Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B21/00—Nitrogen; Compounds thereof
  • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
  • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the present invention relates to surface-modified boron nitride particles, a method for producing surface-modified boron nitride particles, a composition for forming a heat conductive material, a heat conductive material, a heat conductive sheet, and a device with a heat conductive layer.
• Patent Document 1 discloses "a filler characterized by heating boron nitride in an oxidizing atmosphere to increase the weight by 1% by weight or more and 40% by weight or less (claim 1)". It is also disclosed that the filler thus obtained may be reacted with the coupling agent (modified alkoxysilane coupling agent) (paragraph 0012, etc.).
• the heat conductive material is also required to have a sufficiently high peel (peeling) strength when it is adhered to an object (adhesive material) that transfers heat.
• peel peel
• the present inventor examined the heat conductive material using boron nitride described in Patent Document 1, it was found that there is room for improvement mainly in the peel strength.
• Another object of the present invention is to provide a method for producing surface-modified boron nitride particles, a composition for forming a heat-conducting material, a heat-conducting material, a heat-conducting sheet, and a device with a heat-conducting layer, regarding the surface-modified boron nitride particles. ..
• the O / B ratio which is the atomic concentration ratio of the oxygen atomic concentration to the boron atomic concentration on the surface, which is detected by X-ray photoelectron spectroscopy, is 0.12 or more, and is the atomic concentration ratio of the silicon atomic concentration to the boron atomic concentration.
• a certain Si / B ratio is 0.010 or more, and Surface-modified boron nitride particles having a D value obtained by the following formula (1) of 0.010 or less.
• Equation (1): D value B (OH) 3 (002) / BN (002) B (OH) 3 (002): Peak intensity derived from the (002) plane of boron hydroxide having a trichrytic space group measured by X-ray diffraction BN (002): Measured by X-ray diffraction Peak intensity derived from the (002) plane of boron nitride having a hexagonal space group [2] The surface-modified boron nitride particle according to [1], wherein the O / B ratio is 0.20 or more. [3] The surface-modified boron nitride particle according to [1] or [2], wherein the Si / B ratio is 0.020 or more.
• [4] The method for producing surface-modified boron nitride particles according to any one of [1] to [3].
• [5] The method for producing surface-modified boron nitride particles according to any one of [1] to [3].
• a method for producing surface-modified boron nitride particles which comprises a step of plasma-treating the boron nitride particles in the presence of a gas of a compound represented by the following general formula (1) to obtain surface-modified boron nitride particles.
• each of the four Rs independently represents a methyl group or an ethyl group.
• a composition for forming a heat conductive material which comprises the surface-modified boron nitride particles according to any one of [1] to [3] and a resin binder or a precursor thereof.
• [7] The composition for forming a heat conductive material according to [6], wherein the resin binder or a precursor thereof contains at least one selected from the group consisting of an epoxy compound and a silicone compound.
• [11] A heat conductive sheet made of the heat conductive material according to [10].
• the present invention can provide surface-modified boron nitride particles which are excellent in the effect of improving the thermal conductivity of the formed heat conductive material and can be used for producing the heat conductive material having excellent peel strength. Further, regarding the surface-modified boron nitride particles, a method for producing surface-modified boron nitride particles, a composition for forming a heat conductive material, a heat conductive material, a heat conductive sheet, and a device with a heat conductive layer can be provided.
• the surface-modified boron nitride particles of the present invention the composition for forming a heat conductive material, and the like will be described in detail.
• the description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
• the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• (meth) acryloyl group means “either one or both of acryloyl group and methacryloyl group”.
• (meth) acrylamide group means “either one or both of an acrylamide group and a methacrylamide group”.
• the acid anhydride group may be a monovalent group or a divalent group.
• the acid anhydride group represents a monovalent group, a substitution obtained by removing an arbitrary hydrogen atom from an acid anhydride such as maleic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride.
• the group is mentioned.
• the acid anhydride group represents a divalent group, the group represented by * -CO-O-CO- * is intended (* represents a bond position).
• substituents and the like that do not specify substitution or non-substitution if possible, further substituents (for example, a group of substituents described later) are added to the groups as long as the desired effect is not impaired.
• Y may be possessed.
• alkyl group means a substituted or unsubstituted alkyl group (an alkyl group which may have a substituent) as long as the desired effect is not impaired.
• the type of the substituent, the position of the substituent, and the number of the substituents in the case of "may have a substituent” are not particularly limited. Examples of the number of substituents include one or two or more.
• substituent examples include a monovalent non-metal atomic group excluding a hydrogen atom, and a group selected from the following substituent group Y is preferable.
• halogen atom examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
• Substituent group Y Halogen atoms (-F, -Br, -Cl, -I, etc.), hydroxyl groups, amino groups, carboxylic acid groups and their conjugate base groups, anhydrous carboxylic acid groups, cyanate ester groups, unsaturated polymerizable groups, epoxy groups, oxetanyl Group, aziridinyl group, thiol group, isocyanate group, thioisocyanate group, aldehyde group, alkoxy group, allyloxy group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, N-alkylamino group, N, N-dialkylamino Group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ary
• sulfinamoyl group N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfina Moil group, sulfamoyl group, N-alkyl sulfamoyl group, N, N-dialkyl sulfamoyl group, N-aryl sulfamoyl group, N, N-diaryl sulfamoyl group, N-alkyl-N-arylsul Famoyl group, N-acylsulfamoyl group and its conjugated base group, N-alkylsulfonylsulfamoyl group (-SO 2 NHSO 2 (alkyl)) and its conjugated base group, N-arylsulfon
• each of the above-mentioned groups may further have a substituent (for example, one or more groups among the above-mentioned groups), if possible.
• a substituent for example, one or more groups among the above-mentioned groups
• an aryl group which may have a substituent is also included as a group selectable from the substituent group Y.
• the number of carbon atoms of the group is, for example, 1 to 20.
• the number of atoms other than the hydrogen atom of the group selected from the substituent group Y is, for example, 1 to 30.
• these substituents may or may not form a ring by bonding with each other or with a group to be substituted, if possible.
• the alkyl group (or the alkyl group portion in a group containing an alkyl group as a partial structure such as an alkoxy group) may be a cyclic alkyl group (cycloalkyl group) and has one or more cyclic structures as a partial structure. It may be an alkyl group.
• the surface-modified boron nitride particles of the present invention are surface-modified boron nitride particles containing the boron nitride particles and the surface modifier adsorbed on the surface of the boron nitride particles, and are detected by X-ray photoelectron spectroscopy.
• the O / B ratio which is the atomic concentration ratio of the oxygen atom concentration to the boron atom concentration, is 0.12 or more on the surface
• the Si / B ratio which is the atomic concentration ratio of the silicon atom concentration to the boron atom concentration, is 0.01 or more.
• the D value obtained by the following formula (1) is 0.010 or less.
• Equation (1): D value B (OH) 3 (002) / BN (002) B (OH) 3 (002): Peak intensity derived from the (002) plane of boron hydroxide having a trichrytic space group measured by X-ray diffraction BN (002): Measured by X-ray diffraction Peak intensity derived from the (002) plane of boron nitride having a hexagonal space group
• the boron nitride particles have excellent thermal conductivity, they often have insufficient adhesion to the resin binder. Therefore, in a heat conductive material containing ordinary boron nitride particles and a resin binder, the heat conductive material itself breaks (aggregate fracture) due to insufficient adhesion between the resin binder and the boron nitride particles. Was likely to occur, and it was difficult to achieve the desired peel strength. In order to solve such a problem, it was considered to improve the adhesion with the resin binder by using the boron nitride particles as surface-modified boron nitride particles surface-modified with a silane coupling agent or the like.
• the amount of functional groups serving as reaction points with the silane coupling agent is small on the surface of the boron nitride particles, and it is difficult to introduce a sufficient amount of the silane coupling agent.
• the boron nitride particles are subjected to surface modification treatment such as heating in an oxidizing atmosphere to introduce oxygen atoms on the surface of the boron nitride particles, thereby causing the boron nitride particles.
• surface modification treatment such as heating in an oxidizing atmosphere to introduce oxygen atoms on the surface of the boron nitride particles, thereby causing the boron nitride particles.
• this phenomenon is caused by the formation of boron hydroxide on the surface of the boron nitride particles by undergoing a surface modification treatment, and such boron hydroxide has an effect of improving the strength and thermal conductivity of the boron nitride particles. It was speculated that it had an adverse effect on. Therefore, the surface-modified boron nitride particles of the present invention focus on the boron hydroxide content in the surface-modified boron nitride particles, and the (002) plane of boron nitride having a hexagonal space group measured by X-ray diffraction.
• the ratio of the peak intensity derived from the (002) plane of boron hydroxide having a triclinal space group measured by X-ray diffraction to the peak intensity derived from is not more than a predetermined value. There is. That is, since the surface-modified boron nitride particles of the present invention have a low content of boron hydroxide, the strength of the surface-modified boron nitride particles is sufficiently maintained, and the peel strength of the obtained heat conductive material is not adversely affected. It is believed that it is suppressed.
• the surface-modified boron nitride particles of the present invention have a low content of boron hydroxide, it is considered that the surface-modified boron nitride particles have no adverse effect on the effect of improving the thermal conductivity or are sufficiently suppressed. ing. Further, in addition to the above-mentioned regulations, the surface-modified boron nitride particles of the present invention have an atomic concentration ratio (O / B) of oxygen atom concentration and silicon atom concentration on the surface, which is detected by X-ray photoelectron spectroscopy. It stipulates that the ratio and Si / B ratio) should be greater than or equal to the predetermined values.
• the surface-modified boron nitride particles of the present invention a sufficient amount of the surface modifier is introduced into the surface-modified boron nitride particles of the present invention, and the adhesion between the surface-modified boron nitride particles and the resin binder is good, so that excellent peel strength is realized. I'm guessing that it has been done.
• the peel strength of the formed heat conductive material can be improved and / or the effect of improving the heat conductivity of the formed heat conductive material is excellent. Also called the effect of.
• the surface-modified boron nitride particles of the present invention include boron nitride particles.
• the boron nitride particles are particles containing boron nitride, and the content of boron nitride in the boron nitride particles is preferably 90% by mass or more, more preferably 95% by mass or more, and 99 by mass, based on the total mass of the boron nitride particles. More preferably, it is by mass or more.
• the upper limit of the content is, for example, 100% by mass or less, and may be less than 100% by mass.
• the content of the boron nitride particles in the surface-modified boron nitride particles of the present invention is preferably 90% by mass or more, more preferably 95% by mass or more, and 99% by mass or more, based on the total mass of the surface-modified boron nitride particles. Is more preferable, and 99.9% by mass or more is particularly preferable.
• the upper limit of the content is, for example, less than 100% by mass, preferably 99.9999% by mass or less.
• the shape of the surface-modified boron nitride particles of the present invention is not particularly limited, and may be any of a scaly shape, a flat plate shape, rice granules, a spherical shape, a cube shape, a spindle shape, and an indefinite shape. Further, the surface-modified boron nitride particles may be aggregated particles (secondary particles) formed by agglomerating fine particles having these shapes. The aggregated particles as a whole may be, for example, spherical or amorphous. Above all, the surface-modified boron nitride particles are preferably aggregated particles. The shape of the boron nitride particles in the surface-modified boron nitride particles is the same as that described for the surface-modified boron nitride particles.
• the size of the surface-modified boron nitride particles of the present invention is not particularly limited.
• the average particle size of the surface-modified boron nitride particles is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, still more preferably 60 ⁇ m or less, in that the dispersibility of the surface-modified boron nitride particles is more excellent.
• the lower limit is not particularly limited, but in terms of handleability and / or thermal conductivity, 500 nm or more is preferable, 10 ⁇ m or more is more preferable, 20 ⁇ m or more is further preferable, and 40 ⁇ m or more is particularly preferable.
• 500 nm or more is preferable, 10 ⁇ m or more is more preferable, 20 ⁇ m or more is further preferable, and 40 ⁇ m or more is particularly preferable.
• For the average particle size of the surface-modified boron nitride particles 100 surface-modified boronitride particles were randomly selected using an electronic microscope, and the particle size (major diameter) of each surface-modified boron nitride particle was measured. Calculate them by arithmetically averaging them.
• the size of the boron nitride particles in the surface-modified boron nitride particles is the same as that described for the surface-modified boron nitride particles. Further, when the surface-modified boron nitride particles of the present invention are obtained by subjecting commercially available boron nitride particles to a predetermined treatment, if it is recognized that the average particle size of the particles does not change significantly before and after the treatment, The catalog value of the average particle size of the commercially available boron nitride particles may be adopted as the average particle size of the surface-modified boron nitride particles.
• the specific surface area of the surface-modified boron nitride particles of the present invention is preferably 0.1 to 25.0 m 2 / g, more preferably 1.0 to 10.0 m 2 / g, and 1.3 to 6.0 m 2 / g. Is more preferable.
• the specific surface area of the surface-modified boron nitride particles is the BET specific surface area obtained by the BET method.
• the specific surface area of the surface-modified boron nitride particles in the surface-modified boron nitride particles is the same as that described for the surface-modified boron nitride particles.
• Atomic concentration ratio (O / B ratio, oxygen atom concentration (atom) of oxygen atom concentration to boron atom concentration on the surface of surface modified boron nitride particles detected by X-ray photoelectron spectroscopy on the surface modified boron nitride particles of the present invention. %) / Boron atom concentration (atomic%)) is 0.12 or more, preferably 0.15 or more, and more preferably 0.20 or more.
• the upper limit of the atomic concentration ratio is not particularly limited, and is, for example, 0.25 or less.
• Atomic concentration ratio Si / B ratio, silicon atom concentration (atom) of silicon atom concentration to boron atom concentration on the surface of surface-modified boron nitride particles detected by X-ray photoelectron spectroscopy on the surface-modified boron nitride particles of the present invention. %) / Boron atom concentration (atomic%)) is 0.010 or more, preferably 0.020 or more.
• the upper limit of the atomic concentration ratio is not particularly limited, and is, for example, 0.040 or less.
• the O / B ratio and the Si / B ratio on the surface of the surface-modified boron nitride particles are measured as follows. That is, the surface-modified boron nitride particles are measured by an X-ray photoelectron spectroscope (XPS) (manufactured by ULVAC-PHI: Versa Probe II). As detailed measurement conditions, monochrome Al (tube voltage; 15 kV) is used as the X-ray source, and the analysis area is 300 ⁇ m ⁇ 300 ⁇ m. The peak area values of oxygen atom, nitrogen atom, boron atom, carbon atom, and silicon atom obtained by the measurement are corrected by the sensitivity coefficient of each element.
• XPS X-ray photoelectron spectroscope
• the atomic concentration ratio (O / B ratio and Si / B ratio) is calculated based on the obtained ratio of the number of atoms of the oxygen atom, the ratio of the number of atoms of the boron atom, and the number of atoms of the silicon atom. can.
• the method of correcting the peak area values of oxygen atom, nitrogen atom, boron atom, carbon atom, and silicon atom obtained by the measurement by the sensitivity coefficient of each element is specifically for oxygen atom.
• the peak area values from 528 eV to 538 eV are divided by the sensitivity coefficient 0.733 for oxygen atoms, and the peak area values from 394 eV to 403 eV for nitrogen atoms are divided by the sensitivity coefficient 0.499 for nitrogen atoms.
• the peak area value of 187 eV to 196 eV is divided by the sensitivity coefficient of 0.171 for the boron atom, and for the carbon atom, the peak area value of 282 eV to 290 eV is divided by the sensitivity coefficient of 0 for the carbon atom.
• the atomic concentration ratio on the surface of the boron nitride particles is measured as follows.
• the surface-modified boron nitride particles of the present invention have a D value obtained by the following formula (1) of 0.010 or less, preferably 0.005 or less.
• the lower limit of the D value is not particularly limited, and is, for example, 0 or more.
• BN (002): Peak intensity (2 ⁇ 27.5 ° to 28.5 °) derived from the (002) plane of boron nitride having a hexagonal space group measured by X-ray diffraction.
• the surface-modified boron nitride particles of the present invention contain a surface modifier adsorbed on the surface of the boron nitride particles.
• the surface modifier is a compound capable of surface modifying an inorganic component (particularly boron nitride particles).
• surface modification means a state in which an organic substance is adsorbed on at least a part of the surface of an inorganic component (boron nitride particles or the like).
• the form of adsorption is not particularly limited, and may be in a bonded state.
• the surface modification also includes a state in which an organic group obtained by desorbing a part of an organic substance is bonded to the surface of an inorganic component (boron nitride particles or the like).
• the bond may be any bond such as a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a van der Waals bond, and a metal bond.
• the surface modification may be made to form a monomolecular film on at least a part of the surface.
• the monolayer is a monolayer formed by chemisorption of organic molecules and is known as Self-Assembled MonoLayer (SAM).
• SAM Self-Assembled MonoLayer
• the surface modification may be only a part of the surface of the inorganic substance (boron nitride particles or the like) or the whole surface.
• the surface modifier preferably contains a silicon atom. Further, both a surface modifier containing no silicon atom and a surface modifier containing a silicon atom may be contained.
• silane coupling agent examples include a silane coupling agent.
• the silane coupling agent is a compound having a structure in which one or more hydrolyzable groups and one or more groups other than hydrolyzable groups are bonded to a silicon atom.
• the hydrolyzable group include an alkoxy group (preferably 1 to 10 carbon atoms) and a halogen atom such as a chlorine atom.
• the number of hydrolyzable groups directly bonded to the silicon atom of the silane coupling agent is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more. There is no upper limit to the above number, for example, 10,000.
• the silane coupling agent has a reactive group.
• the reactive group is preferably, for example, a group that can be crosslinked with a resin binder or a precursor thereof as described later.
• Specific examples of the reactive group include an epoxy group, an oxetanyl group, a vinyl group, a (meth) krill group, a styryl group, an amino group, an isocyanate group, a mercapto group, and an acid anhydride group.
• the number of reactive groups contained in the silane coupling agent is preferably 1 or more, and may be 2 or more. There is no upper limit to the above number, for example, 10,000.
• silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxylane, and trimethoxy [3- (phenylamino) propyl] silane.
• Aminosilane-based silane coupling agents 3-glycidoxypropyltrimethoxysilanes and epoxysilane-based silane coupling agents such as ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilanes; triethoxyvinylsilanes, and Vinyl silane-based silane coupling agents such as vinyl-tri ( ⁇ -methoxyethoxy) silane; cionic silane-based silanes such as N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane hydrochloride Coupling agents; phenyltrimethoxysilanes and phenylsilane-based silane coupling agents such as phenyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane-based methacrylsilane-based silane coupling agents; 3-acryloxypropyl Acrylic silane si
• Coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; ureidosilane-based silane coupling agents such as 3-ureidopropyltrial koshishisilane. Also, styrylsilane-based silane coupling agents such as p-styryltrimethoxysilane.
• the silane coupling agent may be used alone or in combination of two or more.
• the silane coupling agent may be a polymer type silane coupling agent.
• the molecular weight of the silane coupling agent is preferably 1000 or more, more preferably 2000 or more.
• the upper limit is preferably 100,000 or less, more preferably 10,000 or less.
• the content of the reactive group that can be crosslinked with the resin binder or its precursor is preferably 1000 g / mol or less, more preferably 500 g / mol or less.
• the lower limit of the content is, for example, more than 0 g / mol.
• the silane coupling agent may be in a state in which a part or all of the hydrolyzable groups are hydrolyzed in the surface-modified boron nitride particles.
• each of the four Rs independently represents a methyl group or an ethyl group. That is, the compound represented by the general formula (1) has 1 to 4 hydrolyzable groups (methoxy group or ethoxy group directly bonded to the silicon atom).
• the compound represented by the formula (1) may be in a state in which a part or all of the hydrolyzable groups are hydrolyzed in the surface-modified boron nitride particles.
• the compound represented by the formula (1) may be used alone or in combination of two or more.
• the mass ratio of the surface modifier to the boron nitride particles is not particularly limited.
• the mass ratio is preferably 0.00001 to 0.5, more preferably 0.0001 to 0.1, in that the dispersibility of the surface-modified boron nitride particles is more excellent.
• the method for producing surface-modified boron nitride particles of the present invention is not particularly limited as long as a predetermined surface-modified boron nitride particles can be obtained.
• the ordinary surface-modified boron nitride particles obtained by ordinary surface-modifying ordinary boron nitride particles on the market have an O / B ratio range defined as a requirement for the surface-modified boron nitride particles of the present invention.
• Si / B ratio range and D value range the Si / B ratio is often less than a predetermined range.
• the D value is often out of the predetermined range.
• ⁇ First manufacturing method> As a method for producing surface-modified boron nitride particles of the present invention, for example, the surface of the surface-modified boron nitride particles is modified, and the treated boron nitride particles (surface-modified boron nitride particles) are brought into contact with a surface modifier. There is a method for obtaining surface-modified boron nitride particles. Such a manufacturing method is also hereinafter referred to as a first manufacturing method.
• Step 1A A step of performing plasma treatment on boron nitride particles.
• Step 1B A step of contacting the plasma-treated boron nitride particles (surface-modified boron nitride particles) with a surface modifier (preferably a silane coupling agent) to obtain surface-modified boron nitride particles.
• a surface modifier preferably a silane coupling agent
• Step 1A the boron nitride particles are subjected to plasma treatment. As a result, surface-modified boron nitride particles are obtained.
• the boron nitride particles targeted in step 1A for example, commercially available boron nitride particles can be used.
• the boron nitride particles to be the target of the step 1A the boron nitride particles described as the boron nitride particles contained in the surface-modified boron nitride particles can be used.
• the boron nitride particles targeted in step 1A preferably have an O / B ratio of 0 or more and less than 0.12, a Si / B ratio of 0 or more and less than 0.010, and a D value. It is preferably 0 or more and 0.010 or less (more preferably 0 or more and 0.005 or less).
• Step 1A is preferably performed from the viewpoint of improving the O / B ratio while paying attention so that the D value does not increase as much as possible.
• the surface-modified boron nitride particles obtained in step 1A maintain a D value of 0 or more and 0.010 or less (more preferably 0 or more and 0.005 or less), and an O / B ratio of 0. It is preferable to perform step 1A so as to be in the range of .12 or more (more preferably 0.15 or more, further preferably 0.20 or more, and the upper limit is, for example, 0.25 or less).
• the gas (treatment gas) used in the plasma treatment examples include O 2 gas, Ar gas, N 2 gas, H 2 gas, He gas, and a mixed gas containing one or more of these.
• the treated gas preferably contains at least O 2 gas, and 60 to 100% by volume of the treated gas is O 2 from the viewpoint that it is easy to improve the O / B ratio while suppressing an increase in the D value. It is more preferably a gas, more preferably 90 to 100% by volume of the treated gas is an O 2 gas, and particularly preferably the treated gas is substantially O 2 gas alone. That is, the plasma treatment is preferably oxygen plasma treatment.
• the plasma treatment may be carried out under atmospheric pressure or under reduced pressure (500 Pa or less, preferably 0 to 100 Pa).
• the output in the plasma treatment is preferably 50 to 1000 W, more preferably 70 to 500 W, still more preferably 100 to 300 W, from the viewpoint of controlling the amount of boron hydroxide produced, regardless of whether it is performed under atmospheric pressure or reduced pressure. ..
• the plasma treatment time is preferably 0.2 to 30 hours, more preferably 4 to 15 hours.
• the plasma treatment time is preferably 0.2 to 10 hours, more preferably 0.2 to 3 hours.
• the plasma treatment may be performed continuously or intermittently. When it is performed intermittently, it is preferable that the total processing time is within the above range.
• the treatment temperature when performing plasma treatment is preferably 0 to 200 ° C, more preferably 15 to 100 ° C.
• a surface modifier (preferably a silane coupling agent) is adsorbed on the plasma-treated boron nitride particles (surface-modified boron nitride particles) to obtain surface-modified boron nitride particles.
• a surface modifier preferably a silane coupling agent
• the surface modifier described as the surface modifier contained in the surface-modified boron nitride particles can be used.
• the method of adsorbing the surface modifier to the surface modified boron nitride particles is not limited, and for example, a mixture containing a solvent (organic solvent such as acetonitrile and / or water), the surface modified boron nitride particles, and the surface modifier.
• a method using a liquid can be mentioned. More specifically, the surface modifier is brought into contact with and adsorbed on the surface-modified boron nitride particles in the above mixed solution.
• the surface modifier may be introduced into the mixed solution in a state where the hydrolyzable group in the surface modifier is hydrolyzed in advance when preparing the mixed solution. ..
• a hydroxysilyl group (a group in which a hydroxyl group directly bonds to a silicon atom) generated by pre-hydrolyzing a hydrolyzable group in a surface modifier can cause the surface modifier to undergo a cross-linking reaction with surface-modified boron nitride particles. preferable.
• the time for contacting the surface-modified boron nitride particles with the surface modifier is preferably 0.1 to 24 hours, more preferably 0.5 to 10 hours, and further preferably 1.5 to 6 hours. preferable.
• the temperature of the mixed solution when the surface-modified boron nitride particles are brought into contact with the surface modifier is preferably, for example, 1 to 200 ° C, more preferably 10 to 160 ° C, although it depends on the type of the surface modifier. It is preferable, and more preferably 15 to 140 ° C.
• the obtained surface-modified boron nitride particles may be taken out from the mixed solution.
• the method of extracting the surface-modified boron nitride particles from the above-mentioned mixed solution and examples thereof include a method of filtering the above-mentioned mixed solution and separating the surface-modified boron nitride particles as a filter medium. It is also preferable to wash the extracted surface-modified boron nitride particles with water and / or an organic solvent or the like.
• the washed surface-modified boron nitride particles are dried using an oven or the like.
• a solid content component such as an epoxy compound described later
• other than the surface-modified boron nitride particles constituting the composition for forming a heat conductive material as described later may be added to the mixed liquid, for example, heat conduction.
• surface-modified boron nitride particles may be produced therein.
• ⁇ Second manufacturing method> As a method for producing the surface-modified boron nitride particles of the present invention, for example, the surface of the surface-modified boron nitride particles is modified, and at the same time, the surface-modified boron nitride particles are brought into contact with the surface modifying agent to bring the surface-modified boron nitride particles into contact with the surface-modified boron nitride particles. There is a way to get. Such a manufacturing method is also hereinafter referred to as a second manufacturing method.
• Step 2A A step of subjecting boron nitride particles to plasma treatment in the presence of a gas of a surface modifier (preferably the compound represented by the above general formula (1)) to obtain surface-modified boron nitride particles.
• a gas of a surface modifier preferably the compound represented by the above general formula (1)
• the boron nitride particles targeted in step 2A include the boron nitride particles mentioned as the boron nitride particles that can be used in step 1A.
• the gas (treatment gas) used in the plasma treatment contains at least the gas of the surface modifier (preferably the compound represented by the above general formula (1)).
• the treatment gas may contain, for example, O 2 gas, Ar gas, N 2 gas, H 2 gas, He gas, and a plurality of these as other gases, and preferably contains at least O 2 gas. ..
• the treatment gas contains Ar gas.
• the gas content of the surface modifier (preferably the compound represented by the above general formula (1)) is preferably 1 to 99% by volume, more preferably 5 to 95% by volume, based on the total volume of the treated gas. preferable.
• the content of the O 2 gas is preferably 1 to 99% by volume, more preferably 5 to 95% by volume, based on the total volume of the treated gas.
• the content thereof is preferably 1 to 99% by volume, more preferably 5 to 95% by volume, based on the total volume of the treated gas.
• the ratio (volume ratio) of the content of O 2 gas to the gas content of the surface modifier (preferably the compound represented by the above general formula (1)) is preferably 5/95 to 95/5, preferably 30. / 70 to 70/30 is more preferable, and 45/55 to 55/45 is even more preferable.
• the other conditions of the plasma treatment in the step 2A the conditions other than the matters relating to the type and ratio of the processing gas described for the plasma treatment in the step 1A can be similarly applied.
• the first manufacturing method and the second manufacturing method may be used in combination as desired.
• the surface-modified boron nitride particles obtained by carrying out the second production method are further brought into contact with a surface modifying agent (silane coupling agent or the like) in a mixed solution to obtain the surface-modified boron nitride particles of the present invention. It may be completed.
• a surface modifying agent silane coupling agent or the like
• the surface-modified boron nitride particles of the present invention can be used, for example, in the production of a composition for forming a heat conductive material.
• composition for forming a heat conductive material The present invention also relates to a composition for forming a heat conductive material (hereinafter, also simply referred to as “composition”).
• composition for forming a heat conductive material
• the composition of the present invention comprises the surface-modified boron nitride particles of the present invention and a resin binder or a precursor thereof.
• the composition of the present invention containing the surface-modified boron nitride particles of the present invention can form a heat conductive material having excellent peel strength.
• the heat conductive material has good heat conductivity.
• the surface-modified boron nitride particles of the present invention contained in the composition are as described above.
• the content of the surface-modified boron nitride particles of the present invention is preferably 35% by volume or more, preferably 50% by volume or more, based on the total solid content of the composition, from the viewpoint of more excellent thermal conductivity of the obtained heat conductive material. More preferably, 55% by volume or more is further preferable.
• the upper limit of the content is less than 100% by volume, preferably 80% by volume or less.
• the upper limit of the content is preferably less than 50% by volume from the viewpoint that the peel strength of the heat conductive material is more excellent.
• the content of the surface-modified boron nitride particles is preferably determined as appropriate in consideration of the characteristics of the resin binder or its precursor contained together with the surface-modified boron nitride particles in the composition.
• the surface-modified boron nitride particles of the present invention may be used alone or in combination of two or more.
• the total solid content is intended as a component forming a heat conductive material and does not contain a solvent.
• the component forming the heat conductive material referred to here may be a component whose chemical structure changes by reacting (polymerizing) when forming the heat conductive material. Further, if it is a component forming a heat conductive material, even if its property is liquid, it is regarded as a solid content.
• the composition comprises a resin binder or a precursor thereof.
• the resin binder or its precursor is generically referred to as a binder component.
• the binder component may be the resin binder itself or a precursor of the resin binder.
• the composition using the resin binder itself examples include a composition containing a solvent and a resin binder which is a polymer (resin) dissolved in the solvent. When the solvent of this composition evaporates, the resin binder is precipitated, and a heat conductive material in which the resin binder functions as a binder (binder) can be obtained.
• the composition contains a thermoplastic resin as the resin binder
• the composition may be, for example, a composition containing a resin binder which is a thermoplastic resin and does not contain a solvent. This composition may be heated and melted and then cooled and solidified in a desired form to obtain a heat conductive material in which the resin binder, which is the thermoplastic resin, functions as a binder (binder).
• the precursor of the resin binder is, for example, a component that polymerizes and / or crosslinks under predetermined conditions to become a resin binder (polymer and / or crosslinked body) in the process of forming a heat conductive material from the composition. ..
• the resin binder thus formed functions as a binder (binder) in the heat conductive material.
• the precursor of the resin binder include curable compounds.
• the curable compound include compounds in which polymerization and / or crosslinking proceeds by heat or light (ultraviolet light or the like) to cure. That is, thermosetting compounds and photocurable compounds can be mentioned. These compounds may be polymers or monomers.
• the curable compound may be a mixture of two or more compounds (for example, a main agent and a curing agent).
• the precursor of the resin binder may chemically react with a surface modifier described later.
• the resin binder examples include epoxy resin, silicone resin, phenol resin, polyimide resin, polyester resin, bismaleimide resin, melamine resin, phenoxy resin, and isocyanate resin (polyurethane).
• examples thereof include resins formed by chain polymerization of two or more monomers having a polymerizable double bond, such as resins, polyurea resins, polyurethane urea resins, etc.) and radical polymers ((meth) acrylic resins, etc.).
• the resin binder (including the resin binder formed from the precursor of the resin binder), for example, one or more combinations of the following (functional group 1 / functional group 2) between different monomers and / or prepolymers react.
• the composition may contain a precursor of a resin binder for forming a resin formed by reacting one or more combinations of the following (functional group 1 / functional group 2).
• (Functional group 1 / functional group 2) (polymerizable double bond / polymerizable double bond), (polymerizable double bond / thiol group), (carboxylic acid halide group (carboxylate group, etc.) / Primary or secondary amino group), (carboxyl group / primary or secondary amino group) (carboxylic acid anhydride group / primary or secondary amino group), (carboxyl group / aziridine group), (carboxyl group / isocyanate group), (Carboxy group / epoxy group), (carboxyl group / benzyl halide group), (primary or secondary amino group / isocyanate group), (primary, secondary or tertiary amino group / benzyl halide group), (primary) Amino group / aldehydes), (isocyanate group / isocyanate group), (isocyanate group / hydroxyl group), (isocyanine group / epoxy group), (hydroxy
• the composition preferably contains a precursor of a resin binder as a binder component, and more preferably contains a precursor of a resin binder capable of forming an epoxy resin or a silicone resin.
• the binder component in the composition preferably contains at least one selected from the group consisting of epoxy compounds and silicone compounds.
• the resin binder may be used alone or in combination of two or more.
• the resin binder (particularly, the resin binder formed from the precursor of the resin binder) is preferably an epoxy resin. That is, the composition preferably contains a binder component (that is, an epoxy compound or the like) capable of forming an epoxy resin.
• the epoxy resin can be formed by the epoxy compound alone or by polymerizing the epoxy compound with another compound (active hydrogen group-containing compound such as phenol compound and amine compound, and / or acid anhydride). Above all, the epoxy resin is preferably formed by reacting an epoxy compound with another compound (preferably a phenol compound).
• Epoxy compound is a compound having at least one epoxy group (oxylanyl group) in one molecule.
• the epoxy group is a group obtained by removing one or more hydrogen atoms (preferably one hydrogen atom) from the oxylan ring. If possible, the epoxy group may further have a substituent (a linear or branched alkyl group having 1 to 5 carbon atoms, or the like).
• the number of epoxy groups contained in the epoxy compound is preferably 2 or more, more preferably 2 to 40, still more preferably 2 to 10, and particularly preferably 2 in one molecule.
• the molecular weight of the epoxy compound is preferably 150 to 10000, more preferably 150 to 1000, and even more preferably 200 to 290.
• the epoxy group content of the epoxy compound is preferably 2.0 to 20.0 mmol / g, more preferably 5.0 to 15.0 mmol / g, still more preferably 6.0 to 14.0 mmol / g.
• the epoxy group content is intended to be the number of epoxy groups contained in 1 g of the epoxy compound.
• the epoxy compound also preferably has an aromatic ring group (preferably an aromatic hydrocarbon ring group).
• the epoxy compound may or may not exhibit liquid crystallinity. That is, the epoxy compound may be a liquid crystal compound. In other words, it may be a liquid crystal compound having an epoxy group.
• the epoxy compound is preferably a polyhydroxyaromatic ring type glycidyl ether (polyhydroxyaromatic ring type epoxy compound).
• the polyhydroxyaromatic ring-type glycidyl ether has 2 or more hydroxyl groups in an aromatic ring having 2 or more (preferably 2 to 6, more preferably 2 to 3, more preferably 2) hydroxyl groups as substituents.
• the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, and an aromatic hydrocarbon ring is preferable.
• the aromatic ring may be a polycyclic ring or a monocyclic ring.
• the number of ring members of the aromatic ring is preferably 5 to 15, more preferably 6 to 12, and even more preferably 6.
• the aromatic ring may or may not have a substituent other than the hydroxyl group.
• Examples of the polyhydroxyaromatic ring-type glycidyl ether include 1,3-phenylenebis (glycidyl ether).
• epoxy compound examples include, for example, a compound having a rod-like structure at least partially (a rod-like compound), and a compound having a disk-like structure at least partially.
• a rod-like compound a compound having a rod-like structure at least partially
• a disk-like structure a compound having a disk-like structure at least partially.
• epoxy compounds that are rod-shaped compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, and cyano-substituted phenylpyrimidines.
• examples thereof include alkoxy-substituted phenylpyrimidines, phenyldioxans, trans, and alkenylcyclohexylbenzonitriles.
• low molecular weight compounds as described above, but also high molecular weight compounds can be used.
• the polymer compound is a polymer compound obtained by polymerizing a rod-shaped compound having a low molecular weight reactive group.
• Preferred rod-shaped compounds include rod-shaped compounds represented by the following general formula (XXI).
• Q 1 and Q 2 are independent epoxy groups, and L 111 , L 112 , L 113 , and L 114 independently represent a single bond or a divalent linking group, respectively. ..
• a 111 and A 112 each independently represent a divalent linking group (spacer group) having 1 to 20 carbon atoms.
• M represents a mesogen group.
• the epoxy groups of Q1 and Q2 may or may not have a substituent.
• L 111 , L 112 , L 113 , and L 114 each independently represent a single bond or a divalent linking group.
• the divalent linking groups represented by L 111 , L 112 , L 113 , and L 114 are independently -O-, -S-, -CO-, -NR 112- , and -CO-O, respectively.
• R 112 is an alkyl group or a hydrogen atom having 1 to 7 carbon atoms.
• L 113 and L 114 are preferably —O— independently of each other.
• L 111 and L 112 are preferably single bonds independently of each other.
• a 111 and A 112 each independently represent a divalent linking group having 1 to 20 carbon atoms.
• the divalent linking group may contain heteroatoms such as non-adjacent oxygen and sulfur atoms.
• an alkylene group, an alkenylene group, or an alkynylene group having 1 to 12 carbon atoms is preferable.
• the above-mentioned alkylene group, alkenylene group, or alkynylene group may or may not have an ester group.
• the divalent linking group is preferably linear, and the divalent linking group may or may not have a substituent.
• substituents examples include a halogen atom (fluorine atom, chlorine atom, and bromine atom), a cyano group, a methyl group, and an ethyl group.
• a 111 and A 112 are each independently preferably an alkylene group having 1 to 12 carbon atoms, and more preferably a methylene group.
• M represents a mesogen group, and examples of the mesogen group include known mesogen groups. Among them, the group represented by the following general formula (XXII) is preferable.
• W 1 and W 2 independently represent a divalent cyclic alkylene group, a divalent cyclic alkaneylene group, an arylene group, or a divalent heterocyclic group, respectively.
• L 115 represents a single bond or a divalent linking group.
• n represents an integer of 1 to 4.
• W 1 and W 2 examples include 1,4-cyclohexenediyl, 1,4-cyclohexanediyl, 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,3. 4-Thiadiazole-2,5-diyl, 1,3,4-oxadiazole-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,5-diyl, thiophene-2,5-diyl, And pyridazine-3,6-zyl.
• W 1 and W 2 may each have a substituent.
• substituents include the groups exemplified in the above-mentioned substituent group Y, and more specifically, a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), cyano group, and carbon.
• An alkyl group having a number of 1 to 10 for example, a methyl group, an ethyl group, a propyl group, etc.
• an alkoxy group having 1 to 10 carbon atoms for example, a methoxy group, an ethoxy group, etc.
• a group having 1 to 10 carbon atoms for example, an acyl group.
• An acyl group for example, a formyl group and an acetyl group, etc.
• an alkoxycarbonyl group having 1 to 10 carbon atoms for example, a methoxycarbonyl group, an ethoxycarbonyl group, etc.
• an acyloxy group having 1 to 10 carbon atoms for example, an acyloxy group.
• Acetyloxy group, propionyloxy group, etc.), nitro group, trifluoromethyl group, difluoromethyl group and the like can be mentioned.
• the plurality of W 1s may be the same or different from each other.
• L 115 represents a single bond or a divalent linking group.
• the divalent linking group represented by L 115 include the above-mentioned divalent linking groups represented by L 111 to L 114 , and examples thereof include -CO-O- and -O-CO-. , -CH 2 -O-, and -O-CH 2- .
• the plurality of L 115s may be the same or different from each other.
• the preferred skeleton of the basic skeleton of the mesogen group represented by the above general formula (XXII) is illustrated below.
• the above-mentioned mesogen groups may be substituted with a substituent in these skeletons.
• the biphenyl skeleton is preferable in that the obtained heat conductive material has more excellent heat conductivity.
• the compound represented by the general formula (XXI) can be synthesized by referring to the method described in JP-A No. 11-513019 (WO97 / 00600).
• the rod-shaped compound may be a monomer having a mesogen group described in JP-A No. 11-323162 and Japanese Patent No. 4118691.
• the rod-shaped compound is preferably a compound represented by the general formula (E1).
• LE1 independently represents a single bond or a divalent linking group. Of these, LE1 is preferably a divalent linking group.
• the alkylene group may be linear, branched or cyclic, but a linear alkylene group having 1 to 2 carbon atoms is preferable.
• a plurality of LE1s may be the same or different from each other.
• LE2 is preferably single-bonded, -CO-O-, or -O-CO- independently of each other. When there are a
• LE3 may independently have a single bond or a substituent, respectively, and may have a 5-membered ring or a 6-membered ring aromatic ring group or a 5-membered ring or a 6-membered ring. Represents a non-aromatic ring group of, or a polycyclic group composed of these rings. Examples of the aromatic ring group and the non-aromatic ring group represented by LE3 include 1,4-cyclohexanediyl group, 1,4-cyclohexendyl group and 1,4 which may have a substituent.
• -Phenylene group pyrimidin-2,5-diyl group, pyridine-2,5-diyl group, 1,3,4-thiadiazol-2,5-diyl group, 1,3,4-oxadiazol-2,5 Examples thereof include a diyl group, a naphthalene-2,6-diyl group, a naphthalene-1,5-diyl group, a thiophene-2,5-diyl group, and a pyridazine-3,6-diyl group.
• a transformer body is preferable.
• LE3 is preferably a single bond, a 1,4-phenylene group, or a 1,4-cyclohexenediyl group.
• the substituent of the group represented by LE3 is preferably an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or an acetyl group, and more preferably an alkyl group (preferably 1 carbon number). preferable.
• the substituents may be the same or different.
• the plurality of LE3s may be the same or different.
• pe represents an integer of 0 or more.
• pe is an integer of 2 or more, a plurality of ( -LE3 - LE2- ) may be the same or different from each other.
• pe is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
• LE4 independently represents a substituent.
• the substituent an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or an acetyl group are preferable, and an alkyl group (preferably 1 carbon number) is more preferable.
• a plurality of LE4s may be the same or different from each other. Further, when le described below is an integer of 2 or more, a plurality of LE4s existing in the same ( LE4 ) le may be the same or different.
• le independently represents an integer of 0 to 4. Among them, le is preferably 0 to 2 independently of each other. A plurality of le's may be the same or different from each other.
• the rod-shaped compound preferably has a biphenyl skeleton in that the obtained heat conductive material has better heat conductivity.
• the epoxy compound preferably has a biphenyl skeleton, and the epoxy compound in this case is more preferably a rod-shaped compound.
• -Disc-shaped compound An epoxy compound that is a disc-shaped compound has a disc-shaped structure at least partially.
• the disk-like structure has at least an alicyclic or aromatic ring.
• the disk-shaped compound can form a columnar structure by forming a stacking structure by ⁇ - ⁇ interaction between molecules.
• Angew. Chem. Int. Ed. examples thereof include the triphenylene structure described in 2012, 51, 7990-7993 or JP-A-7-306317, and the tri-substituted benzene structure described in JP-A-2007-2220 and JP-A-2010-244038.
• a heat conductive material showing high heat conductivity can be obtained.
• the rod-shaped compound can conduct heat only linearly (one-dimensionally), whereas the disk-shaped compound can conduct heat planarly (two-dimensionally) in the normal direction, so that the heat conduction path is It is thought that the number will increase and the thermal conductivity will improve.
• the disk-shaped compound preferably has three or more epoxy groups.
• a cured product of a composition containing a disk-shaped compound having three or more epoxy groups tends to have a high glass transition temperature and high heat resistance.
• the number of epoxy groups contained in the disk-shaped compound is preferably 8 or less, and more preferably 6 or less.
• disk-shaped compound examples include C.I. Destrade et al. , Mol. Crysr. Liq. Cryst. , Vol. 71, page 111 (1981); Chemical Society of Japan, Quarterly Review of Chemistry, No. 22, Liquid crystal chemistry, Chapter 5, Chapter 10, Section 2 (1994); B. Kohne et al. , Angew. Chem. Soc. Chem. Comm. , Page 1794 (1985); J. Mol. Zhang et al. , J. Am. Chem. Soc. , Vol.
• compounds having at least one end (preferably three or more) as an epoxy group can be mentioned. Can be mentioned.
• disk-shaped compound examples include Angew. Chem. Int. Ed. At the end of the triphenylene structure described in 2012, 51, 7990-7793, and JP-A-7-306317, and the tri-substituted benzene structure described in JP-A-2007-2220 and JP-A-2010-244038. Examples thereof include compounds having at least one (preferably three or more) epoxy groups.
• nDN represents an integer of 0 or more, preferably 0 to 5, and more preferably 1.
• RDN represents a single bond or a divalent linking group.
• the divalent linking group includes -O-, -O-CO-, -CO-O-, -S-, an alkylene group (preferably 1 to 10 carbon atoms), and an arylene group (the carbon number is preferably 1 to 10). 6 to 20 is preferable), or a group composed of a combination thereof is preferable, an alkylene group is more preferable, and a methylene group is more preferable.
• epoxy compounds include, for example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, and bisphenol AD type epoxy compounds, which are glycidyl ethers such as bisphenol A, F, S, and AD. Etc .; hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol AD type epoxy compound, etc .; phenol novolac type glycidyl ether (phenol novolak type epoxy compound), cresol novolak type glycidyl ether (cresol novolak type epoxy compound), bisphenol A Novolak type glycidyl ether, etc .; Dicyclopentadiene type glycidyl ether (dicyclopentadiene type epoxy compound); Dihydroxypentadiene type glycidyl ether (dihydroxypentadiene type epoxy compound); Polyhydroxybenzene type glycidyl ether (polyhydroxybenzene type) Epoxy compound); benzenepolycarboxylic acid type gly
• a compound in which one or more of the glycidyl ether group and / or the glycidyl ester group in each of the above compounds is replaced with a diglycidylamino group or a diglycidylaminoalkylene group (diglycidylaminomethylene group, etc.) is used as the epoxy compound. You may.
• Each of the above compounds may have a substituent.
• the aromatic ring group, cycloalkane ring group, and / or alkylene group contained in each of the above compounds is other than the glycidyl ether group, the glycidyl ester group, the diglycidyl amino group, and / or the diglycidyl aminoalkylene group. It may have a substituent of.
• the epoxy compound may be used alone or in combination of two or more.
• the epoxy resin is preferably formed by reacting an epoxy compound with an active hydrogen group-containing compound.
• the active hydrogen group-containing compound is a compound having one or more (preferably two or more, more preferably 2 to 10) groups having active hydrogen (active hydrogen group). Examples of the active hydrogen group include a hydroxyl group, a primary or secondary amino group, a mercapto group and the like, and among them, a hydroxyl group is preferable.
• the active hydrogen group-containing compound is preferably a polyol having 2 or more (preferably 3 or more, more preferably 3 to 6) hydroxyl groups.
• the active hydrogen group-containing compound used in combination with the epoxy compound is preferably a phenol compound. That is, the composition of the present invention preferably contains an epoxy compound and a phenol compound as the resin binder or a precursor thereof.
• the phenol compound is a compound having one or more phenolic hydroxyl groups (preferably two or more, more preferably three or more, still more preferably 3 to 6). From the viewpoint that the effect of the present invention is more excellent, examples of the phenol compound include compounds represented by the general formula (P1).
• m1 represents an integer of 0 or more. m1 is preferably 0 to 10, more preferably 0 to 3, still more preferably 0 or 1, and particularly preferably 1.
• na and nc each independently represent an integer of 1 or more. It is preferable that na and nc are 1 to 4 independently of each other.
• R 1 and R 6 independently represent a hydrogen atom, a halogen atom, a carboxylic acid group, a boronic acid group, an aldehyde group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.
• the alkyl group may be linear or branched.
• the alkyl group preferably has 1 to 10 carbon atoms.
• the alkyl group may or may not have a substituent.
• the alkyl group portion of the alkoxy group and the alkyl group portion of the alkoxycarbonyl group are the same as those of the alkyl group.
• R 1 and R 6 are preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom or a chlorine atom, and even more preferably a hydrogen atom.
• R 7 represents a hydrogen atom or a hydroxyl group.
• the plurality of R 7s may be the same or different from each other.
• L x1 represents a single bond, -C (R 2 ) (R 3 )-or-CO-, and -C (R 2 ) (R 3 )-or -CO-.
• L x2 represents a single bond, -C (R 4 ) (R 5 )-or-CO-, and -C (R 4 ) (R 5 )-or-CO- is preferable.
• R2 to R5 each independently represent a hydrogen atom or a substituent.
• the above-mentioned substituent is preferably a hydroxyl group, a phenyl group, a halogen atom, a carboxylic acid group, a boronic acid group, an aldehyde group, an alkyl group, an alkoxy group or an alkoxycarbonyl group, and preferably a hydroxyl group, a halogen atom or a carboxylic acid group.
• Boronic acid group, aldehyde group, alkyl group, alkoxy group, or alkoxycarbonyl group are more preferable.
• the alkyl group may be linear or branched.
• the alkyl group preferably has 1 to 10 carbon atoms.
• the alkyl group may or may not have a substituent.
• the alkyl group portion of the alkoxy group and the alkyl group portion of the alkoxycarbonyl group are the same as those of the alkyl group.
• the phenyl group may or may not have a substituent, and when it has a substituent, it is more preferable to have 1 to 3 hydroxyl groups.
• R 2 to R 5 are preferably a hydrogen atom or a hydroxyl group, and more preferably a hydrogen atom.
• L x1 and Lx2 are preferably -CH2- , -CH (OH)-, -CO-, or -CH (Ph)-independently, respectively.
• the Ph represents a phenyl group which may have a substituent.
• the plurality of R 4s When a plurality of R 4s are present in the general formula (P1), the plurality of R 4s may be the same or different from each other. When there are a plurality of R 5s , the plurality of R 5s may be the same or different from each other.
• Ar 1 and Ar 2 independently represent a benzene ring group or a naphthalene ring group, respectively.
• Ar 1 and Ar 2 are preferably benzene ring groups independently of each other.
• Qa represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, a carboxylic acid group, a boronic acid group, an aldehyde group, an alkoxy group, or an alkoxycarbonyl group.
• the alkyl group may be linear or branched.
• the alkyl group preferably has 1 to 10 carbon atoms.
• the alkyl group may or may not have a substituent.
• the alkyl group portion of the alkoxy group and the alkyl group portion of the alkoxycarbonyl group are the same as those of the alkyl group.
• the phenyl group may or may not have a substituent.
• Q a is preferably bonded to the para position with respect to the hydroxyl group that the benzene ring group to which Q a may have may have.
• Qa is preferably a hydrogen atom or an alkyl group.
• the alkyl group is preferably a methyl group.
• the phenol compound is also preferably a compound having a triazine skeleton.
• a phenol compound means having one or more (for example, 1 to 5) triazine ring groups in the compound. Examples of such a phenol compound include a compound represented by the general formula (Z).
• E 1 to E 6 independently represent a single bond, -NH-, or -NR-.
• R represents a substituent.
• the substituent represented by R include a linear or branched alkyl group having 1 to 5 carbon atoms.
• E 1 to E 6 are preferably -NH- or -NR-, and more preferably -NH-.
• B 1 represents a single bond or a k + 1 valent organic group.
• B 2 represents a single bond or an l + 1 valent organic group.
• B 3 represents a single bond or m + 1 valent organic group.
• B 4 represents a single bond or an n + 1 valent organic group.
• the values of k, l, m, and n in the above-mentioned k + 1-valent organic group, l + 1-valent organic group, m + 1-valent organic group, and n + 1-valent organic group are specified in the general formula (Z). , K, l, m, and n.
• the value of m in the m + 1 valent organic group represented by B 3 indicates the number of X 3 to which the B 3 is bonded. Is the same as the value of.
• Examples of the organic group represented by B 1 to B 4 include a group obtained by removing j hydrogen atoms from a hydrocarbon group which may have a hetero atom having 1 to 20 carbon atoms.
• j means k + 1, l + 1, m + 1, or n + 1.
• the hydrocarbon group before removing j hydrogen atoms may have, for example, an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent. Examples thereof include one or more groups selected from the group consisting of an aliphatic ring group having 3 to 20 carbon atoms and an aromatic ring group having 3 to 20 carbon atoms which may have a substituent.
• the group further consists of -O-, -S-, -CO-, -NR N- ( RN is a hydrogen atom or a substituent), and -SO 2- . It may be a group consisting of a combination of one or more of the selected divalent linking groups.
• Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include methane, ethane, propane, butane, pentane, hexane, and heptane.
• Examples of the aliphatic ring group having 3 to 20 carbon atoms include a cyclohexane ring group, a cycloheptane ring group, a norbornane ring group, and an adamantane ring group.
• Examples of the aromatic ring group having 3 to 20 carbon atoms include an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms.
• Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring and the like, and examples of the aromatic heterocyclic group having 3 to 20 carbon atoms include a furan ring and a pyrrole ring. , Thiophene ring, pyridine ring, thiazole ring, carbazole ring, indole ring, benzothiazole ring and the like.
• k, l, m, and n each independently represent an integer of 0 or more.
• the total of k, l, r ⁇ m, and n is 2 or more, preferably an integer of 2 to 12, and more preferably an integer of 4 to 8.
• the value of m in "r ⁇ m" is an average value of m that may exist in a plurality of values.
• k, l, m, and n are preferably 0 to 5, and more preferably 1 to 2.
• k is preferably 1 or more (for example, 1 to 2)
• l is preferably 1 or more (for example, 1 to 2)
• m is preferably 1 or more (for example, 1 to 2).
• n is 1 or more (for example, 1 to 2).
• B 1 does not have X 1 .
• B 2 does not have X 2 .
• m does not have X 3 .
• B 4 does not have X 4 .
• B 1 is a single bond
• k is 1.
• B 2 is a single bond
• l is 1.
• B 3 is a single bond
• m is 1.
• B 4 is a single bond
• n is 1.
• L represents a divalent organic group.
• the organic group include an aromatic ring group which may have a substituent, an aliphatic hydrocarbon group which may have a substituent, an aliphatic ring group which may have a substituent, and-. Examples thereof include O-, -S-, -N (RN)-, -CO-, and a group combining these.
• RN represents a substituent. Examples of the substituent represented by RN include a linear or branched alkyl group having 1 to 5 carbon atoms. Further, examples of the substituent which the aromatic ring group, the aliphatic hydrocarbon group and the aliphatic ring group may have include a linear or branched alkyl group having 1 to 5 carbon atoms. Can be mentioned.
• Examples of the aromatic ring group include an aromatic hydrocarbon group having 6 to 20 carbon atoms and an aromatic heterocyclic group having 3 to 20 carbon atoms.
• Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a monocyclic aromatic ring group such as a benzene ring; a polycyclic aromatic ring group such as a naphthalene ring and an anthracene ring; and the like, and the number of carbon atoms is increased.
• Examples of the 3 to 20 aromatic heterocyclic groups include monocyclic aromatic ring groups such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, and a thiazole ring; a benzothiazole ring, a carbazole ring, and an indole ring. And the like; polycyclic aromatic ring groups; and the like.
• monocyclic aromatic ring groups such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, and a thiazole ring
• benzothiazole ring a carbazole ring
• an indole ring and the like
• polycyclic aromatic ring groups and the like.
• As the aromatic ring group as L a group obtained by removing two hydrogen atoms from the above example can be mentioned.
• Examples of the aliphatic hydrocarbon group include an alkylene group having 1 to 12 carbon atoms, and specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and a methylhexylene group. , And a heptylene group and the like.
• Examples of the aliphatic ring group include a cyclohexane ring group, a cycloheptane ring group, a norbornane ring group, and an adamantane ring group.
• As the aliphatic ring group as L a group obtained by removing two hydrogen atoms from the above example can be mentioned.
• An aromatic ring group which may have a substituent an aliphatic hydrocarbon group which may have a substituent, an aliphatic ring group which may have a substituent, or -O-, -S.
• a group in which -, -NR N- or -CO- is combined not only a divalent linking group consisting of a combination of two or more of these, but also a group of the same type (for example, an aromatic ring group) is connected via a single bond. It may be a divalent linking group in which two or more are combined.
• L in the above general formula (P2) may have a divalent aromatic ring group or a substituent which may have a substituent. It is a divalent organic group having at least one selected from the group consisting of a divalent aliphatic ring group which may have and an alkylene group which may have a branch having 2 or more carbon atoms. It is preferable, and a divalent organic group having a divalent aromatic ring group which may have a substituent may be more preferable because the thermal conductivity is more excellent.
• r is an integer of 0 or more. r is preferably an integer of 0 to 20, and more preferably an integer of 0 to 10.
• X 1 to X 4 each independently represent an aromatic ring group having a phenolic hydroxyl group.
• the "aromatic ring group having a phenolic hydroxyl group” may be any aromatic ring group having one or more (for example, 1 to 4) hydroxyl groups (phenolic hydroxyl groups) directly bonded to the aromatic ring.
• the aromatic ring group may or may not have a substituent other than the hydroxyl group.
• the aromatic ring group may be monocyclic or polycyclic, and may have a heteroatom as a ring member atom.
• the number of ring member atoms of the aromatic ring group is preferably 5 to 15, more preferably 6 to 10, and even more preferably 6.
• the aromatic ring group is preferably a benzene ring group.
• a substituent that the aromatic ring group may have other than the hydroxyl group a substituent having 1 to 6 carbon atoms is preferable, a hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a linear chain having 1 to 6 carbon atoms is more preferable. Alternatively, a branched alkyl group is more preferable.
• k X 1 , l X 2 , r ⁇ m X 3 , and n X 4 is a phenolic hydroxyl group. It is also preferable that the aromatic ring group has a substituent arranged at the ortho position of the phenolic hydroxyl group.
• the value of m in "r ⁇ m" is an average value of m that may exist in a plurality of values.
• the "substituted group arranged at the ortho position" is preferably a substituent having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and a linear or branched chain having 1 to 6 carbon atoms.
• Alkyl groups in the form are more preferable.
• the aromatic ring groups other than "the aromatic ring group having the phenolic hydroxyl group and the substituent arranged at the ortho position of the phenolic hydroxyl group” are It may or may not have a substituent other than a hydroxyl group (phenolic hydroxyl group).
• the aromatic ring group other than the "aromatic ring group having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group” include a hydroxyphenyl group.
• aromatic ring groups having phenolic hydroxyl groups represented by any of X 1 to X 4
• at least one is “phenolic hydroxyl group and phenol”. It is also preferable that it is an aromatic ring group other than the "aromatic ring group having a substituent arranged at the ortho position of the sex hydroxyl group”.
• aromatic ring groups having phenolic hydroxyl groups represented by X 1 to X 4 there are also aromatic ring groups other than "aromatic ring groups having a phenolic hydroxyl group and a substituent arranged at the ortho position of the phenolic hydroxyl group”. It is considered that the symmetry of the compound as a whole is broken, the melting point of the compound is lowered, and the handleability of the semi-cured film formed from the composition is improved.
• phenol compounds include, for example, benzene polyols such as benzenetriol, biphenylaralkyl-type phenol resins, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadienephenol-added resins, and phenols.
• benzene polyols such as benzenetriol, biphenylaralkyl-type phenol resins, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadienephenol-added resins, and phenols.
• Aralkyl resin polyhydric phenol novolac resin synthesized from polyhydric hydroxy compound and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol phenol co-condensed novolak resin, naphthol cresol co-condensed Novolac resins, biphenyl-modified phenolic resins, biphenyl-modified naphthol resins, aminotriazine-modified phenolic resins, alkoxy group-containing aromatic ring-modified novolak resins and the like are also preferred.
• the lower limit of the hydroxyl group content of the phenol compound is preferably 3.0 mmol / g or more, more preferably 7.0 mmol / g or more.
• the upper limit is preferably 25.0 mmol / g or less, more preferably 20.0 mmol / g or less.
• the hydroxyl group content is intended to be the number of hydroxyl groups (preferably phenolic hydroxyl groups) possessed by 1 g of the phenol compound.
• the phenol compound may have an active hydrogen-containing group (carboxylic acid group or the like) capable of polymerizing with the epoxy compound.
• the lower limit of the active hydrogen content (total content of hydrogen atoms in hydroxyl groups, carboxylic acid groups, etc.) of the phenol compound is preferably 3.0 mmol / g or more, and more preferably 7.0 mmol / g or more.
• the upper limit is preferably 25.0 mmol / g or less, more preferably 20.0 mmol / g or less.
• the content of the active hydrogen is intended to be the number of active hydrogen atoms contained in 1 g of the phenol compound.
• the upper limit of the molecular weight of the phenol compound is preferably 600 or less, more preferably 500 or less, further preferably 450 or less, and particularly preferably 400 or less.
• the lower limit is preferably 110 or more, more preferably 300 or more.
• the phenol compound may be used alone or in combination of two or more.
• the ratio of the content of the epoxy compound to the content of the active hydrogen group-containing compound is the epoxy group of the epoxy compound and the active hydrogen group-containing compound.
• the equivalent ratio (“number of epoxy groups” / “number of active hydrogen groups”) with the active hydrogen group is preferably 30/70 to 70/30. , 40/60 to 60/40 is more preferable, and 45/55 to 55/45 is even more preferable.
• the total content of the epoxy compound and the active hydrogen group-containing compound is preferably 20 to 100% by volume, preferably 60% by volume, based on the total binder components. ⁇ 100% by volume is more preferable, and 90 to 100% by volume is further preferable.
• the viscosity (also referred to as "viscosity X") of the binder component (for example, a mixture thereof when the binder component is composed of an epoxy compound and a phenol compound) at 120 ° C. is preferably 10 Pa ⁇ s or less. 1 Pa ⁇ s or less is more preferable.
• the lower limit of the viscosity X is, for example, 0.001 Pa ⁇ s or more.
• the equivalent ratio of the hydroxyl group contained in the phenol compound to the epoxy group contained in the epoxy compound is 1 in the phenol compound and the epoxy compound. It is also preferable that the composition T blended in the above-mentioned viscosity range is satisfied.
• the binder component contains two or more kinds of phenol compounds
• the composition T also contains two or more kinds of phenol compounds. In this case, the composition ratio of the two or more kinds of phenol compounds contained in the composition T is the same as the composition ratio of the two or more kinds of phenol compounds in the binder component. The same applies when the binder component contains two or more kinds of epoxy compounds.
• the viscosity X and the viscosity of the above composition T are measured in the range of 100 to 180 ° C. using RheoStress RS6000 (manufactured by Eiko Seiki Co., Ltd.), and the value obtained by reading the viscosity at 120 ° C. is adopted.
• the temperature rise rate is 3 ° C./min, and the shear rate is 10 (1 / s).
• the resin binder (particularly, the resin binder formed from the precursor of the resin binder) is a silicone resin.
• Silicone resin as a resin binder is preferable because it easily imparts flexibility to the heat conductive material.
• the silicone resin include an addition reaction curable silicone resin and a condensation curable silicone resin, and an addition reaction curable silicone resin is preferable.
• a precursor capable of forming a silicone resin is also referred to as a silicone compound. That is, the composition of the present invention preferably contains a silicone compound as a binder component.
• the silicone resin is formed by chemically bonding two or more resin binder precursors, the precursors of the two or more resin binders are also referred to as silicone compounds.
• the silicone resin is preferably one that is crosslinked and cured by the silicone compound A and the silicone compound B described below as binder components.
• an organopolysiloxane having two or more alkenyl groups is used as the silicone compound A.
• the organopolysiloxane having two or more alkenyl groups is preferably an organopolysiloxane having two or more vinyl groups, and an organopolysiloxane having vinyl groups at both ends is more preferable.
• Examples of the organopolysiloxane having vinyl groups at both ends include vinyl double-ended polydimethylsiloxane, vinyl double-ended polyphenylmethylsiloxane, vinyl double-ended dimethylsiloxane-diphenylsiloxane copolymer, and vinyl double-ended dimethylsiloxane-phenylmethylsiloxane copolymer.
• the weight average molecular weight of the organopolysiloxane having two or more alkenyl groups is preferably 4000 to 50000, more preferably 7500 to 25000.
• the silicone compound A may be used alone or in combination of two or more.
• the silicone compound B it is sufficient that the silicone compound A can be crosslinked, and examples thereof include compounds having two or more hydrosilyl groups (SiH).
• Polyorganosiloxane having two or more hydrosilyl groups hereinafter, “hydrosilyl group-containing polyorganosiloxane”). ”) Is preferable.
• Polyorganosiloxanes having 3 or more hydrosilyl groups eg 3 to 1000 are more preferred.
• hydrosilyl group-containing polyorganosiloxane examples include methylhydrosiloxane-dimethylsiloxane copolymer, polymethylhydrosiloxane, polyethylhydrosiloxane, and methylhydrosiloxane-phenylmethylsiloxane copolymer. These may or may not have a hydrosilyl group at the ends, for example, both ends may be blocked by a trimethylsilyl group, a triethylsilyl group, or the like.
• the weight average molecular weight of the hydrosilyl group-containing polyorganosiloxane is preferably 800 to 5000, more preferably 1500 to 4000.
• the content of the silicone compound B is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 7 parts by mass, and 0.3 by mass with respect to 100 parts by mass of the silicone compound A. ⁇ 3 parts by mass is more preferable.
• the silicone compound B may be used alone or in combination of two or more. In the composition of the present invention, the silicone compound A and the silicone compound B may partially react with each other.
• the content of the binder component in the composition is the total solid content of the composition. 5 to 90% by volume is preferable with respect to the minute. Above all, when the composition contains an epoxy compound and an active hydrogen group-containing compound used in combination with the epoxy compound as a binder component, the content thereof is 10 to 50% by volume with respect to the total solid content of the composition. More preferably, 20 to 45% by volume is further preferable. When the composition contains a silicone compound as a binder component, the content thereof is more preferably 20 to 85% by volume and further preferably 40 to 80% by volume with respect to the total solid content of the composition.
• the composition may further contain a curing accelerator.
• a curing accelerator for forming the resin binder from the precursor of the resin binder.
• the type of the curing accelerator to be used may be appropriately determined in consideration of the type of the precursor of the resin binder and the like.
• curing accelerator examples include tris-orthotrilphosphine, triphenylphosphine, boron trifluoride amine complex, and the compounds described in paragraph 0052 of JP2012-67225A.
• phosphonium salt-based curing accelerators such as quaternary phosphonium-based
• 2-methylimidazole (trade name; 2MZ), 2-undecylimidazole (trade name; C11-Z), 2-heptadecylimidazole (trade name; C17Z), 1,2-dimethylimidazole (trade name).
• triarylphosphine-based curing accelerator the compound described in paragraph 0052 of JP-A-2004-43405 can also be mentioned.
• Examples of the phosphorus-based curing accelerator to which triphenylborane is added to triarylphosphine include the compounds described in paragraph 0024 of JP-A-2014-5382. These curing accelerators are particularly preferably used when the composition contains an epoxy compound as a precursor of a resin binder.
• curing accelerator examples include platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, and the like. These curing accelerators are particularly preferably used when the composition contains a silicone compound (preferably both silicone compound A and silicone compound B) as a precursor of the resin binder.
• the curing accelerator may be used alone or in combination of two or more.
• the content of the curing accelerator is preferably 0.01 to 10% by volume, more preferably 0.10 to 5% by volume, based on the total amount of the epoxy compound.
• the content of the curing accelerator is preferably 0.1 to 200% by volume, more preferably 0.5 to 100% by volume, based on the total amount of the silicone compound. preferable.
• the content of the curing accelerator is preferably 0.000002 to 2% by volume, for example, with respect to the total solid content of the composition.
• the composition may further contain an inorganic substance.
• the inorganic substance is an inorganic substance other than boron nitride contained in the surface-modified boron nitride particles of the present invention.
• the above-mentioned inorganic substance may form a surface-modifying inorganic substance together with a surface-modifying agent.
• a surface modifier for example, a surface modifier that can be contained in the surface-modified boron nitride particles of the present invention can be used.
• the surface-modified inorganic substance is other than the surface-modified boron nitride particles of the present invention.
• the inorganic substance for example, any inorganic substance conventionally used for an inorganic filler of a heat conductive material may be used.
• the inorganic substance preferably contains an inorganic nitride or an inorganic oxide, and more preferably contains an inorganic nitride, because the heat conductive material is more excellent in thermal conductivity and insulating property.
• the shape of the inorganic substance is not particularly limited, and may be in the form of particles, a film, or a plate.
• Examples of the shape of the particulate inorganic substance include rice granules, spherical shape, cube shape, spindle shape, scale shape, agglomerate shape, and indefinite shape.
• the inorganic oxide examples include zirconium oxide (ZrO 2 ), titanium oxide (TIO 2 ), silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), and iron oxide (Fe 2 O 3 , FeO, Fe 3 ).
• O 4 copper oxide (CuO, Cu 2 O), zinc oxide (ZnO), yttrium oxide (Y 2 O 3 ), niobium oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), indium oxide (In 2 ).
• the inorganic oxide is preferably titanium oxide, aluminum oxide, or zinc oxide, and more preferably aluminum oxide.
• the inorganic oxide may be an oxide produced by oxidizing a metal prepared as a non-oxide in an environment or the like.
• inorganic nitride examples include boron nitride (BN), carbon nitride (C 3 N 4 ), silicon nitride (Si 3 N 4 ), gallium nitride (GaN), indium nitride (InN), and aluminum nitride (AlN).
• BN boron nitride
• C 3 N 4 carbon nitride
• Si 3 N 4 silicon nitride
• GaN gallium nitride
• InN indium nitride
• AlN aluminum nitride
• the inorganic nitride preferably contains an aluminum atom, a boron atom, or a silicon atom, more preferably aluminum nitride, boron nitride, or silicon nitride, and even more preferably aluminum nitride or boron nitride. It is particularly preferable to contain boron nitride. As the above-mentioned inorganic nitride, only one kind may be used, or two or more kinds may be used.
• the size of the inorganic substance is not particularly limited, but the average particle size of the inorganic substance is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 200 ⁇ m or less, in that the dispersibility of the inorganic substance is more excellent.
• the lower limit is not particularly limited, but in terms of handleability, 10 nm or more is preferable, and 100 nm or more is more preferable.
• the catalog value is adopted when a commercially available product is used. If there is no catalog value, the average particle size is calculated by randomly selecting 100 inorganic substances using an electron microscope, measuring the particle size (major axis) of each inorganic substance, and arithmetically averaging them. ..
• the content thereof is preferably 0.5 to 60% by volume, more preferably 1 to 50% by volume, still more preferably 2 to 40% by volume, based on the total solid content of the composition. ..
• the inorganic substance one kind may be used alone, or two or more kinds may be used.
• the boron nitride particles contained in the surface-modified boron nitride particles of the present invention and the above-mentioned inorganic substances are collectively referred to as an inorganic component.
• the content of the inorganic component in the composition is preferably 35% by volume or more, more preferably 50% by volume or more, still more preferably 55% by volume or more, based on the total solid content of the composition.
• the upper limit of the content is less than 100% by volume, preferably 80% by volume or less. Further, particularly when the binder component contains a silicone compound, the upper limit of the content is preferably less than 50% by volume from the viewpoint that the peel strength of the heat conductive material is more excellent.
• the content of the boron nitride particles contained in the surface-modified boron nitride particles of the present invention is preferably 10 to 100% by volume, more preferably 25 to 100% by volume, and 50 to 100% by volume with respect to the total mass of the inorganic components. Is more preferable.
• the composition may further contain a solvent.
• the type of solvent is not particularly limited, and it is preferably an organic solvent.
• the organic solvent include cyclopentanone, cyclohexanone, ethyl acetate, methyl ethyl ketone, dichloromethane, tetrahydrofuran and the like.
• the content of the solvent is preferably 20 to 90% by volume, more preferably 30 to 80% by volume, and 40 to 60% by volume. Is more preferable. That is, when the composition contains a solvent, the content thereof is preferably 10 to 80% by volume, more preferably 20 to 70% by volume, still more preferably 20 to 70% by volume, based on the total amount of the composition.
• the composition may be substantially free of solvent, in which case the solid content concentration of the composition is preferably 98-100% by volume, more preferably 99-100% by volume, further 99.5-100% by volume. preferable.
• the composition may contain other components other than those described above.
• examples of other components include a dispersant and a polymerization initiator (photopolymerization initiator, thermal polymerization initiator, etc.).
• the method for producing the composition is not particularly limited, and a known method can be adopted.
• the above-mentioned various components can be mixed and produced.
• various components may be mixed all at once or sequentially.
• the method of mixing the components is not particularly limited, and a known method can be used.
• the mixing device used for mixing is preferably a liquid disperser, for example, a stirrer such as a rotating revolution mixer, a high-speed rotary shear type stirrer, a colloid mill, a roll mill, a high-pressure injection disperser, an ultrasonic disperser, a bead mill, etc. And a homogenizer can be mentioned.
• the mixing device may be used alone or in combination of two or more. Degassing may be performed before, after, and / or at the same time as mixing.
• the composition of the present invention is cured to obtain a heat conductive material.
• the curing method of the composition is not particularly limited, but a thermosetting reaction is preferable.
• the heating temperature during the thermosetting reaction is not particularly limited. For example, it may be appropriately selected in the range of 50 to 250 ° C. Further, when the thermosetting reaction is carried out, heat treatments having different temperatures may be carried out a plurality of times.
• the curing treatment is preferably performed on a film-like or sheet-like composition. Specifically, for example, the composition may be applied to form a film and a curing reaction may be carried out. When performing the curing treatment, it is preferable to apply the composition on the substrate to form a coating film and then cure.
• a different base material may be brought into contact with the coating film formed on the base material, and then the curing treatment may be performed.
• the cured product (heat conductive material) obtained after curing may or may not be separated from one or both of the substrates.
• the composition may be applied on different substrates to form coating films, and the curing treatment may be performed in a state where the obtained coating films are in contact with each other.
• the cured product (heat conductive material) obtained after curing may or may not be separated from one or both of the substrates.
• press working may be performed.
• the press used for press working is not limited, and for example, a flat plate press may be used or a roll press may be used.
• a substrate with a coating film obtained by forming a coating film on the substrate is sandwiched between a pair of rolls in which two rolls face each other, and the above pair of rolls is used. It is preferable to apply pressure in the film thickness direction of the coated substrate while rotating the substrate to pass the coated substrate.
• the base material may be present on only one side of the coating film, or the base material may be present on both sides of the coating film.
• the substrate with a coating film may be passed through the roll press only once or may be passed a plurality of times. Only one of the treatment by the flat plate press and the treatment by the roll press may be carried out, or both may be carried out.
• the curing treatment may be completed when the composition is in a semi-cured state.
• the heat conductive material of the present invention in a semi-cured state may be arranged so as to be in contact with the device or the like to be used, and then further cured by heating or the like to be finally cured. It is also preferable that the device and the heat conductive material of the present invention are adhered to each other by heating or the like during the main curing.
• heat conductive materials including curing reaction refer to "High heat conductive composite material" (CMC Publishing, by Yutaka Takezawa).
• the shape of the heat conductive material is not particularly limited, and can be molded into various shapes depending on the application.
• a typical shape of the molded heat conductive material is, for example, a sheet shape. That is, the heat conductive material of the present invention is preferably a heat conductive sheet. Further, the thermal conductivity of the heat conductive material of the present invention may be anisotropic or isotropic.
• the heat conductive material is preferably insulating (electrically insulating).
• the composition of the present invention is preferably a thermally conductive insulating composition.
• the volume resistivity of the heat conductive material at 23 ° C. and 65% relative humidity is preferably 10 10 ⁇ ⁇ cm or more, more preferably 10 12 ⁇ ⁇ cm or more, and even more preferably 10 14 ⁇ ⁇ cm or more.
• the upper limit is not particularly limited, but is usually 10 18 ⁇ ⁇ cm or less.
• the heat conductive material of the present invention preferably has few voids and the like in the heat conductive material, and preferably has a high filling rate obtained by the following formula (X).
• the filling rate of the heat conductive material is preferably 90 to 100%, preferably 95 to 100%.
• Filling rate (%) Membrane density / theoretical density ⁇ 100 formula (X)
• the film density is the density of the heat conductive material actually obtained, and can be measured by the Archimedes method or the like.
• the theoretical density is the ideal density of the heat conductive material assuming that the heat conductive sheet is formed without including voids, etc., and is calculated from the density of each component contained in the heat conductive material. You may guide with.
• the density of the surface-modified boron nitride particles is set to 2.23 g / cm 3 , and the density of other components is set.
• the theoretical density may be calculated by setting 1.30 g / cm 3 and calculating from the solid content composition of the composition used for forming the heat conductive material.
• the density of the surface-modified boron nitride particles is set to 2.23 g / cm 3 and other than that.
• the theoretical density may be calculated by calculating from the composition of the solid content of the composition used for forming the heat conductive material, with the density of the components being 1.00 g / cm 3 .
• the heat conductive material can be used as a heat dissipation material such as a heat dissipation sheet, and can be used for heat dissipation of various devices. More specifically, a device with a heat conductive layer can be produced by arranging a heat conductive layer containing the heat conductive material of the present invention on the device, and heat generated from the device can be efficiently dissipated by the heat conductive layer. Since the heat conductive material has sufficient heat conductivity and high heat resistance, it is used for heat dissipation of power semiconductor devices used in various electric devices such as personal computers, general household appliances, and automobiles. Is suitable.
• the heat conductive material has sufficient heat conductivity even in a semi-cured state, heat dissipation is arranged in a part where it is difficult for light for photocuring to reach, such as a gap between members of various devices. It can also be used as a material. In addition, since it has excellent adhesiveness, it can also be used as an adhesive having thermal conductivity.
• the heat conductive material may be used in combination with other members other than the members formed from the present composition.
• the sheet-shaped heat conductive material may be combined with another sheet-shaped support of the layer formed from the present composition.
• the sheet-shaped support include a plastic film, a metal film, or a glass plate.
• the material of the plastic film include polyester such as polyethylene terephthalate (PET), polycarbonate, acrylic resin, epoxy resin, polyurethane, polyamide, polyolefin, cellulose derivative, and silicone.
• PET polyethylene terephthalate
• the metal film include a copper film.
• ⁇ Silane coupling agent> The silane coupling agents used to produce the surface-modified boron nitride particles are shown below.
• KBM-403 3-glycidoxypropyltrimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd.)
• X-12-984S Polymer-type polyfunctional epoxysilane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd.)
• the boron nitride particles (boron nitride particles A described above) were treated by the production method described later to obtain surface-modified boron nitride particles.
• ⁇ Manufacturing method A Silane coupling agent treatment after plasma treatment> Vacuum plasma treatment (gas type: O 2 , pressure: 30 Pa, flow rate: 10 sccm) for 150 g of boron nitride particles using "YHS-D ⁇ S" manufactured by Kaoru Semiconductor Co., Ltd. for the treatment time shown in the table shown in the subsequent stage. , Output: 300W).
• the obtained surface-modified boron nitride particles (50 g) were stirred in acetonitrile (100 ml). Further, a hydrolysis adjusting solution (1.25 g) of each silane coupling agent described in the table below was added to the acetonitrile.
• the acetonitrile was stirred at room temperature for 3 hours for adsorption treatment.
• the acetonitrile was filtered, the obtained filtrate was washed with acetonitrile (100 ml), and the filtrate was dried in an oven at 40 ° C. to obtain surface-modified boron nitride particles.
• the hydrolysis preparation solution of the silane coupling agent is prepared by mixing the silane coupling agent (1 g) with ethanol (500 ⁇ l), 2-propanol (500 ⁇ l), water (720 ⁇ l), and acetic acid (100 ⁇ l). Prepared by stirring for hours.
• the formulation of the hydrolysis preparation solution of the silane coupling agent is the same unless otherwise specified.
• ⁇ Manufacturing method B Surface modification treatment at the same time as vacuum plasma treatment> Vacuum plasma treatment (gas type: TEOS / O 2 , pressure: 70 Pa, output) for 150 g of boron nitride particles using "YHS-D ⁇ S" manufactured by Kaoru Semiconductor Co., Ltd. for the treatment time shown in the table shown below. : 300 W) was carried out to obtain surface-modified boron nitride particles. (TEOS: Tetraethoxysilane)
• ⁇ Manufacturing method D Silane coupling agent treatment after firing treatment> Boron nitride particles were heated at 850 ° C. for 8 hours in the air using "FP410" manufactured by Yamato Kagaku Co., Ltd. The obtained surface-modified boron nitride particles (50 g) were stirred in acetonitrile (100 ml). Further, a hydrolysis adjusting solution (1.25 g) of the silane coupling agent described in the table below was added to the acetonitrile. The acetonitrile was stirred at room temperature for 3 hours for adsorption treatment. The acetonitrile was filtered, the obtained filtrate was washed with acetonitrile (100 ml), and the filtrate was dried in an oven at 40 ° C. to obtain surface-modified boron nitride particles.
• Atomic concentration (atomic%)) and atomic concentration ratio of silicon atom concentration to boron atom concentration (Si / O ratio, silicon atom concentration (atomic%) / boron atom concentration (atomic%)) were calculated.
• composition composition for forming a heat conductive material
• composition for forming a heat conductive material was prepared by using the above-mentioned surface-modified boron nitride particles or untreated boron nitride particles. The features of the composition and the test methods carried out using the composition are shown below.
• Binder resin or its precursor (binder component) used in Examples and Comparative Examples is shown below.
• the following A-1 corresponds to an epoxy compound
• B-1 and B-2 correspond to a phenol compound
• C-1 corresponds to a silicone compound.
• TPP triphenylphosphine
• composition was prepared by the method shown below. Hereinafter, preparation methods for each of a composition containing an epoxy compound and a phenol compound as a binder component and a composition containing a silicone compound will be shown.
• composition containing epoxy compound and phenol compound A mixture was prepared in which the combinations of the epoxy compound and the phenol compound shown in the table below were blended in equivalent amounts (the number of the epoxy groups of the epoxy compound in the system equal to the number of hydroxyl groups of the phenol compound).
• surface-modified boron nitride particles or untreated boron nitride particles
• the obtained mixed solution was treated with a rotation / revolution mixer (THINKY, Awatori Rentaro ARE-310) for 5 minutes to obtain a composition (composition for forming a heat conductive material) of each Example or each Comparative Example. rice field.
• the untreated boron nitride particles are the boron nitride particles A themselves used for producing the surface-modified boron nitride particles.
• the amount of the solvent added was such that the solid content concentration of the composition was 42.5% by volume.
• the amount of the curing accelerator added was such that the content of the curing accelerator in the composition was 3% by volume with respect to the content of the epoxy compound.
• the total content of the binder component (epoxy compound and phenol compound) and the curing accelerator in the composition is the total content of the components derived from the binder component and the curing accelerator with respect to the total volume of the heat conductive material to be formed. (Volume%) was adjusted to be 37.0% by volume.
• the total content (% by volume) of the binder component and the curing accelerator with respect to the total solid content in the composition is a component derived from the binder component and the curing accelerator with respect to the total volume of the heat conductive material to be formed. It is substantially the same as the total content (% by volume) of.
• the content of the surface-modified boron nitride particles (or untreated boron nitride particles) in the composition is the content of the surface-modified boron nitride particles (or untreated boron nitride particles) with respect to the total volume of the heat conductive material formed.
• the amount (% by volume) was adjusted to be 63.0% by volume.
• the content (% by volume) of the surface-modified boron nitride particles (or untreated boron nitride particles) with respect to the total solid content in the composition is the surface-modified boron nitride particles with respect to the total volume of the heat conductive material to be formed. It is substantially the same as the content (% by volume) of (or untreated boron nitride particles).
• composition containing silicone compound A mixture of Agent A and Agent B of the binder component C-1 (KE-1012 A / B) in a ratio of 1: 1 (volume ratio) was obtained. Further, toluene as a solvent was added to the mixture, if desired. Surface-modified boron nitride particles (or untreated boron nitride particles) were added to the above mixture to obtain a mixed solution. The obtained mixed solution was treated with a rotation / revolution mixer (Awatori Rentaro ARE-310, manufactured by THINKY) for 10 minutes to obtain a composition (composition for forming a heat conductive material) of each Example or each Comparative Example. rice field.
• the untreated boron nitride particles are the boron nitride particles A themselves used for producing the surface-modified boron nitride particles.
• the amount of toluene added was such that the solid content concentration of the composition (composition for forming a heat conductive material) became 55% by volume.
• the polyester film is peeled off from the obtained semi-cured film, the semi-cured film is sandwiched between an aluminum plate and a copper foil, and heat pressed under air (hot plate temperature 180 ° C., pressure 10 MPa for 5 minutes, and then further. It was treated at 180 ° C. for 90 minutes under normal pressure) to obtain an aluminum base substrate with a copper foil.
• the density of the surface-modified boron nitride particles is set to 2.23 g / cm 3 .
• the theoretical density was calculated from the composition of the solid content of the composition, assuming that the densities of the other components were 1.30 g / cm 3 .
• the density of the surface-modified boron nitride particles is set to 2.23 g / cm 3
• the density of other components is set to 2.23 g / cm 3.
• the theoretical density was calculated by calculating from the composition of the solid content of the composition at 1.00 g / cm 3 .
• Tables 1 and 2 below show the characteristics of the surface-modified boron nitride particles, the characteristics of the composition, and the test results in each Example or Comparative Example.
• the "Production method” column indicates which of the above-mentioned production methods A to D produced the surface-modified boron nitride particles used in the production of the composition.
• the “Treatment conditions” column indicates what kind of treatment was performed on the boron nitride particles used as the material to obtain surface-modified boron nitride particles.
• the description of “vacuum” in the “treatment condition” column indicates that the vacuum plasma treatment was performed.
• the description of "atmospheric pressure” indicates that the atmospheric pressure plasma treatment was performed.
• the description of "firing” indicates that the firing process has been performed.
• the description of "untreated” indicates that the untreated boron nitride particles (boron nitride particles A) shown as a material were used as they were in the preparation of the composition.
• the “gas type” column indicates the type of processing gas used when plasma treatment (vacuum plasma treatment or atmospheric pressure plasma treatment) is performed.
• the “Treatment intensity” column shows the output (unit: W) when plasma treatment (vacuum plasma treatment or atmospheric pressure plasma treatment) is performed, and the treatment temperature (unit: ° C) when firing treatment is performed. show.
• the “treatment time [h]” column indicates the length (unit: time) of the time during which the plasma treatment or the firing treatment was performed.
• the "silane coupling agent” column indicates the type of silane coupling agent used for surface modification.
• the "Particle Parameters” column shows the characteristics of the surface-modified boron nitride particles (or untreated boron nitride particles) used in the preparation of the composition of each Example or Comparative Example.
• XPS O / B ratio the oxygen atom concentration with respect to the boron atom concentration detected by analyzing the surface of the surface-modified boron nitride particles (or untreated boron nitride particles) by XPS (X-ray photoelectron spectroscopy). Shows the atomic concentration ratio of.
• XPS Si / B ratio silicon oxygen atoms with respect to the boron atom concentration detected by analyzing the surface of surface-modified boron nitride particles (or untreated boron nitride particles) by XPS (X-ray photoelectron spectroscopy). Shows the atomic concentration ratio of the concentration.
• the "XRD peak ratio” column shows the D value obtained by the above equation (1).
• the “Amount [%]” column in the "Surface-modified Boron Nitride Particles or Untreated Boron Nitride Particles” column indicates the surface-modified Boron Nitride Particles (or untreated Boron Nitride Particles) with respect to the total volume of the formed heat conductive material.
• the "Binder component and curing accelerator” column indicates the types of epoxy compounds, phenol compounds, and silicone compounds used in the preparation of the compositions of each Example or Comparative Example. When the composition contains an epoxy compound and a phenol compound, the type of the curing accelerator used and the viscosity X of the binder component (viscosity X is as described above) are shown. Further, the “amount [%]” column in the “binder component and curing accelerator” column is the total content (volume) of the component derived from the binder component and the curing accelerator with respect to the total volume of the formed heat conductive material. %) Is shown.
• the "solvent” column shows the type of solvent used for preparing the composition of each Example or Comparative Example, and the solid content concentration (% by volume) of the composition when the solvent is used.
• the obtained heat conductive material heat conductive sheet
• the heat conductive sheet could not be formed.
• the surface-modified boron nitride particles of the present invention can solve the problems of the present invention. Specifically, from the comparison between Examples 1 to 7 and Comparative Examples 1 and 2, it was confirmed that the heat conductive material using the composition containing the surface-modified boron nitride particles of the present invention has excellent peel strength. It was also confirmed that when the binder resin of the heat conductive material is an epoxy resin, the effect of improving the heat conductivity of the heat conductive material by the surface-modified boron nitride particles of the present invention is good.
• the thermal conductivity of the material was further excellent. This is because the surface-modified boron nitride particles of the present invention are sufficiently surface-modified, so that the surface-modified boron nitride particles are well dispersed in the silicone resin, and the heat is higher than that when ordinary boron nitride particles are used. It is presumed that the thermal conductivity of the conductive material has been enhanced.
• the peel strength or the thermal conductivity of the obtained heat conductive material is It was confirmed to be superior (see comparison of Examples 1, 4 to 7, comparison of Examples 2 to 3, etc.).

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• 2021
  • 2021-08-30 JP JP2022553559A patent/JP7500750B2/ja active Active
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