a distillate by an aliphatic hydrocarbon. When the surface treatment of the distillate is carried out with an aliphatic hydrocarbon, high water resistance is obtained. [Problems to be Solved by the Invention] However, in the method of coating aluminum nitride with an organic material as described in Japanese Laid-Open Patent Publication No. 2004- 1 155 369, the thermal conductivity of the coating material is greatly reduced. . Further, since the affinity of the surface-treated mash and the liquid crystalline resin is low, the alignment of the liquid crystalline resin around the mash is disturbed, so that the thermal conductivity is lowered. An object of the present invention is to provide a liquid crystalline resin composition capable of forming a cured product having excellent thermal conductivity and excellent in water resistance, a method for producing the same, and a high thermal conductive heat dissipating material precursor formed using the liquid crystalline resin composition and Still thermal conductive material. [Means for Solving the Problem] The present invention includes the following aspects: <1> A liquid crystalline resin composition containing a liquid crystalline epoxy resin represented by the following formula (i), a curing agent, and nitrogen Aluminum composite particles,

S -6-201231487 The composite particles have aluminum nitride particles, a region covering at least a part of the surface of the aluminum nitride particles, and a first coating layer containing a-alumina and a region other than the coating layer and covering the nitriding The second coating layer containing the organic substance on the surface of the aluminum particle 'Chemical 1】

The formula (1 valent group represents a carbon group, a fluorogenic sulfhydryl group; η 〜 8 is a whole [Chemical 2] - Ν = Ν - ) where 'X represents a single bond or a group selected from the following chemical formula 2 At least one of the linking groups; γ each independently having an aliphatic hydrocarbon group of 1 to 8; an aliphatic alkoxy group having 1 to 8 carbon atoms; a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group or a An integer of 0 to 4 is represented, k represents an integer of 0 to 7, and m represents a number of 0 '1 represents an integer of 0 to 12. c III c

CH

N

CH II CH

Η3 CIC II CH

CHO I CH II CH o

CMO

Nfo II N —C=N— Η » Ο

The liquid crystal resin composition according to the above-mentioned <1>, wherein the organic substance is a reaction product of the aluminum nitride and an organic compound, and the organic compound has at least an alcoholic hydroxyl group and a carboxyl group. One, and a hydrocarbon group having a carbon number of 1 to 24. <3> The liquid crystalline resin composition described in the above <1> or <2>, wherein the content of the aluminum nitride composite particles is 50% by mass to 95% by mass. The liquid crystalline resin composition according to any one of the above-mentioned, wherein the aluminum nitride composite particles correspond to the X-ray diffraction spectrum of the CuKa line. The peak of the (1 〇〇) plane of the α-alumina is less than or equal to 1 on the basis of the area ratio of the peak corresponding to the (1 1 3 ) plane of the aluminum nitride. &lt;5&gt; The semi-cured material of the liquid crystalline resin composition according to any one of the above-mentioned items of the above-mentioned. &lt;6&gt; A flaky semi-cured material of the liquid crystalline resin composition according to any one of <1> to <4>. &lt;7&gt; A prepreg comprising a fiber base material and a half of the liquid crystalline resin composition described in any one of the above-mentioned &lt;1&gt; Hardened material. &lt;8&gt; A heat-dissipating material, which is a cured product of the liquid crystalline resin composition according to any one of the above-mentioned items. The heat-dissipating material according to the above-mentioned <9>, wherein the cured product of the liquid crystalline epoxy resin has an alignment surface, and the alignment surface has a surface of 50 to 90 with respect to the surface of the aluminum nitride composite particles. . Angle.

The slab of the liquid crystal resin composition according to any one of the above-mentioned items, The resin sheet of the above-mentioned &lt;6&gt; and the hardened layer of at least one resin-containing layer selected from the prepreg according to the above &lt;7&gt;. &lt;11&gt; A metal substrate comprising a metal foil, a metal plate, and any one of the above-mentioned &lt;1&gt; to &lt;4&gt;, supported by the metal foil and the metal plate A resin layer composed of a resin composition, a B-stage sheet according to the above &lt;6&gt;, and a cured layer of at least one resin-containing layer selected from the prepreg described in <7>. &lt;1 2&gt; A printed wiring board having a wiring layer, a metal substrate, and any one of the above-mentioned <1> to <4> between the wiring layer and the metal substrate. A resin layer composed of a resin composition, a resin sheet described in the above &lt;6&gt;, and a cured product of at least one resin-containing layer selected from the prepreg described in <7>. &lt; 1 3 &gt; A method for producing a liquid crystalline resin composition, comprising: calcining an aluminum nitride particle in an oxygen-containing atmosphere, and forming an α-oxidation having cracks on a surface of the aluminum nitride particle a step of forming an aluminum layer; forming a cracked portion of the aluminum nitride particles having an α-alumina layer on the surface, and exposing the organic compound having at least one of an alcoholic hydroxyl group and a carboxyl group and a hydrocarbon group having 1 to 24 carbon atoms The aluminum nitride is reacted to obtain aluminum nitride composite particles: and the aluminum nitride composite particles are dispersed in a composition containing a liquid crystalline epoxy resin and a hardener represented by the following general formula (1) Steps: 201231487 【化3】

(Y)n (Υ)η In the formula (1), 'X represents a single bond or an aliphatic hydrocarbon group which at least independently represents a carbon number of 1 to 8 in a group selected from a divalent group represented by the following chemical formula, Carbon number 1 alkoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom or ethylidene group; η represents an integer of 0 to 4, k represents 0 to represent an integer of 0 to 8, and 1 represents an integer of 〇~12. 【化4】—N=N一—CEC—-Sa N· -c=c— Η I CH3 S=f Self-family m Each fat nitrate, Y fat, number;

,c=c- H I CN •O-C· II O ♦ o •C=N-H , O

&lt;14&gt; A heat-dissipating material. The method for producing a precursor, which comprises the step of heat-treating the liquid crystalline resin composition described in any one of the above &lt;1&gt; to &lt;4&gt;&lt;15&gt; A method for producing a heat-dissipating material, which comprises heating the liquid resin composition according to any one of the above-mentioned items, wherein the liquid resin composition is -10 -

S 201231487 The step of hardening. [Effects of the Invention] According to the present invention, it is possible to provide a liquid crystalline resin composition capable of forming a cured product having excellent thermal conductivity and having excellent water resistance, a method for producing the same, and a high thermal conductivity formed by using the liquid crystalline resin composition. [Embodiment] [Embodiment] The term "step" in this specification is not only an independent step, but when it is not clearly distinguishable from other steps, The intended function of the step is also included in the term. Further, the numerical range indicated by "~" in the present specification means that the number 含有 described before and after the "~" is regarded as the range of the minimum 値 and the maximum 各自. In addition, in the present specification, when the amount of each component in the composition is present, when the substance corresponding to each component in the composition is present in plural, unless otherwise specified, it means that the plural exists in the composition. The total amount of matter. &lt;Liquid Crystal Resin Composition&gt; The liquid crystal resin composition of the present invention contains a liquid crystalline epoxy resin represented by the following formula (1), a curing agent, and aluminum nitride composite particles (hereinafter also referred to as "composite particles"), the composite particles having aluminum nitride particles, a region covering at least a part of a surface of the aluminum nitride particles, and a first coating layer containing α -11 - 201231487 alumina, and coating the aluminum nitride particles The area other than the first coating layer on the surface and the second coating layer under the second coating layer containing the organic material may be composed of other components. 【化5】

In the formula (1), X represents a single bond or a linking group selected from at least one of the group consisting of a divalent group represented by the following chemical formula; and γ each independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms. , an aliphatic oxy group having a carbon number of 1 to 8, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group or an ethyl fluorenyl group; η represents an integer of 〇~4, and k represents an integer of 〇~7 , m represents an integer from 0 to 8, and 1 represents an integer from 〇 to 12^ [Chem. 6]

The present invention is applicable to a high heat conductive heat dissipating material such as a laminate sheet of a resin component, a printed wiring board, or a heat dissipating sheet, which is a component of an electronic component or an electronic device. Further, as the precursor of the heat dissipating material, a material of a semi-hardened state of the resin composition of -12 to 201231487 and a liquid crystal resin composition to which the materials are applied can be applied. By coating the surface of the aluminum nitride particles with alumina which is vertically aligned by the liquid crystalline epoxy resin represented by the above formula (1), the thermal resistance due to the disorder of the alignment of the liquid crystalline epoxy resin can be reduced. In the present invention, the surface of the aluminum nitride particles is coated with α-alumina having a relatively good thermal conductivity, and the thermal conductivity of the resin composition can be suppressed as compared with the case of coating with an inorganic substance such as an organic substance or an alumina other than α-alumina. Reduced. Further, by coating the surface of the aluminum nitride with α-alumina and an organic material, the water resistance can be improved as compared with the case of coating only with α-alumina. Further, by coating the surface of the aluminum nitride with an organic compound having a carboxyl group or an alcoholic hydroxyl group having a hydrophilic group, the affinity between the resin component and the aluminum nitride particles can be improved as compared with the case of coating with an organic substance having only a hydrocarbon. It can suppress the decrease in thermal conductivity. Further, when the cured product is formed by the introduction of the hydrophilic group, the alignment property of the liquid crystalline epoxy resin represented by the above formula (1) can be suppressed. Particularly, by controlling the alignment property of the resin component, the liquid crystalline epoxy resin represented by the above formula (1) is vertically aligned with the aluminum nitride particles, and the thermal resistance at the interface between the composite particles and the resin component can be reduced. The term "vertical alignment" as used in the present invention means that the molecules of the liquid crystalline epoxy resin are inclined and aligned with respect to the surface of the composite particles. The inclination angle is 50 to 90 in the present invention, preferably 70 to 90. That is, the liquid crystalline epoxy resin forms a cured product having an alignment surface, and the alignment surface of the cured product is preferably aligned at a predetermined inclination angle with respect to the surface of the composite particles. Fig. 3 schematically shows an example of the alignment state of the cured product on the surface of the composite particles -13 - 201231487. As shown in FIG. 3, on the surface 22 of the composite particle, the liquid crystal group 20 of the liquid crystalline epoxy resin is aligned in a certain direction, and the cured system of the liquid crystalline epoxy resin has a specified inclination angle. The alignment is on the surface of the composite particles. In particular, it is considered that when the surface of the composite particles is coated with an organic compound having a hydrophilic group of a carboxyl group or an alcoholic hydroxyl group, an alignment state as shown in Fig. 3 is easily obtained. Further, it is considered that excellent thermal conductivity is exhibited by this. On the other hand, it is considered that when the composite particle surface 24 is covered with an organic substance having only a hydrocarbon group, as shown in Fig. 4, the alignment of the liquid crystal group 20 is in a slightly chaotic state. (Aluminum nitride composite particles) The liquid crystalline resin composition of the present invention contains at least one kind of aluminum nitride composite particles, and the composite particles have aluminum nitride particles and a region covering at least a part of the surface of the aluminum nitride particles and contain α. The first coating layer of alumina and the second coating layer containing an organic substance in a region other than the first coating layer covering the surface of the aluminum nitride particles. In the composite particles, the surface of the aluminum nitride particles is coated with the first coating layer containing α-alumina and the second coating layer containing the organic material, and is excellent in heat conductivity and water resistance. In addition, when the second coating layer contains an organic substance, for example, it is excellent in compatibility and dispersibility with a resin, when the resin composition is formed, the viscosity can be suppressed, and a resin composition excellent in moldability and adhesion can be formed. When the first coating layer containing α-alumina having good thermal conductivity is formed on the surface of the aluminum nitride particles, it is necessary to heat-treat at a high temperature. Therefore, to contain -14-

S 201231487 The first coating layer of α-alumina is difficult to cover the entire surface of the aluminum nitride particles, and cracks occur in the first coating layer to form a region where the aluminum nitride is exposed. By providing the second coating layer containing an organic substance in the region where the aluminum nitride is exposed, it is possible to form composite particles excellent in water resistance while maintaining excellent thermal conductivity. The surface state of such a composite particle can be analyzed, for example, by using a scanning electron microscope (SEM-EDX) equipped with an energy dispersive X-ray analyzer, and the oxygen atom (0) corresponding to the first coating layer containing α-alumina, It is observed corresponding to the distribution of the carbon atom (C) of the second coating layer containing the organic substance and the aluminum atom (Α1) corresponding to the α-alumina and the aluminum nitride. In the present invention, the ratio of the amount of the first coating layer on the surface of the aluminum nitride particles to the amount of the second coating layer present is not particularly limited, but from the viewpoint of thermal conductivity and water resistance, on the atomic basis The second coating layer/first coating layer is preferably from 0.01 to 1.0, more preferably from 0.1 to 0.5. Further, the amount of the first coating layer on the surface of the aluminum nitride particles and the amount of the second coating layer present can be calculated by SEM-EDX to quantify the distribution amounts of oxygen atoms and carbon atoms, respectively. In addition, the content ratio of the organic substance contained in the composite particles is not particularly limited, but is preferably from 0. 01% by mass to 0.5% by mass, more preferably from 0% by mass to 0.5% by mass, based on the thermal conductivity and water resistance. 〇.〇2% by mass to 0.05% by mass. Further, the content ratio of the organic substances contained in the composite particles can be calculated by thermogravimetric analysis. Specifically, the thermogravimetric analysis device (TGA) can be used to measure the heating of the composite particles under the conditions of a measurement range of 25° C. to 800° C. and a temperature increase rate of 15 to 201231487 of 10° C./min. The change in weight is calculated by measuring the weight loss associated with the thermal decomposition of the organic matter. The content ratio of the organic substance contained in the composite particles can be controlled, for example, by appropriately selecting various conditions in the organic layer formation step to be described later. Specifically, for example, by appropriately selecting the kind or concentration of the compound in contact with the aluminum nitride particles on which the first coating layer is formed, the contact time or the contact temperature, the content ratio of the organic substances contained in the composite particles can be desired. In the present invention, the layer thickness of the coating layer (first coating layer of X alumina) formed on the surface of the aluminum nitride particles is not particularly limited. The layer thickness of the first coating layer is from heat conduction. From the viewpoint of the water resistance and the water resistance, it is preferably 1 nm or more and 300 nm or less, more preferably 1 nm or more and 500 nm or less from the viewpoint of thermal conductivity, and particularly preferably 10 nm or more from the viewpoint of water resistance. 500 nm or less. The layer thickness of the first coating layer may correspond to the (10 〇) plane peak (a) of a alumina and the (113) plane corresponding to aluminum nitride in the X-ray diffraction of the CuKa line. The peak (B) is estimated from the area-based intensity ratio (a/b). Specifically, the layer thickness of the first coating layer containing a-alumina can be calculated from the obtained intensity ratio. Specifically, it is calculated as follows. Layer thickness of the first coating layer 〇 first coating layer The layer thickness is for the (100) plane peak (a) of a alumina and the peak (B) of the (113) plane corresponding to nitriding in the X-ray diffraction of the C u K a line. ICDD( International -16- s 201231487

Based on the data, the Centre for Diffraction Data) normalizes the integrated intensity ratio (A/B) of each peak to a volume ratio of alpha alumina to aluminum nitride. The layer thickness of the first coating layer can be calculated from the volume ratio of the α alumina to the aluminum nitride and the particle diameter of the composite particles. Further, the intensity ratio of the peak corresponding to the (100) plane of the α-alumina in the X-ray diffraction with respect to the peak corresponding to the (Π3) plane of the aluminum nitride was determined as follows. An X-ray diffraction spectrum (XRD) was measured using RINT2 5 0 0HL (manufactured by Rigaku Co., Ltd.) as an X-ray diffraction device and a CuKa line as an X-ray source. From the obtained X-ray diffraction spectrum, the peak corresponding to the (100) plane of α-alumina in the vicinity of 4 2.5° to 44.5° and the range of 32.5° to 33.5° in the vicinity of 2Θ to 33.5° are respectively identified. (113) The peak of the surface, and the peak intensity is obtained from the peak area. Based on the obtained peak intensity, the intensity ratio of the peak corresponding to the (100) plane of the α alumina to the area reference of the peak corresponding to the (1 1 3 ) plane of the aluminum nitride can be calculated. In the present invention, from the viewpoint of thermal conductivity and water resistance, the intensity ratio of the peak corresponding to the (1 〇〇) plane of the α alumina to the peak corresponding to the (! j 3 ) plane of the aluminum nitride, It is preferably 1 or less, more preferably 0.001 or more and 1 or less, and still more preferably 0.003 or more and 0.1 or less, and particularly preferably 0.003 or more 〇.〇2 or less from the viewpoint of thermal conductivity. When the intensity ratio is 1 or less, the ratio of the α-oxide crystallization crystal to the aluminum nitride in the composite particles is small, and the effect of high thermal conductivity due to compositing can be more effectively obtained. -17- 201231487 The layer thickness of the first coating layer containing α-alumina can be controlled, for example, by appropriately selecting various conditions in the oxidation step and the gelation step which will be described later. Specifically, for example, by appropriately selecting the amount of oxygen used in the oxidation step and the gelation step, or the amount of hydrolysis of the surface of the aluminum nitride, etc., the desired layer thickness and the particle shape of the composite particles can be, for example, Slightly spherical, flat, block, plate, and scale. From the viewpoint of dispersibility and thermal conductivity, it is preferably slightly spherical or flat. Further, the particle diameter of the composite particles is not particularly limited. For example, the volume average particle diameter may be 〇.5μτη~300μηι, and from the viewpoint of thermal conductivity and charging of the resin, it is preferably Ιμηη~ΙΟΟμηι, more preferably ΙΟμηι~ 5 0 μηι. The volume average particle diameter is measured using a laser diffraction method. The laser diffraction method can be carried out using a laser diffraction scattering particle size distribution measuring apparatus (for example, LS230 manufactured by Beckman-Coulter Co., Ltd.). The composite particles 10 coated with α-alumina and organic matter, for example, as shown in FIG. 2, can be obtained by calcining aluminum nitride particles 1 in an oxygen-containing gas atmosphere to form aluminum on the surface of the particles. a step of an oxide, (2) a step of crystallizing α-formed alumina on the surface to form an α-alumina layer 2 having a fine crack portion 3, and (3) having an alpha-alumina layer on the surface The aluminum nitride particles 1 of 2 and at least one of an alcoholic hydroxyl group and a carboxyl group are preferably an organic compound 4 and aluminum nitride containing two or more compounds and a hydrocarbon having 1 to 24 carbon atoms. The crack portion 3 of the α-alumina layer 2 is formed by a reaction step. -18-

S 201231487 Fig. 1 is an electron micrograph of an aluminum nitride particle having an α-alumina layer formed thereon, and cracks indicated by thick lines on the surface of the particles are not clearly shown on the drawing but fine cracks are formed on the entire surface of the particles. The aluminum nitride particles which can be used in the present invention can be applied, for example, to aluminum nitride particles formed by any one of a direct nitridation method, a reduction nitridation method, and a gas phase reaction method. Further, the aluminum nitride particles which can be used in the present invention may be a plurality of sintered particles of a single crystal of aluminum nitride or a crystal of aluminum nitride. Further, examples of the shape of the aluminum nitride particles include a slightly spherical shape, a flat shape, a block shape, a plate shape, and a scale shape. From the viewpoint of dispersibility and thermal conductivity, it is preferably slightly spherical or flat. Further, the particle diameter of the aluminum nitride particles is not particularly limited. For example, the volume average particle diameter may be from 55 μm to 300 Å, and from the viewpoint of thermal conductivity and recombination to the resin, it is preferably Ιμιη to ΙΟΟμιη, from the viewpoints of thermal conductivity and recombination to the resin. Look, better for ΙΟμιη~50μηι. The volume average particle diameter is measured using a laser diffraction method. The laser diffraction method can be carried out using a laser diffraction scattering particle size measuring device (for example, LS230 manufactured by Beckman-Coulter Co., Ltd.). The composite particles used in the present invention are composite particles in which a coating layer is formed on the surface of the aluminum nitride particles, and the coating layer is composed of α-alumina having cracks and is reacted with aluminum nitride in the crack portion. The formed organic compound is modified. In other words, the composite particles have aluminum nitride particles, a first coating layer containing α-alumina in a region covering at least a part of a surface of the aluminum nitride particles, and the first coating covering a surface of the aluminum nitride particles. Composite particles of a second coating layer containing a region other than the layer -19-201231487. The cracked α-alumina layer can be obtained by calcining the aluminum nitride particles in an oxygen-containing gas atmosphere at a temperature at which crystallization proceeds, preferably under nitrogen or an inert gas atmosphere. It is formed by gelatinization. Further, by calcining aluminum nitride in a limited amount of oxygen, alumina is formed at a temperature at which crystallization does not occur, and then crystallization occurs in an oxygen-free or oxygen-free environment, and α-alumina can be formed. Further, after the surface of the aluminum nitride is hydrolyzed, it can be formed by subjecting the produced alumina to α by calcination under nitrogen or an inert gas atmosphere. When the aluminum nitride particles having the α-alumina layer are formed, the alumina layer formed on the surface of the aluminum nitride is calcined in an oxygen atmosphere by calcination to crystallize the alumina, which is accompanied by crystallization. The interior of the resulting crack is further oxidized. When the inside of the crack is oxidized, it is difficult to mechanically coat the cracked portion only when the organic coating of the crack is performed after the firing. Therefore, it is preferred to cover the entire surface of the aluminum nitride particles other than the crack of the α-alumina layer by the α-alumina layer. That is, only the organic coating of the cracked portion is formed by calcination to form an α-alumina layer having cracks on the surface of the aluminum nitride, and then the particles are not reactive with alumina in the dehydrated organic solvent. The organic compound of the substituent reacted with aluminum nitride is reacted. After the reaction, by removing the excess organic compound, the composite particles of the coating layer are formed on the surface of the aluminum nitride particles, thereby forming aluminum nitride composite particles containing α-alumina having cracks in the coating layer and having Organic compound formed by reacting at least one of an alcoholic hydroxyl group and a carboxyl group and a hydrocarbon group having 1 to 24 carbon atoms in a crack portion and aluminum nitride

-20- S 201231487. Therefore, the calcination of aluminum nitride is preferably performed by crystallization of the first system at a temperature (for example, less than 1 1 oot), or after formation of alumina, or in an inert gas atmosphere, thereby forming α-oxygen. The aluminum nitride is calcined in a limited amount of oxygen, and after the formation of alumina at the crystallization temperature, the α-alumina can also be formed by crystallization of oxygen or oxygen. Further, it is known that when α-oxidation water resistance is formed on the surface of aluminum nitride, the formation method of the α-alumina layer formed on the surface is reduced. In the present invention, by reacting at least one aluminum nitride having an alcoholic hydroxyl group and a carboxyl group in the portion of the alpha alumina, the surface of the highly aluminum nitride particles having hydrophilicity is formed in the crack portion. The affinity of the resin. Therefore, as is known, the public cracking of the organic compound does not sufficiently coat the aluminum nitride, and the affinity between the particles and the resin cannot be improved, and the heat conduction is difficult. The coating thickness of the α alumina is determined by the known example (Japanese Patent Publication No. 2005-225947). In the intensity ratio of the (100) plane in the X-ray diffraction to the (113) plane of the aluminum nitride, the α-alumina (1 1 3 ) plane in the X-ray diffraction in the composite particles is obtained. The intensity ratio is preferably 1 or less. The strength tt is such that the ratio of α-alumina crystal to aluminum nitride is large, and it is difficult to obtain a high thermal conductivity effect, and it is impossible to compare the effect on the aluminum nitride alone. The effect of high thermal conductivity is obtained. The second system of crystallization is in aluminum nitride. Compounds and substances that cause cracking in the absence of a junction to increase the occurrence of cracks can be reported. The decrease in the surface rate of the particles is caused by the change of α-oxidation. Also, at 00) plane and nitrogen: if it exceeds 1, the particles coated to the composite machine are described in more detail below - 201131487 on the surface of aluminum nitride. A method of forming a cracked alpha alumina layer thereon. On the surface of the aluminum nitride particles, a coating layer containing α-alumina is formed by heat treatment at a temperature of 1 l ° C or higher. The coating layer (first coating layer) containing α-alumina is formed on the surface of the aluminum nitride particles by heat treatment at a temperature of 1 10000 ° C or more. On the other hand, when the temperature of the heat treatment is less than 1 00 ° C, the α crystallization is insufficient, and a coating layer containing α alumina cannot be formed. The method of forming the coating layer containing α-alumina on the surface of the aluminum nitride particles is not particularly limited, and may be appropriately selected from the methods generally used, and may directly form α-alumina on the surface of the aluminum nitride particles. The coating layer may be formed by forming alumina other than α-alumina such as γ-alumina on the surface of the aluminum nitride particles, and heat-treating at 1100° C. or higher to crystallize α to form α-alumina. The method of covering the layer. In the present invention, from the viewpoint of thermal conductivity and film thickness control, a method comprising forming a coating layer of alumina other than α-alumina containing γ-alumina or the like on the surface of the aluminum nitride particles is preferable. The oxidation step and the α-crystallization step of crystallizing α by heat treatment of the aluminum oxide particles on the surface of the aluminum nitride particles. Here, the oxidation step and the α formation step may be independently The oxidation step of forming a coating layer containing alumina other than α-alumina such as γ-alumina on the surface of the aluminum nitride particles may, for example, be an aluminum nitride particle. Heat treatment in an oxygen gas atmosphere to form alumina, heat treating the aluminum nitride particles in a limited amount of oxygen to form oxygen

-22- S 201231487 A method of aluminum forming, which is obtained by subjecting a surface of aluminum nitride to hydrolysis, and inerting to form alumina. Here, the inert gas environment is synonymous with the environment of the α-forming step described later. The aluminum nitride particles are preferably heated in an atmosphere of a limited amount of oxygen in accordance with the thickness of oxygen formed on the surface of the aluminum nitride particles. For example, the amount of oxygen may be from 5 ml to 50 ml with respect to the mass of l〇〇g. Further, as a method of hydrolyzing the surface of the aluminum nitride, the aluminum nitride particles may be placed in the atmosphere for 1 hour to 1 hour by stirring in a solvent having water. In the present invention, from the viewpoint of thermal conductivity, a method of alumina in an inert gas atmosphere after the particles are heat-treated to form oxygen or to hydrolyze the surface of the aluminum nitride in an atmosphere of a limited amount of oxygen. The heat treatment temperature of the oxidation step is preferably a temperature of not more than alumina, more preferably less than 1 00 ° C, and particularly preferably, the heat treatment time of the oxidation step can be suitably selected according to heat. From the viewpoint of thermal conductivity, it is preferably 10 minutes, more preferably 30 minutes to 120 minutes. The heat treatment in the oxidation step can be carried out at a constant temperature, for example, by raising the temperature from room temperature to a predetermined temperature, and it is preferred to carry out the temperature rise to a predetermined temperature from the viewpoint of thermal conductivity and productivity. Heat treatment. The aluminum nitride particles of the aluminum coating layer in the treatment of the inert gas in the heat in the gas atmosphere are exemplified in the usual method, and the method of heat-treating the aluminum aluminide is preferably carried out to form the crystallization of the aluminum alloy. The processing temperature is less than 1 000 ° C. The temperature is waited for ~2 0 minutes, and the example is carried out. In the present invention, when the heat treatment in the oxidation step is carried out from room temperature to 23-201231487 when the temperature is raised from the room temperature to the specified temperature, the specified temperature is preferably 1 1 oo ° C, and the temperature rise time is preferably 10 °c / min, the specified temperature is preferably 1 000 ° C, and the heating time is more preferably 10 ° C / min. Alpha crystallization can be performed by heat-treating alumina other than α-alumina formed on the surface of aluminum nitride at a high temperature (α-forming step). The heat treatment temperature in the α-crystallization step is preferably ll 〇〇 ° C or more, and more preferably H 50 ° C or more from the viewpoint of thermal conductivity. Further, the heat treatment time in the gelation step can be appropriately selected in accordance with the heat treatment temperature and the like. From the viewpoint of thermal conductivity, it is preferably 〇 2 hours to 3 hours, more preferably 〇. 5 hours to 1 hour. The heat treatment in the α-forming step can be carried out at a constant temperature, and can be carried out, for example, after the temperature is raised from the heat treatment temperature of the oxidation step to a predetermined temperature. In the present invention, from the viewpoint of thermal conductivity and productivity, it is preferred to carry out heat treatment by maintaining a predetermined temperature after raising the temperature from the heat treatment temperature of the oxidation step to a predetermined temperature. When the temperature is raised from the heat treatment temperature of the oxidation step to the specified temperature, the temperature specified is '1 〇〇 ° C 〜 1 3 0 〇 ° C 'specified temperature when the specified temperature is maintained to perform the heat treatment of the oxidation step. The maintenance time is preferably 0.2 hours to 3 hours, and the specified temperature is more preferably H50 ° C to 1 200 ° C. The maintenance time is preferably 〇. 5 hours to 2 hours. The heat treatment in the α-crystallization step is preferably carried out in an inert gas atmosphere from the viewpoint of thermal conductivity. The content of oxygen in the inert gas atmosphere is preferably 0. 1% by volume or less. Further, examples of the inert gas include nitrogen, argon, and -24-

S 201231487 Nitrogen, etc. The composite particles may be organically obtained by subjecting an aluminum nitride particle having a coating layer containing α-alumina formed on the surface as described above to a substituent having no reactivity with alumina but reacting only with aluminum nitride. The compound (hereinafter also referred to as "organic coating agent") is in contact with each other, and a coating layer containing an organic substance (second coating layer) is formed on the surface of the aluminum nitride particle in a region where the coating layer containing α-alumina is not formed. ). Here, examples of the organic compound having a substituent which is not reactive with aluminum oxide and reacting only with aluminum nitride include a hydrocarbon group having 1 to 24 carbon atoms and at least one of a hydroxyl group and a carboxyl group (hereinafter also Called "specific compounds"). This can be considered, for example, as follows. When a coating layer containing α-alumina is formed on the surface of aluminum nitride as described above, cracking occurs in the formed coating layer containing α-alumina. Thereby, a region covered by the coating layer not containing the α alumina is formed on the surface of the aluminum nitride particles. A region covered with the coating layer containing no α alumina on the surface of the aluminum nitride particles is brought into contact with a compound containing at least one of a hydrocarbon group having 1 to 24 carbon atoms and a hydroxyl group and a carboxyl group. Since the specific compound is selectively reactive with aluminum oxide and selectively reacts with aluminum nitride, a specific compound and nitrogen are formed on a region of the surface of the aluminum nitride particle which is not covered with the coating layer containing α-alumina. A coating layer of an organic substance of a reaction product of aluminum. As the organic compound having a substituent which is not reactive with alumina and reacts only with aluminum nitride, an organochemical-25-201231487 compound having an alcoholic hydroxyl group or a carboxyl group can be used. It is preferable to use a compound having a hydrocarbon group having 1 to 24 carbon atoms and an alcoholic hydroxyl group, and it is more preferable to use a method in which a hydrophilic group is left on the surface after reacting with aluminum nitride particles, and the mixture has two or more alcoholic hydroxyl groups. And at least one of the carboxyl groups and an organic compound having a hydrocarbon having a carbon number of from 1 to 24. Specific examples of the organic compound having an alcoholic hydroxyl group or a carboxyl group include the following organic compounds. Examples of the compound having a hydrocarbon group having 1 to 24 carbon atoms and an alcoholic hydroxyl group include methanol, ethanol, propanol, isopropanol, butanol, hexanol, cyclohexanol, octanol, lauryl alcohol, and stearyl alcohol. A cyclic, linear or branched monohydric alcohol such as behenyl alcohol. Examples of the organic compound having two or more alcoholic hydroxyl groups include glycols such as ethylene glycol, propylene glycol, trimethylene glycol, butanediol, and diethylene glycol, and glycols and glycerol. Polyols such as erythritol, glucose alcohol, and mannitol. Further, as long as it has two or more alcoholic hydroxyl groups, a saccharide or a polysaccharide can also be used. As the organic compound having a hydrocarbon group having 1 to 24 carbon atoms and a carboxyl group, acetic acid, propionic acid, octanoic acid, lauric acid, endomyric acid, palmitic acid, stearic acid, behenic acid, acrylic acid, crotonic acid, oleic acid can also be used. A monocarboxylic acid such as linoleic acid. As the organic compound having two or more carboxyl groups, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, undecane can be used. An aromatic carboxylic acid such as di- or tricarboxylic acid such as diacid or dodecanedioic acid or phthalic acid, isophthalic acid, terephthalic acid or trimellitic acid.

In the above, from the viewpoint of thermal conductivity and water resistance, a compound having a hydrocarbon group of 2 to 20 carbon atoms and at least one of a hydroxyl group and a carboxyl group is preferred, and more preferably has a carbon number. The compound of at least one of a hydrocarbon group of 2 to 20 and 1 to 2 of a hydroxyl group and a carboxyl group is preferably a compound having a hydrocarbon group of 2 to 20 carbon atoms and a combination of at least one of two or more hydroxyl groups and carboxyl groups. The coating layer is formed on the surface 22 of the composite particles by a compound having a hydrocarbon group of 2 to 20 carbon atoms and at least one of two or more hydroxyl groups and carboxyl groups, and as shown in FIG. On the surface 22, a cured product in which the liquid crystal group 20 is aligned in a certain direction is easily formed. Further, from the viewpoint of thermal conductivity and water resistance, it is preferred to use at least one selected from the group consisting of a compound having a hydrocarbon group and a carboxyl group having 1 to 24 carbon atoms and a hydrocarbon group having a carbon number of 1 to 24 and a hydroxyl group. Preferably, at least one selected from the group consisting of a compound having a hydrocarbon group of 2 to 24 carbon atoms and 1 to 2 carboxyl groups, and a compound having a hydrocarbon group of 2 to 24 carbon atoms and 1 to 2 hydroxyl groups is used, and it is particularly preferred to use carbon. At least one selected from the group consisting of a compound having 4 to 24 hydrocarbon groups and 2 carboxyl groups, and a compound having a hydrocarbon group having 4 to 24 carbon atoms and 2 hydroxyl groups. In addition, one or more of the organic compounds having an alcoholic hydroxyl group or a carboxyl group exemplified above may be used in combination. In a part of the organic compound having an alcoholic hydroxyl group or a carboxyl group to be used, by using a compound having a large number of alcohol groups or carboxyl groups, the polarity of the surface of the composite particles can be controlled, and the alignment of the surrounding liquid crystalline resin can be adjusted. The nitrided -27-201231487 aluminum particles having a coating layer containing α-alumina formed on the surface thereof are in contact with a compound (specific compound) containing at least one of a hydrocarbon group having 1 to 24 carbon atoms and a hydroxyl group and a carboxyl group. As the method, the usual method can be used without particular limitation. For example, a method of immersing aluminum nitride particles having a coating layer containing α-alumina on a surface thereof in a specific compound or a solution thereof, and nitriding a coating layer containing α-alumina on the surface thereof may be mentioned. A method of applying a specific compound or a solution thereof to an aluminum particle, a method of bringing an aluminum nitride particle having a coating layer containing α-alumina formed on a surface thereof into contact with a gas of a specific compound, or the like. In the present invention, from the viewpoint of reactivity, a method of impregnating a specific compound or a solution thereof with aluminum nitride particles having a coating layer containing α alumina formed on the surface thereof is preferred. When the aluminum nitride particles having the coating layer containing α-alumina formed on the surface are immersed in a solution of a specific compound, the concentration of the specific compound is not particularly limited, but from the viewpoint of reactivity and dispersibility, It is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 5% by mass. Further, the solvent of the solution constituting the specific compound is not particularly limited, but is preferably an organic solvent. Examples of the organic solvent include a hydrocarbon solvent such as toluene, xylene or chlorobenzene, a halogenated alkyl solvent such as chloroform, dichloromethane, trichloroethane or carbon tetrachloride, or diethyl ether or two. An ether solvent such as isopropyl ether or THF; an ester solvent such as ethyl acetate or butyl acetate; or the like. In particular, it is preferably at least one selected from the group consisting of a hydrocarbon solvent and an ether solvent, and more preferably a hydrocarbon solvent, from the viewpoint of water content and compatibility with a specific compound. In addition, the time period in which the nitrogen-containing -28-201231487 chemical-coated particles having the coating layer containing the α-oxide is formed on the surface is not particularly limited, and may be appropriately selected depending on the type of the specific compound, the contact temperature, and the like. For example, it may be from 1 minute to 12 hours, and from the viewpoint of thermal conductivity and water resistance, it is preferably from 1 hour to 4 hours, more preferably from 2 hours to 4 hours. In addition, the temperature at which the aluminum nitride particles having the coating layer containing the α-alumina formed on the surface are in contact with the specific compound is not particularly limited, and may be appropriately selected depending on the type of the specific compound, the contact time, and the like. For example, it may be from 25 ° C to 150 ° C, and from the viewpoint of thermal conductivity and water resistance, it is preferably from 30 ° C to 120 ° C, more preferably from 50 ° C to 120 ° C. In the organic layer formation step of the present invention, from the viewpoint of thermal conductivity and water resistance, it is preferred that the aluminum nitride particles having a coating layer containing α-alumina formed on the surface thereof are immersed in a carbon number of 1 to 24 And a specific compound selected from the group consisting of a hydrocarbon group and at least one of a hydroxyl group and a carboxyl group, wherein the step of contacting for 1 to 12 hours at a temperature of from 25 ° C to 150 ° C is preferably immersed on the surface. a specific compound selected from the group consisting of aluminum nitride particles containing a coating layer of α-alumina and a compound containing at least one of a hydrocarbon group having 1 to 24 carbon atoms and a hydroxyl group and a carboxyl group, 'at a temperature of 50 ° C to 120 ° C makes the step of contacting for 2 to 4 hours. The composite particles obtained by bringing the aluminum nitride particles having the coating layer containing α-alumina formed on the surface thereof into contact with a specific compound may be subjected to post-treatment such as washing or drying as needed. The content of the composite particles in the liquid crystalline resin composition is not particularly limited, but the content in the solid content of the resin composition is preferably 50% from the viewpoint of thermal conductivity and moldability. /. The above is more preferably 60 -29-201231487 mass%~9 8 mass%, and particularly preferably 80 mass%~9 5 mass%. Here, the solid content means the total amount of the nonvolatile components in the components constituting the liquid crystalline resin composition. In addition, the composite particles contained in the liquid crystalline resin composition may be used alone or in combination of two or more. When two or more types of composite particles are used in combination, examples of the composite particles of two or more types include layers having different particle diameters, different organic substances, different organic structures, and layers of a coating layer containing α-alumina. Thick and different, and combinations of these. The liquid crystalline resin composition preferably contains other inorganic particles (such as molten vermiculite, crystalline vermiculite, alumina, boron nitride, aluminum nitride, etc.) in addition to the aluminum nitride composite particles. In order to increase the thermal conductivity, the content of the aluminum nitride composite particles is preferably 20% by mass or more based on the total amount of the pigment. (Epoxy Resin) The liquid crystalline resin composition of the present invention contains at least one of the liquid crystalline epoxy resin monomers represented by the following formula (1). A liquid crystalline epoxy resin single system is an epoxy resin monomer having a liquid crystal group. Since it is a resin composition containing a liquid crystalline epoxy resin monomer, it can be easily molded, and the cured product is excellent in insulation properties. In the formula (1), X represents a single bond or a divalent linking group composed of at least one selected from the group consisting of a divalent group represented by the following chemical formula. By having this specific structure, an epoxy resin hardened material having an alignment property is formed.

S 201231487

[化8] ~~N=N—CEC- C^N—C=C--C=C--C=C_C· M Η H HI Η Η II CH3 0

The 'preferable single bond, a phenyl group which may have a substituent, a cyclohexyl group which may have a substituent, or a cyclohexanediyl group which may have a substituent, more preferably a single bond, may have a substituent a cyclohexenediyl group or a cyclohexanediyl group which may have a substituent. Further, Y each independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aliphatic alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group or an ethyl group. However, from the viewpoint of thermal conductivity of the cured product, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aliphatic alkoxy group or a chlorine atom is preferred, and an aliphatic hydrocarbon group having 1 to 8 carbon atoms is more preferred. η represents an integer of 〇~4, preferably 〇~3, more preferably 〇~2. k -31 - 201231487 The integer of ~7 is preferably 〇~4, more preferably 〇~2. m represents an integer of 0 to 8, preferably 0 to 4, more preferably 〇~2. 1 represents an integer of 0 to 12, preferably 0 to 4, more preferably 〇2. In the following, specific examples of the liquid crystalline epoxy resin monomer usable in the present invention include 4,4,-biphenol epoxypropyl ether, 1-{(3-methyl-4-epoxyethyl) Methoxy)phenyl}-4-(4-oxiranylmethoxyphenyl)-1-cyclohexene, 4-(oxiranylmethoxy)benzoic acid-1, 8-octanediylbis(oxy·1,4-phenylene) ester, 2,6-bis[4-[4-[2-(oxiranylmethoxy)ethoxy]benzene The phenoxy]pyridine or the like is not limited to the above-mentioned liquid crystal resin composition in the liquid crystal resin composition, and the content ratio of the liquid crystal epoxy resin monomer is not particularly limited, but from thermal conductivity and hardenability. From the viewpoint of the liquid crystal resin composition, it is preferably 1.0% by mass to 20.0% by mass, more preferably 3.0% by mass to 15.0% by mass, based on the total mass of the liquid crystal resin composition. The liquid crystallinity of the thermotropic liquid crystal which exhibits liquid crystallinity as a function of temperature changes, or the liquid crystal property of the lyotropic liquid crystal which exhibits liquid crystallinity with respect to density. Further, the transferred liquid crystal phase may be any one of a nematic liquid crystal phase, a smectic liquid crystal phase, and a discotic liquid crystal. It is preferably a smectic liquid crystal phase or a disk-shaped liquid crystal phase having a high alignment order and excellent thermal conductivity. In addition to the liquid crystalline epoxy resin represented by the above formula (n, the liquid crystal resin composition may further contain other epoxy resins not related to the liquid crystalline epoxy resin represented by the general formula (1). As another epoxy resin, a phenol novolak type is specifically mentioned.

S -32- 201231487 Epoxy resin, o-cresol novolac type epoxy resin, epoxidized by a novolac resin including epoxy resin having a triphenylmethane skeleton. Further, examples of the novolac resin include phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F, and α-naphthol and β-naphthalene. A novolac resin such as a naphthol such as phenol or dihydroxynaphthalene or a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde or salicylaldehyde, which is condensed or co-condensed under an acidic catalyst. Further, polybasic acids such as bisphenol A, bisphenol F, bisphenol S, anthracene epoxy resin, hydroquinone type epoxy resin, phthalic acid, and dimer acid, and epichlorohydrin may also be mentioned. a glycidyl acrylate epoxy resin obtained by the reaction, a glycidyl amide epoxy resin obtained by reacting a polyamine such as diaminodiphenylmethane or isomeric cyanuric acid with epichlorohydrin, An epoxide of a co-condensation resin of dicyclopentadiene and a phenol, an epoxy resin having a naphthalene ring, a phenol·aralkyl resin, a phenol·aralkyl resin containing a biphenyl group, naphthol·fang An epoxide of an aralkyl type phenol resin such as an alkyl resin, a trimethylolpropane type epoxy resin, a terpene-modified epoxy resin, or a linear form obtained by oxidizing an olefin bond with a peracid such as peracetic acid An aliphatic epoxy resin, an alicyclic epoxy resin, a sulfur atom-containing epoxy resin, or the like. These epoxy resins may be used singly or in combination of two or more. When the liquid crystalline resin composition contains another epoxy resin, the content of the other epoxy resin is not particularly limited. The content of the solid content of the resin composition is preferably 50% by mass or less, and more preferably 20% by mass or less, from the viewpoints of thermal conductivity and moldability. -33- 201231487 (hardener) The liquid crystalline resin composition contains at least one hardener. The above-mentioned curing agent can be suitably selected according to the purpose of the curing agent which is usually used in the thermosetting resin composition containing an epoxy resin. Specific examples thereof include a phenol-based curing agent such as an aromatic or aliphatic amine-based curing agent, an acid anhydride-based curing agent, and a novolac resin, a thiol-based curing agent, a polyamine amide-based curing agent, and an isocyanate-based curing agent. Agent, blocked isocyanate curing agent, and the like. Among these, it is preferably at least one selected from the group consisting of an aromatic amine-based curing agent, an acid anhydride-based curing agent, and a phenolic curing agent, and more preferably an aromatic amine-based curing agent. The content of the curing agent in the liquid crystal resin composition can be appropriately set in consideration of the type of the curing agent or the physical properties of the obtained thermally conductive epoxy resin molded body. Specifically, the content of the hardener is preferably such that the chemical equivalent of the hardener is 0.005 equivalents to 5 equivalents, more preferably 〇.〇1 equivalent, relative to the epoxy group 1 mole contained in the epoxy resin. 〜3 equivalents, particularly preferably 0.5 equivalents to 1.5 equivalents, particularly preferably 0.8 equivalents to 1.3 equivalents. When the content of the hardener is 0.005 equivalent or more with respect to the epoxy group 1 mol, the epoxy resin can be hardened rapidly. On the other hand, when it is 5 equivalent or less, the hardening reaction can be suppressed too fast. Further, the chemical equivalent here, for example, when an amine-based curing agent is used as the curing agent, means the number of moles of active hydrogen of the amine group which the amine-based curing agent has with respect to the epoxy group 1 mole. The cured product of the liquid crystalline resin composition preferably exhibits a liquid crystal structure. This -34-

The liquid crystal phase shown in S 201231487 may be any one of a nematic liquid crystal phase, a smectic liquid crystal phase, and a disk-shaped liquid crystal. It is preferably a smectic liquid crystal phase or a discotic liquid crystal phase which is highly ordered and has excellent thermal conductivity. The resin composition of the present invention may contain other components as needed in addition to the above-mentioned essential components. As other components, for example, a solvent, a dispersing agent, a sedimentation inhibitor, and the like can be given. The solvent ' is not particularly limited as long as it does not interfere with the curing reaction of the resin composition. The organic solvent which is usually used can be appropriately selected. &lt;Heat Dissipating Material Precursor&gt; The semi-cured material of the liquid crystal resin composition of the heat dissipating material precursor system of the present invention. Thereby, a heat dissipating material excellent in operability and excellent in thermal conductivity can be formed. The heat-dissipating material precursor includes a B-stage sheet of a sheet-like semi-cured material of the liquid crystal resin composition, and a semi-cured material having a fiber base material and the liquid crystalline resin composition impregnated into the fiber base material. Prepreg. (B-stage sheet) The above-mentioned sheet B sheet is composed of a semi-cured material of the liquid crystal resin composition and has a sheet-like shape.

The B-stage sheet can be produced, for example, by a method comprising: coating and drying the liquid crystalline resin composition on the release film to form a resin composition layer, and heat-treating the resin composition layer to B -35 - Steps up to the 201231487 level. The liquid crystal resin composition is formed by heat treatment, and has excellent heat conductivity, and is excellent in flexibility and service life of the B-stage sheet. The above-mentioned so-called B-stage sheet means that the viscosity with respect to the resin sheet is 104 to 105 Pa. at normal temperature (25 ° C), and the viscosity at 100 ° C is lowered to 1200 to 1 03 Pa. Further, the cured resin (heat dissipating material) after curing described later is not melted even if it is heated. Further, the above viscosity was measured by kinetic energy viscoelasticity measurement (frequency 1 Hz, load 40 g, heating rate 3 ° C/min). Specifically, for example, a varnish-like liquid crystalline resin composition (hereinafter also referred to as a resin varnish) to which a solvent such as methyl ethyl ketone or cyclohexanone is added is applied to a release film such as a PET film. Drying forms a resin composition layer. The coating system can be carried out by a well-known method. Specific examples of the coating method include a method such as comma coating, die coating, lip coating, and gravure coating. As a coating method for forming a resin composition layer at a predetermined thickness, a die coating method in which a coated object passes through a gap, a die coating method in which a resin varnish having a flow rate adjusted from a nozzle is applied, or the like can be used. For example, when the thickness of the resin composition layer before drying is from 50 μm to 500 μm, it is preferred to use a Cooma coating method. The resin composition layer after coating has almost no progress in the curing reaction system, and although it has flexibility, it lacks flexibility as a sheet, and in the state in which the PET film of the support is removed, the sheet is not self-supporting, and the operation system is lacking. difficult. Therefore, the resin composition layer is semi-hard by heat treatment described later.

S -36- 201231487, B-class. The conditions for heat-treating the resin composition layer are not particularly limited as long as the resin composition is semi-cured to the B-stage state, and can be appropriately selected in accordance with the configuration of the liquid crystal resin composition. It is preferable to select a pressure treatment method by hot vacuum pressurization, hot roll lamination, or the like. Thereby, voids (voids) in the resin which occur during coating can be reduced, and a flat B-stage can be efficiently produced, for example, preferably by heating at a temperature of 80 ° C to 2 to 30 seconds. The resin composition layer is semi-hardened to a B-stage state by heating under reduced pressure (for example, 1 Μ P a ). The thickness of the above-mentioned B-stage sheet may be suitably 50 μm or more and 500 μm or less in accordance with the purpose, and is preferably 60 μm or more and 300 μm or less from the viewpoint of thermal conductivity and sheet. Further, the crucible sheet may be produced by hot pressing while laminating two or more layers. (Prepreg) The prepreg has a fibrous base material and a semi-cured material impregnated with the liquid crystal resin composition described above, and may be formed of another layer such as a film as needed. The semi-cured material of the liquid crystalline resin composition is excellent in thermal conductivity because it contains a precursor. The fiber base material constituting the prepreg is not a heat-added composition layer sheet which restricts the liquid crystal to the heating portion as long as it is used in the production of the laminated board or the multilayer printed wiring board. 1 3 0 °C calendar 1 pressure treatment, selection, for example, the concept of flexibility, resin film, fiber substrate, protection, composite particles, metal foil, special limit -37- 201231487. For example, a fibrous substrate such as woven or non-woven fabric is usually used. However, in the case of a fiber in which the pores are easily clogged, the material such as the composite particles is filled and the impregnation is difficult, so that the mesh is preferably at least 5 times the volume average particle diameter of the composite particles. The material of the fiber base material is inorganic fiber such as glass, alumina, boron, vermiculite alumina glass, vermiculite glass, titanium oxide, tantalum carbide, tantalum nitride or zirconium oxide, or aromatic polyamine or polyether. Organic fibers such as ether ketone, polyether oxime, polyether oxime, carbon, cellulose, etc., and such blended systems. Among them, a woven fabric using glass fibers is particularly preferred. Thereby, a flexible printed wiring board having flexibility can be obtained. Further, it is also possible to reduce the dimensional change of the substrate due to the temperature of the process, moisture absorption, and the like. The thickness of the fiber base material is not particularly limited, but is preferably 30 μm or less from the viewpoint of imparting more flexibility, and is preferably 15 μηη or less from the viewpoint of impregnation. The lower limit of the thickness of the fibrous base material is not particularly limited and is usually about 5 μη. In the prepreg, the impregnation amount of the liquid crystalline resin composition is preferably from 50% by mass to 9.9% by mass based on the total mass of the fibrous base material and the liquid crystalline resin composition. The prepreg can be produced by impregnating a fibrous base material with a resin varnish prepared in the same manner as above, and removing the solvent by heating at 80 ° C to 180 ° C. The residual amount of the solvent in the prepreg is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.7% by mass. /. the following. Solvent residual amount is to cut the prepreg into 40mm square, and dry in a thermostat preheated to 1 90t for 2 hours, the mass change before and after drying -38-

S 201231487 to come. The drying time for removing the solvent by heating is not particularly limited. Further, the method of impregnating the fibrous base material with the liquid crystalline resin composition is not particularly limited, and for example, a method of coating by a coater is exemplified. Specifically, a vertical coating method in which a fibrous base material is immersed in a liquid crystalline resin composition, and a liquid crystalline resin composition is applied onto a support film, and then the fibrous base material is pressed and impregnated. In the horizontal coating method or the like, from the viewpoint of suppressing the presence of the thermal conductive material in the fiber base material, it is preferable that the horizontal coating method 0 is impregnated into the fiber substrate in the prepreg. The liquid crystalline resin composition is semi-hardened and is in a B-stage state. The B-stage state of the prepreg is the same as the B-stage state of the B-stage sheet, and the same conditions can be employed for the B-stage method. Further, the prepreg may be subjected to a heat and pressure treatment by pressurization or roll lamination, or the like, and the surface may be smoothed before lamination or pasting. The method of heat and pressure treatment is the same as that exemplified for the above-mentioned crucible sheet. Further, the heating temperature, the degree of vacuum, and the conditions of the pressurization of the prepreg are also the same as those exemplified for the heat and pressure treatment of the bismuth resin sheet. The thickness of the prepreg may be appropriately selected according to the purpose, and may be, for example, 5 Ομηη or more and 50,000 μηι or less. From the viewpoint of thermal conductivity and flexibility, it is preferably 60 μm or more and 300 μm or less. Further, the prepreg can also be produced by laminating two or more prepregs and performing hot pressing. -39-201231487 &lt;heat-dissipating material&gt; The heat-dissipating material of the present invention is a cured product of the liquid crystal resin composition. Specific examples of the heat dissipating material include a laminate having a cured product of the liquid crystal resin composition, a metal substrate, a printed wiring board, and the like. The hardened material of the liquid crystalline epoxy resin represented by the above formula (1) and the composite particles described above have excellent thermal conductivity. Further, since the surface of the aluminum nitride particles is coated with an organic substance having a hydrophilic group of a carboxyl group or an alcoholic hydroxyl group, the resin and the aluminum nitride particles can be improved as compared with the case of being coated with an organic substance having only a hydrocarbon group. Affinity can suppress the decrease in thermal conductivity. Further, the alignment of the hydrophilic group can control the alignment of the liquid crystalline epoxy resin represented by the above formula (1). Particularly, by controlling the alignment of the resin, the liquid crystalline epoxy resin represented by the formula (1) is vertically aligned with the aluminum nitride particles, and the thermal resistance of the interface between the particles and the resin can be reduced. The term "vertical alignment" as used in the present invention means that the molecules of the liquid crystalline epoxy resin are aligned at an inclination angle with respect to the surface of the particles. In the present invention, the inclination angle is 50 to 90, preferably 70 to 90. In the heat dissipating material, it is preferable that the cured product of the liquid crystalline epoxy resin has an alignment surface, and the alignment surface has an angle of 50 to 90 with respect to the surface of the aluminum nitride composite particles, preferably 70°~90°. The inclination angle of the surface of the liquid crystalline epoxy resin in the heat dissipating material with respect to the surface of the composite particles can be estimated as follows. -40-

In the same manner as in the method for producing aluminum nitride composite particles, a composite substrate in which a coating layer of α-alumina and an organic compound is formed on the surface is obtained in the same manner as in the production method of the aluminum nitride composite particles. A resin composition containing the liquid crystalline epoxy resin and a curing agent is applied onto the composite substrate, and is subjected to heat curing to form a cured resin layer on the composite substrate. A wide-angle X-ray diffraction apparatus (RINT25 00HL manufactured by Rigaku) can be used for the obtained cured resin layer, and the period length of the periodic structure formed in the vertical direction with respect to the composite substrate can be determined, and the period length of the resin molecules can be obtained. The inclination angle of the resin molecules with respect to the substrate was obtained. (Laminated board) The laminated board of the present invention has a hardened layer of a resin-containing layer and a material to be attached. The resin-containing layer is composed of a resin layer composed of the liquid crystal resin composition, the B-stage sheet, and at least one layer selected from the prepreg. A laminate having a resin-containing layer formed of the liquid crystalline resin composition is provided as a laminate having excellent thermal conductivity and insulation properties. In the laminate, the cured layer of the resin-containing layer may be in the form of any one of the resin layer, the B-stage sheet, or the prepreg, or may have two or more layers. When two or more layers of the hardened layer are provided, two or more layers of the above-described resin layer may be provided, or two or more sheets of the above-described class B sheets may be provided, or two or more sheets of the prepreg may be provided. . Further, any two or more of the resin layer, the B-stage sheet, and the prepreg are also provided in combination. The laminate may be formed by, for example, coating the resin composition -41 - 201231487 on the material to be attached to form a resin layer, heating and pressurizing the resin layer to harden the resin layer while adhering to the material to be attached. obtain. Alternatively, by laminating a laminate in which the above-mentioned Class B sheet or the prepreg is laminated on the attached material, the laminate is heated and pressurized to harden the B-stage sheet or the prepreg. It is obtained by intimately attached to the attached material. The heating temperature for curing the resin-containing layer is not particularly limited, but is usually in the range of 80 ° C to 250 ° C, preferably in the range of 130 ° C to 2 30 ° C. Further, the conditions of the pressurization are not particularly limited, and are usually in the range of 0.5 MPa to 15 MPa, preferably in the range of 2 MPa to 10 MPa. Further, in heating and pressurization, vacuum pressurization is preferably used. As a material to be attached, a metal foil, a metal plate, etc. are mentioned. The attached material may be attached only to one surface of the hardened layer of the resin-containing layer, or may be attached to both surfaces. The metal foil may be a gold foil, a copper foil, an aluminum foil or the like without particular limitation, and a copper foil is generally used. The thickness of the metal foil is not particularly limited as long as it is ι μπ 1 to 5 00 μηη, and an appropriate thickness can be selected in accordance with the electric power used. Further, as the metal foil, an intermediate layer of nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy or the like may be used, and copper of 〇·5μηι 1515ηηι is provided on both surfaces thereof. A composite foil having a three-layer structure of a copper layer of a layer of ΙΟμιη to 300 μηι, or a two-layer composite foil of aluminum and copper foil. The metal plate is made of a metal material having a high thermal conductivity and a large heat capacity, and examples thereof include copper, aluminum, iron, and an alloy for a lead frame. The thickness of the board can be selected according to the application. When lightweight or processability is preferred, the metal substrate -42-

S 201231487 selects aluminum, selects copper when heat dissipation is preferred, and selects material according to the purpose. The thickness of the laminate is preferably 200 μm or less, and more preferably 5 〇μηι to 180 μιη. When the thickness is 200 μm or less and more than 180 μm, the resin is excellent in flexibility. In the bending process, the occurrence of cracks is suppressed. Further, when the thickness is 50 μm or more, workability is excellent. (The cured metal foil and the metal substrate) As an example of the laminated plate, a cured metal foil and a metal substrate used for producing a wiring board to be described later are exemplified. In the cured metal foil, two metal foils were used as the material to be attached to the laminate. Specifically, two sheets of the above-described metal foil are prepared, and a hardened layer of the resin-containing layer is provided between the two metal foils. In the above metal substrate, a metal foil and a metal substrate are used as the material to be attached to the laminate. Specifically, the metal substrate is provided with a cured layer of the resin-containing layer between the metal foil and the metal substrate. From the viewpoint of improving productivity, it is preferable to form a metal substrate in a large size and to cut the size to be used after mounting the electronic component. Therefore, the metal plate used for the metal substrate is preferably excellent in cutting workability. When aluminum is used as the metal plate, the material may be selected from aluminum or an alloy containing aluminum as a main component, and various types of materials may be obtained depending on the chemical composition and heat treatment conditions, but it is preferable to select high workability such as high cutting ease. A type with excellent strength. -43-201231487 (Printed wiring board) The printed wiring board of the present invention has a wiring layer, a metal substrate, and a cured layer of a resin-containing layer between the wiring layer and the metal substrate. The resin-containing layer is at least one layer selected from the resin layer formed of the liquid crystalline resin composition, the B-stage sheet, and the prepreg. The printed wiring board can be manufactured by circuit-processing the metal foil-attached cured metal or metal foil in the metal substrate. In the circuit processing of metal foil, the usual lithography method can be employed. By using the resin composition of the present invention, a printed wiring board excellent in thermal conductivity and insulation can be obtained. The preferred embodiment of the printed wiring board is the same as the printed wiring board described in paragraph number 0064 of JP-A-2009-214525 or paragraph number 0056 to 0059 of Japanese Patent Laid-Open Publication No. 2009-275086. . [Examples] Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. Furthermore, "%" is based on quality unless otherwise specified. [Example 1] (Preparation of composite particles) Hereinafter, a method for producing the sample 1 and a method for measuring the physical properties of the sample 1 will be described. 5 g of aluminum nitride sintered particles having a volume average particle diameter of 30 μm was placed in a high-temperature tubular furnace (35 mm &lt; t &gt; x 200 mm) while flowing Ar gas at 0.5 L/min - 44 -

S 201231487 moves from room temperature to 1200 °c in 100 minutes. After holding at 1200 ° C for 2 hours, the temperature was lowered from 1 200 ° C to 240 ° C for 240 minutes to obtain an aluminum nitride particle having an α alumina coating layer formed on the surface. The obtained particles were added to dehydrated toluene, and 25 g of yttrium adipate as an organic coating agent was added, followed by reflux for 2 hours. After the particles were washed with toluene, they were dried at room temperature to obtain composite particles in which a coating layer of α-alumina and an organic compound was formed on the surface (Sample 1). The intensity ratio of the (1 〇〇 ) plane of the α alumina to the ( 1 1 3 ) plane of the aluminum nitride was measured by XRD, and the α alumina coating thickness was calculated. Further, the XRD system was carried out by measuring an X-ray diffraction light using an X-ray diffraction apparatus (RINT25 00HL, manufactured by Rigaku Co., Ltd.) using a CuKa line as a line source. The results shown in Table 1 are water resistance. 2 g of the sample was added to 200 mL of water at 60 ° C, and the pH of the aqueous dispersion after 30 minutes and 60 minutes was measured to investigate the influence of ammonia due to hydrolysis. The results are shown in Table 1. (Preparation of Liquid Crystal Resin Composition) In the sample 1 obtained above, a liquid crystalline epoxy resin (丨_(3-methyl-4-oxiranylmethoxyphenyl)-4-(cyclo) was added. Ethoxyethyl methoxyphenyl)-1 -cyclohexene, a liquid crystalline epoxy resin represented by the formula (1), hereinafter also referred to as "resin 1"), a hardener (1,5-diamine) Naphthalene) to prepare a liquid crystalline resin composition. The mixing ratio of the liquid crystalline epoxy resin and the hardener is 1:1 'mixed ratio of the composite particles in the ratio of -45 to 201231487 in terms of epoxy/amine, relative to the liquid crystalline epoxy resin, hardener, and composite The volume ratio of the entire liquid crystal resin composition of the particles was 60% by volume. A single-sided (upper) roughened copper foil (thickness 70 μm) was used as a substrate, and the obtained liquid crystalline resin composition was applied by casting to a specified thickness 'heating at a heating temperature of 1 60 ° C ' The resin sheet (B-stage sheet) in the B-stage state as a precursor of the heat-dissipating material was obtained by heating and drying at a time of 5 minutes. The resin coated surface was placed thereon, and the obtained resin sheet was placed, and a single-sided (lower) copper foil (thickness 70 μm) was laminated so that the roughened surface contacted the resin composition layer at 145 ° C. Vacuum heating and pressurization was carried out at 2 MPa, and thermal hardening was carried out to proceed. Further, it was completely cured by a heat treatment at a temperature of 2 0 5 ° C for 2 hours to obtain a flaky resin cured product (laminate) as a heat dissipating material. The test piece was cut out from the obtained cured product, and the copper foil on both sides was removed by acid etching, and only the sheet-like resin cured product was taken out. The thermal diffusivity of the cured resin was measured by a flash evaporation apparatus (Nanoflash LFA447 manufactured by NETZSCH Co., Ltd.), and the thermal diffusivity was multiplied by the density measured by the Archimedes method and the specific heat measured by the DSC method. The thermal conductivity in the thickness direction is obtained. The results are shown in Table 1. (Evaluation of the inclination angle) The aluminum nitride sintered particles were treated in the same manner as the composite particles except for the aluminum nitride sintered substrate having a thickness of 1 mm, and were obtained on the surface -46-

S 201231487 A composite substrate in which a coating layer of alpha alumina and an organic compound is formed. On the obtained composite substrate, a liquid crystalline epoxy resin and a curing agent are heated to cure the resin composition into a film shape of 5 μm to 20 μm. Using a wide-angle X-ray diffraction apparatus (RINT2500HL manufactured by Rigaku), the period length of the periodic structure formed in the vertical direction with respect to the aluminum nitride sintered substrate was determined, and the resin molecules were obtained from the molecular length of the liquid crystalline epoxy resin. The angle of inclination with respect to the substrate. The results are shown in Table 1.

[Examples 2 to 7J Next] Samples 2 to 7 were prepared as follows, and evaluated in the same manner as Sample 1. The evaluation results are shown in Table 1. Sample 2: The environment at the time of calcination was changed to the atmosphere, and the aluminum nitride sintered particles having a volume average particle diameter of 30 μm φ and the aluminum nitride sintered substrate in the sealed state were treated with adipic acid in the same manner as the sample 1 to prepare Sample 2. A flaky resin cured product (laminate) as a heat dissipating material is formed by the same method as described above. Sample 3: When calcining the aluminum nitride sintered particles having a volume average particle diameter of 30 μπιφ and the aluminum nitride sintered substrate, the dry air was calcined while flowing at a rate of 1 L/min. 'Adipic acid was used in the same manner as the sample 1 Processing is performed to prepare a sample. A sheet-like resin cured product (laminate) as a heat dissipating material is formed by the same method as described above. s material 4: A sample was prepared by the same method as that of the sample 1, in place of the adipic acid used in the sample 1, using trimellitic acid. A sheet-like resin cured product as a heat dissipating material was formed by the same force &amp; as described above (Laminated Plate - 47 - 201231487 Sample 5: Substituting adipic acid for Sample 2, using trimellitic acid' by means of a sample 2, a sample was prepared in the same manner. A sheet-like resin cured product (laminate) as a heat dissipating material was formed by the same method as described above. Sample 6: Instead of the adipic acid used in the sample 3, trimellitic acid was used. A sample was prepared in the same manner as in Sample 3. A heat-dissipating sheet was formed in the same manner as in Example 1. Sample 7: Instead of adipic acid used in Sample 1, hydrazine, 3·butanediol was used. Samples were prepared in the same manner as in Sample 1. A sheet-like resin cured product (laminate) as a heat dissipating material was formed by the same method as described above. [Examples 8 to 10] Samples 8 to 1 0 were prepared as follows. The evaluation results are shown in the same manner as in the above. The evaluation results are shown in Table 1. However, regarding the tilt angle, the liquid crystalline epoxy resin (due to hard acid having no hydroxyl group) was not vertically aligned, and was not evaluated. test The adipic acid used was prepared by the same method as the sample 1 using stearic acid, and a sheet-like resin cured product (laminate) as a heat dissipating material was formed by the same method as above. 9: In place of the adipic acid used in the sample 2, the stearic acid was used, and the sample 9 was produced in the same manner as the n-type material 2. The same as described above.

S-48-201231487 Method of forming a sheet-like resin cured product (laminate) as a heat dissipating material. Sample 10: Substituting adipic acid for sample 3, using stearic acid, by the same method as sample 3 Sample 10. A sheet-like resin cured product (laminated sheet) as a heat dissipating material was formed by the same method as described above (Example 11) Except that in Example 1, Sample 1 was used as a composite particle instead of 1-(3-methyl group). 4-Othylene oxide methoxyphenyl)-4_(oxiranylmethoxyphenyl)-1-cyclohexene, using biphenyl liquid crystalline epoxy resin (Mitsubishi Chemical Co., Ltd. YL6121H, a liquid crystal epoxy resin represented by the formula (1) (hereinafter also referred to as "resin 2"), a resin composition as described above is prepared, and a sheet as a heat dissipating material is formed by the same method as described above. [Comparative Example 1 to 2] Samples 1 to 1 2 were prepared and evaluated in the same manner as above. The evaluation results are shown in Table 1. Sample 1 1 : In the same manner as Sample 1 After the nitriding sintered particles having a volume average particle diameter of 3 μm ηφ and the aluminum nitride sintered substrate were fired, the organic coating treatment was carried out, and the sample 1 was obtained. The resin composition was prepared in the same manner as described above except that the obtained sample 1 1 was used. 'by the same method as above, shape -49-201231487 flaky resin cured product (laminate). The sample 11 and the sheet-like resin cured product were evaluated in the same manner as above. The evaluation results are shown in Table 1. Sample 12: Volume average The aluminum nitride sintered particles having a particle diameter of 30 μm φ and the nitriding sintered substrate were not subjected to the smouldering, and were subjected to an organic coating treatment in the same manner as the sample 1 to prepare a sample 12. The sample was prepared in the same manner as described above except that the obtained sample 1 2 was used. In the resin composition, a sheet-like resin cured product (laminate) as a heat dissipating material was formed by the same method as described above. The sample 12 and the sheet-like resin cured product were evaluated in the same manner as described above. [Comparative Example 3] The aluminum nitride sintered particles having a volume average particle diameter of 30 μηιφ and the nitrided sintered substrate 'are not subjected to the sonication treatment and the organic coating treatment, and were used as the sample 13. The modulation tree was formed in the same manner as described above. The heat-dissipating material is a sheet-like resin cured product in the same manner as described above except that the obtained lipid composition other than the obtained sample 13 is used. Plywood). For the sample I3 and a sheet of the cured resin, as described above was evaluated. Table 1 shows the evaluation results. [Comparative Example 4] except that in Example 1, using the sample i as composite particles, use

S-50. 201231487 A bismuth A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation, hereinafter also referred to as "resin 3") is prepared in the same manner as described above except for the liquid crystalline epoxy resin. In the same manner, a sheet-like resin cured product (laminate) as a heat dissipating material is formed. The sheet-like resin cured product was evaluated in the same manner as above. The evaluation results are shown in Table 1. [Table 1] m Organic coating agent epoxy resin calcination environment α-alumina thickness S inm) XRD Strength ratio PH (after 3 shovel) pH (after 60 minutes) Thermal conductivity CW/πι-Κ) Tilt angle (S) 1 Adipic acid Ar 80 0.0056 7.7 7.9 3.7 81 2 Atmosphere 400 0.029 7.6 7.7 3.2 80 3 Dry air 5800 1.2 7.5 7.6 2.7 78 4 Trimellitic acid Ar 80 0. 0056 8.1 8.2 3.7 73 5 Atmosphere 400 0.029 7.9 8.1 3.1 75 6 Resin 1 Dry air 5800 1.2 7.8 8.1 2.8 72 贲 Example 7 7 1,3-butanediol Ar 80 0.0056 7.6 7.7 3.7 80 Example 8 8 Stearic acid Ar 80 0. 0056 7.4 7.5 3.5 Example 9 9 Gas 400 0.029 7.9 7.9 2.8 • Example 10 10 Dry air 5 &amp; 00 1.2 7.8 7.9 2.1 Example 11 1 Adipic acid resin 2 Ar 80 0.0056 7.7 7.9 3.7 80 Comparative Example 1 11 Ar 80 0.0D56 9.8 10.3 3.7 78 12 Adipic acid resin 1 - - - 7.9 9.1 2.6 80 13 — - - - 10.2 10.4 3.9 Vertical comparison example 4 Adipic acid resin 3 Ar 80 0.0056 7.9 7.9 1.1 81 The bisphenol a type epoxy resin of Comparative Example 4 was used. Comparison of the cured resin formed, using liquid crystalline epoxy resin and testing The cured resin is formed out of the square 1~1 composite particles are any one of a high thermal conductivity. Further, in any of the samples 1 to 10, compared with the samples 11 to 13, the water resistance was also remarkable. When the thermal conductivity of the resin cured product formed by the samples 1, 4, and 7 and the sample 8 was compared, the resin cured product formed using the samples 1, 4, and 7 exhibited a high thermal conductivity. It is considered that this is because when an organic compound having two or more hydroxyl groups or carboxyl groups is used in the organic film material -51 - 201231487, the liquid crystalline epoxy resin forms 50 with respect to the surface of the composite particles. ~9 0. The inclination is aligned with the angle. Similarly, when the thermal conductivity of the cured resin formed by the samples 2, 5 and the sample 9, the samples 3 and 6 and the sample 1 比较 are compared, the resin cured product formed by the samples 2, 5, or the samples 3 and 6 is used. The invention discloses a higher thermal conductivity. The disclosure of Japanese Patent Application No. 20 1 1 -008482 is hereby incorporated by reference in its entirety in the entire entire entire entire entire entire entire entire entire entire entire entire disclosure The incorporation of each of the documents, the invention patent application, and the technical specifications will be incorporated herein by reference to the same extent as the respective descriptions. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a microscope photograph of aluminum nitride composite particles of the present embodiment. Fig. 2 is a flow chart showing an example of a method for producing the aluminum nitride composite particles of the present embodiment. 3 is a model diagram showing an example of the alignment state of the liquid crystalline epoxy resin on the surface of the aluminum nitride composite particles in the resin cured product of the present embodiment. FIG. 4 is a view showing nitrogen in the resin cured product of the present embodiment. An example of the disorder of the alignment of the liquid crystalline epoxy resin on the surface of the aluminum composite particles-52-

S 201231487 pattern. [Explanation of main component symbols] 1 : Aluminum nitride particles 2 : α Alumina layer 3 · Cracks 4 : Organic compounds 1 〇 : Composite particles 2 0 : Liquid crystal group 22 : Composite particle surface 24 : Composite particle surface -53

Claims (1)

201231487 VII. Patent application range: 1. A liquid crystalline resin composition containing: a liquid crystalline epoxy resin represented by the following formula (1), a curing agent, and aluminum nitride composite particles, the composite particles having nitrogen The aluminum-coated particles and the first coating layer containing the α-alumina in a region covering at least a part of the surface of the aluminum nitride particles, and a region other than the first coating layer covering the surface of the aluminum nitride particles and containing an organic substance Second coating layer (In the formula (1), X represents a single bond or a linking group selected from at least one of the group consisting of a valent group represented by the following chemical formula; and Υ each independently represents an aliphatic group having 1 to 8 carbon atoms; a hydrocarbon group, an aliphatic alkoxy group having 1 to 8 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano 'nitro group or an ethyl fluorenyl group; η represents an integer of 〇~4, and k represents 〇~7 Integer, m means 〇~8 integer '1 means 〇~12 integer) -54- S 201231487 2. The liquid crystalline resin composition of claim 1, wherein the organic substance is a reaction product of the aluminum nitride and an organic compound, and the organic compound has at least one of an alcoholic hydroxyl group and a carboxyl group, and a carbon number It is a hydrocarbon group of 1 to 2 4 . 3. The liquid crystalline resin composition of claim 1, wherein the content of the aluminum nitride composite particles is 50% by mass to 95% by mass. /〇. (4) The liquid crystalline resin composition of claim 1, wherein the aluminum nitride composite particles correspond to a peak of a (1 〇〇) plane of the α alumina in an X-ray diffraction spectrum of the CuKa line, The intensity ratio of the peak corresponding to the (1 1 3 ) plane of the aluminum nitride is 1 or less on the basis of the area. A heat-dissipating material precursor which is a semi-cured material of a liquid crystalline resin composition according to any one of claims 1 to 4. A flaky semi-cured material of a liquid crystalline resin composition according to any one of claims 1 to 4, which is a bismuth-grade material. 7. A prepreg comprising a fibrous base material and a semi-hardened material of a liquid crystalline resin composition as claimed in any one of claims 1 to 4 of the above-mentioned fiber-55-201231487-dimensional substrate. . A heat-dissipating material, which is a cured product of a liquid crystalline resin composition according to any one of claims 1 to 4. 9. The heat dissipating material according to claim 8, wherein the cured product of the liquid crystalline epoxy resin has an alignment surface, and the alignment surface has an angle of 50 to 90 with respect to a surface of the aluminum nitride composite particle. . A laminated layer comprising a resin layer composed of a liquid crystal resin composition according to any one of claims 1 to 4, as claimed in claim 6 A resin sheet and a hardened layer of at least one resin-containing layer selected from the prepreg of claim 7 of the present invention, a metal substrate having a metal case, a metal plate, and the aforementioned metal foil and the aforementioned metal plate A resin layer composed of a resin composition as set forth in any one of claims 1 to 5, a B-grade sheet as claimed in claim 6 and a pre-requisite as in claim 7 A hardened layer of at least one resin-containing layer selected from the dip. 1. A printed wiring board comprising a wiring layer, a metal substrate, and a resin composition according to any one of claims 1 to 4, wherein the wiring layer and the metal substrate are formed. A resin layer, a resin sheet as claimed in claim 6 and a cured product of at least one resin-containing layer selected from the prepreg of claim 7 of the patent application. The method for producing a liquid crystalline resin composition according to any one of claims 1 to 4, which has the following method: -56- S 201231487 calcining aluminum nitride particles in an oxygen-containing environment, a step of forming an alpha alumina layer having a cracked portion of aluminum nitride on the surface of the aluminum nitride particle; and having at least one of an alcoholic hydroxyl group and a carboxyl group and a carbon number of 1 in the crack portion a step of reacting an aromatic compound of a hydrocarbon group of 24 with the exposed aluminum nitride to obtain an aluminum nitride composite particle; and dispersing the aluminum nitride composite particle in a liquid crystalline epoxy having a formula (1) Steps in the composition of the resin and hardener (In the formula (1), X represents a single bond or a linking group selected from at least one of the group consisting of a valent group represented by the following chemical formula; and Y each independently represents an aliphatic group having 1 to 8 carbon atoms; a hydrocarbon group, an aliphatic oxy group having 1 to 8 carbon atoms, a fluorine atom, a gas atom, a desert atom, a transatomic atom, a cyano group, a nitro group or an ethyl fluorenyl group; η represents an integer of 0 to 4', and k represents 0 to 7 The integer 'm' represents an integer from 0 to 8 '1 represents an integer from 0 to 12) -57- 201231487 2 CH II CH -- N II CHII c III c -- N II N H3 C-C II CH CMO I CH II CH N CIC II CH o CNO N Nfo Nio II CH (Y)k (Y)m (Y)l (Y)n 1 4 . A method for producing a heat-dissipating material precursor, which comprises the liquid crystalline resin composition according to any one of claims 1 to 4 Heat treatment to perform the step of semi-hardening. A method for producing a heat-dissipating material, which comprises the step of heat-treating a liquid crystalline resin composition according to any one of items 1 to 4 of the above-mentioned patents to be hardened. -58- s