WO2015170744A1 - 放熱部材用組成物、放熱部材、電子機器 - Google Patents
放熱部材用組成物、放熱部材、電子機器 Download PDFInfo
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- WO2015170744A1 WO2015170744A1 PCT/JP2015/063316 JP2015063316W WO2015170744A1 WO 2015170744 A1 WO2015170744 A1 WO 2015170744A1 JP 2015063316 W JP2015063316 W JP 2015063316W WO 2015170744 A1 WO2015170744 A1 WO 2015170744A1
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
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- C09K19/00—Liquid crystal materials
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- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
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- C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
Definitions
- the present invention relates to a composition for a heat dissipation member.
- the present invention relates to a heat radiating member composition capable of forming a heat radiating member that efficiently conducts and transmits heat generated in an electronic device.
- thermoelectric material heat-dissipating member
- a heat-generating part is brought into contact with a highly heat-conductive material (heat-dissipating member) to guide heat to the outside and dissipate heat.
- materials having high thermal conductivity include inorganic materials such as metals and metal oxides.
- inorganic materials have problems in processability, insulation, and the like, and it is very difficult to use them alone as a filler for semiconductor packages. Therefore, development of a heat radiating member in which these inorganic material and resin are combined to increase heat conductivity has been performed.
- Patent Document 1 discloses a heat dissipating member obtained by polymerizing a liquid crystal composition by controlling the alignment with an alignment control additive or a rubbing treatment method as a method for improving the thermal conductivity of the resin.
- the heat dissipation member is always required to have higher thermal conductivity with the development of electronic equipment. Then, this invention makes it a subject to provide the composition and heat dissipation member which can form the heat dissipation member which has high thermal conductivity.
- the inventors of the present invention have the main heat conduction in a heat dissipating member made of a polymer having a fixed molecular arrangement obtained by polymerizing by aligning mesogenic sites of a polymerizable compound having liquid crystallinity in a certain direction.
- the transmission loss of the phonon, which is an element, is suppressed, and higher heat conductivity is attempted by utilizing the fact that higher heat conductivity of the resin can be expected.
- the present inventors polymerize by developing a liquid crystal phase of a resin containing a monomer having such a mesogen moiety, when combined with a specific high thermal conductive inorganic filler (high thermal conductive inorganic filler), the combination
- high thermal conductive inorganic filler high thermal conductive inorganic filler
- the composition for a heat dissipation member according to the first aspect of the present invention includes a polymerizable liquid crystal compound having a structure containing an oxiranyl group or an oxetanyl group at both ends; a curing agent that cures the polymerizable liquid crystal compound; and a nitride.
- the curing temperature is not less than the temperature range in which the polymerizable liquid crystal compound exhibits a liquid crystal phase and not more than the temperature range in which an isotropic phase is exhibited.
- “Temperature range showing liquid crystal phase” refers to a temperature range showing a nematic phase, a smectic phase, or a cholesteric phase.
- the composition for heat radiating members will harden
- the film (heat radiating member) formed from the heat radiating member composition has high thermal conductivity due to the synergistic effect of the thermal conductivity of the polymerized liquid crystal compound and the thermal conductivity of the inorganic filler formed of nitride. Can have.
- composition for heat radiating member according to the second aspect of the present invention is the composition for heat radiating member according to the first aspect of the present invention, wherein the polymerizable liquid crystal compound is represented by the following formula (1-1). At least one compound.
- R a1 -Z- (A-Z) m1 -R a1 ⁇ (1-1) [In the above formula (1-1), R a1 is a polymerizable group represented by any of the following formulas (2-1) to (2-2); A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] Oct-1,4-diyl, or bicyclo [3.1.0] hex-3,6-diyl, In these rings, arbitrary —CH 2 — may be replaced with —O
- the composition for heat radiating members can contain a more preferable compound as a polymeric liquid crystal compound.
- These compounds are thermosetting, can be cured without being affected by the amount of filler, and are excellent in heat resistance.
- the molecular structure has symmetry and linearity, which is considered advantageous for phonon conduction.
- composition for a heat radiating member according to the third aspect of the present invention is the composition for a heat radiating member according to the second aspect of the present invention, wherein A is 1,4-cyclohexane in the above formula (1-1). Silene, 1,4-cyclohexylene, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen, 1,4-phenylene in which arbitrary hydrogen is replaced with halogen or methyl group, fluorene-2,7-diyl, Or fluorene-2,7-diyl in which any hydrogen is replaced by a halogen or methyl group.
- the composition for heat radiating members can contain a further preferable compound as a polymeric liquid crystal compound. These compounds are considered to be more advantageous for phonon conduction because of higher molecular linearity.
- the composition for a heat radiating member according to the fourth aspect of the present invention is the composition for a heat radiating member according to the third aspect of the present invention, wherein Z is a single bond in the above formula (1-1),-( CH 2 ) a —, —O (CH 2 ) a —, — (CH 2 ) a O—, —O (CH 2 ) a O—, —CH ⁇ CH—, —C ⁇ C—, —COO—, —OCO—, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH—, —CH 2 CH 2 —COO—, —OCO—CH 2 CH 2 —, —CH ⁇ N—, —N ⁇ CH—, —N ⁇ N—, —OCF 2 — or —CF 2 O—, and a is an integer of 1-20.
- the composition for heat radiating members can contain a compound especially preferable as a polymeric liquid crystal compound. These compounds are preferable because
- the composition for a heat dissipating member according to the fifth aspect of the present invention is the composition for a heat dissipating member according to any one of the first to fourth aspects of the present invention, wherein the inorganic filler is nitrided At least one selected from boron, aluminum nitride, and silicon nitride. If comprised in this way, the composition for heat radiating members can contain a more preferable compound as an inorganic filler.
- the composition for a heat radiating member according to the sixth aspect of the present invention is the composition for a heat radiating member according to any one of the first to fifth aspects of the present invention, wherein the curing agent is: It is at least one diamine compound represented by the formula (3-1). H 2 NZ— (AZ) m2 —NH 2 (3-1) [In the above formula (3-1), A is 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in these rings may be replaced by halogen or alkyl having 1 to 10 carbons; Each Z is a single bond or alkylene having 1 to 10 carbon atoms; m2 is an integer of 1 to 7.
- the composition for heat radiating members can contain a more preferable compound as a hardening
- the diamine compound is preferable because it can be cured without inhibiting the liquid crystallinity of the polymerizable liquid crystal compound.
- the composition for a heat radiating member according to the seventh aspect of the present invention is the composition for a heat radiating member according to any one of the first to sixth aspects of the present invention, wherein the inorganic filler is a cup.
- Surface modification means that a polymerizable liquid crystal compound is further bonded to a coupling agent bonded to a coupling-treated filler. If comprised in this way, since the heat dissipation member using the filler by which the coupling process was carried out, and the filler by which surface modification was carried out, high thermal conductivity can be obtained by the thickness direction, it is preferable.
- the heat dissipating member according to the eighth aspect of the present invention is obtained by curing the composition for a heat dissipating member according to any one of the first to seventh aspects of the present invention after performing an orientation treatment.
- the heat dissipating member obtained in this manner contains 20 to 95% by weight of the inorganic filler. If comprised in this way, a thermal radiation member can have high thermal conductivity by the synergistic effect of the thermal conductivity of the polymerized liquid crystal compound, and the thermal conductivity of the inorganic filler formed with the nitride.
- An electronic apparatus includes the heat dissipating member according to the eighth aspect of the present invention; an electronic device having a heat generating part; and the heat dissipating member in contact with the heat generating part. Located in electronic device. If comprised in this way, the heat which generate
- the heat radiating member formed from the composition for heat radiating member of the present invention has high thermal conductivity. In addition, it has excellent properties such as chemical stability, heat resistance, hardness and mechanical strength.
- the said heat radiating member is suitable for a heat sink, a heat radiating sheet, a heat radiating coating film, a heat radiating adhesive, etc., for example.
- An inorganic filler contained in the composition for a heat dissipation member of the present invention which is an unmodified filler (left), a filler treated with a coupling agent (center), a surface treated with a polymerizable liquid crystal compound after the coupling treatment It is an image figure of the modified filler (right). It is a graph which shows the relationship between the volume fraction (horizontal axis) of a filler, and thermal conductivity (vertical axis) about the heat-dissipating member containing the unmodified filler or the filler processed with the coupling agent.
- (A) is the thermal conductivity in the xy direction
- (b) is the thermal conductivity in the thickness direction.
- filler volume fraction horizontal axis
- thermal conductivity vertical axis
- Liquid crystal compound and “liquid crystal compound” are compounds that exhibit a liquid crystal phase such as a nematic phase or a smectic phase.
- a group in which any —CH 2 — in C 4 H 9 — is replaced by —O— or —CH ⁇ CH— includes C 3 H 7 O—, CH 3 —O— (CH 2 ) 2 —, CH 3 —O—CH 2 —O— and the like.
- groups in which any —CH 2 CH 2 — in C 5 H 11 — is replaced by —CH ⁇ CH— include H 2 C ⁇ CH— (CH 2 ) 3 —, CH 3 —CH ⁇ CH
- the term “arbitrary” means “at least one selected without distinction”.
- CH 3 —O—CH 2 —O— in which oxygen and oxygen are not adjacent to each other is more preferable than CH 3 —O—O—CH 2 — in which oxygen and oxygen are adjacent to each other. Is preferred.
- any hydrogen may be replaced by halogen, alkyl having 1 to 10 carbons, or halogenated alkyl having 1 to 10 carbons” with respect to ring A is, for example, 2 of 1,4-phenylene. , 3, 5 and 6 positions are substituted with a substituent such as fluorine or methyl group, and the substituent is “halogenated alkyl having 1 to 10 carbon atoms” Examples of these include examples such as a 2-fluoroethyl group and a 3-fluoro-5-chlorohexyl group.
- Compound (1-1) means a liquid crystal compound represented by the following formula (1-1), and may mean at least one compound represented by the following formula (1-1). is there.
- the “heat dissipating member composition (1)” means a liquid crystal composition containing at least one compound selected from the compounds (1-1).
- Polymer (1) means a liquid crystal polymer obtained by polymerizing the composition (1). When one compound (1-1) has a plurality of A, any two A may be the same or different. When a plurality of compounds (1-1) have A, any two A may be the same or different. This rule also applies to other symbols and groups such as R a1 and Z.
- composition for heat dissipation member includes a polymerizable liquid crystal compound having a structure containing an oxiranyl group or an oxetanyl group at both ends; a curing agent that cures the polymerizable liquid crystal compound; and nitriding And an inorganic filler formed of a product.
- the curing temperature of the heat radiating member composition is not less than the temperature range in which the polymerizable liquid crystal compound exhibits a liquid crystal phase and not more than the temperature range in which an isotropic phase is exhibited.
- liquid crystal phase of the polymerizable liquid crystal compound By using the liquid crystal phase of the polymerizable liquid crystal compound, it is possible to form a polymerized (cured) resin phase in a state where the molecules are ordered. Heat can flow through oriented molecules and inorganic fillers aligned along the orientation to obtain highly heat conducting properties.
- the compound (1-1) used in the present invention means a liquid crystal compound represented by the following formula (1-1), has a liquid crystal skeleton and a polymerizable group, has high polymerization reactivity, and a wide liquid crystal phase temperature range. Have good miscibility. This compound (1-1) tends to be uniform easily when mixed with other liquid crystalline compounds or polymerizable compounds.
- Preferred R a1 is hydrogen, fluorine, chlorine, cyano, —N ⁇ C ⁇ O, —N ⁇ C ⁇ S, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, alkenyl, alkenyloxy, alkenyloxy Alkyl, alkoxyalkenyl, alkynyl, alkynyloxy and the like can be mentioned.
- a group in which at least one hydrogen is replaced with a halogen is also preferable.
- Preferred halogens are fluorine and chlorine, more preferably fluorine.
- monofluoroalkyl polyfluoroalkyl, perfluoroalkyl, monofluoroalkoxy, polyfluoroalkoxy, perfluoroalkoxy and the like.
- These groups are preferably straight chains rather than branched chains from the viewpoint of easy conduction of phonons, that is, ease of heat transfer.
- R a1 is hydrogen, fluorine, chlorine, cyano, —CF 3 , —CF 2 H, —CFH 2 , —OCF 3 , —OCF 2 H, alkyl having 1 to 10 carbons, or 1 to 10 carbons Or alkoxyalkyl having 2 to 10 carbon atoms.
- alkyl, alkoxy and alkoxyalkyl examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, Examples include octyloxy, nonyloxy, decyloxy, methoxymethyl, methoxyethyl and the like.
- Particularly preferred R a1 is alkyl having 1 to 10 carbons and alkoxy having 1 to 10 carbons.
- Preferred examples of A include 1,4-cyclohexylene, 1,4-cyclohexenylene, 2,2-difluoro-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2 , 3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, naphthalene -2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9
- 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis. Since 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are structurally identical, the latter is not illustrated. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.
- A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene and the like.
- Particularly preferred A is 1,4-cyclohexylene and 1,4-phenylene.
- the bonding group Z of the compound (1-1) is a single bond, — (CH 2 ) 2 —, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH ⁇ CH
- —, —CF ⁇ CF— or — (CH 2 ) 4 — in particular, a single bond, — (CH 2 ) 2 —, —CF 2 O—, —OCF 2 —, —CH ⁇ CH— or —
- the viscosity becomes small.
- the bonding group Z is —CH ⁇ CH—, —CH ⁇ N—, —N ⁇ CH—, —N ⁇ N— or —CF ⁇ CF—
- the temperature range of the liquid crystal phase is wide.
- the bonding group Z is alkyl having about 4 to 10 carbon atoms, the melting point is lowered.
- Preferred Z a single bond, - (CH 2) 2 - , - (CF 2) 2 -, - COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 —, —CH ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, — (CH 2 ) 4 —, — (CH 2 ) 3 O—, —O (CH 2 ) 3 —, — ( CH 2 ) 2 COO—, —OCO (CH 2 ) 2 —, —CH ⁇ CH—COO—, —OCO—CH ⁇ CH— and the like.
- Z is a single bond, — (CH 2 ) 2 —, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH ⁇ CH—, —C ⁇ C— and the like can be mentioned.
- Particularly preferred Z is a single bond, — (CH 2 ) 2 —, —COO— or —OCO—.
- a 6-membered ring and a condensed ring containing a 6-membered ring are regarded as a ring, and for example, a 3-membered ring, a 4-membered ring or a 5-membered ring alone is not regarded as a ring.
- a condensed ring such as a naphthalene ring or a fluorene ring is regarded as one ring.
- the compound (1-1) may be optically active or optically inactive.
- the compound (1-1) may have an asymmetric carbon or an axial asymmetry.
- the configuration of the asymmetric carbon may be R or S.
- the asymmetric carbon may be located at either R a1 or A.
- the compatibility of the compound (1-1) is good.
- the compound (1-1) has axial asymmetry, the twist-inducing force is large.
- the light application property may be any.
- a compound having desired physical properties can be obtained by appropriately selecting the terminal group R a1 , the type of the ring structure A and the bonding group Z, and the number of rings.
- Compound (1-1) can also be represented by the following formula (1-a) or (1-b).
- A, Z and R a have the same meanings as A, Z and R a1 defined in the above formula (1-1), and P represents the above formula (2- 1) to (2-2) represents a polymerizable group, and Y represents a single bond or alkylene having 1 to 20 carbon atoms, preferably alkylene having 1 to 10 carbon atoms.
- CH 2 — may be replaced by —O—, —S—, —CO—, —COO—, —OCO— or —CH ⁇ CH—.
- Particularly preferred Y is alkylene in which —CH 2 — at one or both ends of alkylene having 1 to 10 carbon atoms is replaced by —O—.
- m is an integer of 1 to 6, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.
- Preferred examples of the compound (1-1) include the following compounds (a-1) to (g-20).
- R a , P and Y are as defined in the above formulas (1-a) and (1-b).
- Z 1 is a single bond, — (CH 2 ) 2 —, — (CF 2 ) 2 —, — (CH 2 ) 4 —, —CH 2 O—, —OCH 2 —, — (CH 2 ) 3 O— , —O (CH 2 ) 3 —, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, —CH ⁇ CHCOO—, —OCOCH ⁇ CH—, — (CH 2 ) 2 COO— , —OCO (CH 2 ) 2 —, —C ⁇ C—, —C ⁇ C—COO—, —OCO—C ⁇ C—, —C ⁇ C—CH ⁇ CH—, —CH ⁇ CH—C ⁇ C —, —CH ⁇ N—, —N ⁇ CH—,
- Z 2 represents — (CH 2 ) 2 —, — (CF 2 ) 2 —, — (CH 2 ) 4 —, —CH 2 O—, —OCH 2 —, — (CH 2 ) 3 O—, —O (CH 2 ) 3 —, —COO—, —OCO—, —CH ⁇ CH—, —CF ⁇ CF—, —CH ⁇ CHCOO—, —OCOCH ⁇ CH—, — (CH 2 ) 2 COO—, —OCO (CH 2 ) 2 —, —C ⁇ C—, —C ⁇ C—COO—, —OCO—C ⁇ C—, —C ⁇ C—CH ⁇ CH—, —CH ⁇ CH—C ⁇ C—, — CH ⁇ N—, —N ⁇ CH—, —N ⁇ N—, —OCF 2 — or —CF 2 O—.
- Z 3 represents a single bond, alkyl having 1 to 10 carbon atoms, — (CH 2 ) a —, —O (CH 2 ) a O—, —CH 2 O—, —OCH 2 —, —O (CH 2 ).
- Z 3 may be the same or different.
- a is an integer of 1 to 20.
- X is a substituent of 1,4-phenylene and fluorene-2,7-diyl in which arbitrary hydrogen may be replaced by halogen, alkyl or fluorinated alkyl, and represents halogen, alkyl or fluorinated alkyl.
- More preferred compound (1-1) can be represented by the following formula (1-c) or (1-d).
- A, Y, Z, R a and m are as defined above, and P 1 represents a polymerizable group represented by the following formulas (2-1) to (2-2).
- two P 1 represent the same polymerizable group (2-1) to (2-2)
- two Y represent the same group
- two Y are symmetrical. Combine to be.
- the compound (1-1) can be synthesized by combining known methods in organic synthetic chemistry. Methods for introducing the desired end groups, ring structures and linking groups into the starting materials are described, for example, by Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons. , Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. . Reference may also be made to JP-A-2006-265527.
- ⁇ Curing agent> examples of preferred curing agents are shown below.
- diamine is preferable because the polymerizable liquid crystal compound can be cured without inhibiting the liquid crystal property of the polymerizable liquid crystal compound. What is necessary is just to select the quantity of a hardening
- Examples of the high thermal conductive filler include nitrides such as aluminum nitride, boron nitride, and silicon nitride.
- Inorganic filler and metal filling such as aluminum nitride, boron nitride, silicon nitride, magnesium hydroxide, aluminum hydroxide, gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, stainless steel It may be a material.
- the shape of the filler examples include a spherical shape, an amorphous shape, a fiber shape, a rod shape, a cylindrical shape, and a plate shape.
- the shape of the filling is preferably a shape that does not hinder the alignment when the polymerizable liquid crystal compound exhibits a liquid crystal phase.
- the type, shape, size, addition amount, and the like of the filler can be appropriately selected depending on the purpose. When the obtained heat radiating member requires insulation, a conductive filler may be used as long as the desired insulation is maintained.
- Boron nitride and aluminum nitride are preferable.
- hexagonal boron nitride (h-BN) and aluminum nitride are preferable.
- Boron nitride and aluminum nitride are preferable because they have a very high thermal conductivity in the plane direction, a low dielectric constant, and a high insulating property.
- it is preferable to use boron nitride of a plate-like crystal because the plate-like structure is easily arranged along the alignment of the liquid crystal compound or the liquid crystal compound is easily arranged along the plate-like structure.
- the average particle diameter of the filler is preferably 0.1 to 200 ⁇ m. More preferably, it is 1 to 100 ⁇ m. When it is 0.1 ⁇ m or more, the thermal conductivity is good, and when it is 200 ⁇ m or less, the filling rate can be increased.
- the average particle size is based on particle size distribution measurement by a laser diffraction / scattering method. That is, when the powder is divided into two from a certain particle size by the wet method using the analysis based on the Franhofer diffraction theory and Mie's scattering theory, the larger side and the smaller side are equivalent (volume basis). Was the median diameter.
- the amount of the filler is preferably such that the cured heat radiating member contains 20 to 95% by weight of the filler. More preferably, it is 50 to 95% by weight. When the content is 20% by weight or more, the thermal conductivity is preferably increased.
- the heat dissipation member is preferably 95% by weight or less because it does not become brittle.
- an unmodified one (left in FIG. 2) may be used as it is.
- what processed the surface with the coupling agent (FIG. 2 center) may be used.
- boron nitride (h-BN) is treated with a silane coupling agent.
- the silane coupling agent is bonded only around the periphery.
- Boron nitride treated with a coupling agent can form a bond with the polymerizable liquid crystal compound in the composition for heat dissipation member, and this bond is considered to contribute to heat conduction.
- the coupling agent preferably reacts with an oxiranyl group or the like or a curing agent, an amine-based or oxiranyl group or the like is preferred.
- an amine-based or oxiranyl group or the like is preferred.
- Silica Ace S310, S320, S330, S360, S510, S530 and the like are available from JNC Corporation.
- bonding increases so that there are many modifications with a coupling agent, it is preferable.
- a filler that has been treated with a coupling agent and further surface-modified with a polymerizable liquid crystal compound (right in FIG. 2) may be used.
- boron nitride (h-BN) treated with a silane coupling agent is surface-modified with a polymerizable liquid crystal compound.
- Boron nitride surface-modified with a polymerizable liquid crystal compound can form a bond with the polymerizable liquid crystal compound in the heat dissipation member composition, and this bond is considered to contribute to heat conduction.
- the polymerizable liquid crystal compound is preferably a compound represented by the above formula (1-1).
- polymerizable liquid crystal compounds may be used, and polymerizable compounds having no liquid crystallinity may be used.
- the surface modification with a polymerizable liquid crystal compound or the like is more preferable as the number of the surface modification is increased as the number of bonds increases.
- the heat radiating member composition (1) of the present application comprises at least one compound (1-1) and is combined with an inorganic filler as a high thermal conductive inorganic filler.
- the composition (1) may be composed of two or more compounds (1-1), and at least one compound (1-1) and at least one other than the compound (1-1). It may be composed of a combination with a seed compound.
- the constituent elements other than the compound (1-1) are not particularly limited.
- polymerizable compounds other than the compound (1-1) hereinafter also referred to as “other polymerizable compounds”
- non-polymerizable Liquid crystal compounds non-polymerizable Liquid crystal compounds
- polymerization initiators and solvents.
- the composition for heat radiating member (1) may contain other polymerizable compounds as constituent elements.
- a polymerizable compound a compound that does not lower the film formability and the mechanical strength is preferable.
- This polymerizable compound is classified into a compound having no liquid crystallinity and a compound having liquid crystallinity.
- the polymerizable compound having no liquid crystallinity include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, and the like.
- the composition for heat radiating member (1) may contain a liquid crystalline compound having no polymerizable group as a constituent element.
- a liquid crystal database database LiqCryst, LCI Publisher GmbH, Hamburg, Germany.
- a composite material of the polymer of the compound (1-1) and the liquid crystal compound can be obtained.
- a non-polymerizable liquid crystal compound exists in a polymer network such as a polymer dispersed liquid crystal.
- the composition for heat radiating member (1) may contain a polymerization initiator as a constituent element.
- a polymerization initiator for example, a radical photopolymerization initiator, a cationic photopolymerization initiator, or a thermal radical polymerization initiator may be used depending on the polymerization method of the composition (1).
- Preferred initiators for thermal radical polymerization include, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxide.
- Oxide (DTBPO) t-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), etc.
- DTBPO diisopropyl peroxydicarbonate
- t-butylperoxy-2-ethylhexanoate t-butylperoxypivalate
- di-t-butylperoxide Oxide
- MAIB dimethyl 2,2′-azobisisobutyrate
- AIBN azobisisobuty
- the composition for heat radiating member (1) may contain a solvent.
- the polymerization of the composition (1) may be performed in a solvent or without a solvent.
- the composition (1) containing a solvent may be applied on a substrate by, for example, a spin coating method and then photopolymerized after removing the solvent. Further, after photocuring, it may be heated to an appropriate temperature and post-treated by heat curing.
- Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, ⁇ -butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, cyclohexane, methylcyclohexane, cyclopentanone , Cyclohexanone, PGMEA and the like.
- the said solvent may be used individually by 1 type, or may mix and use 2 or more types.
- there is not much meaning in limiting the use ratio of the solvent at the time of polymerization and it may be determined for each case in consideration of polymerization efficiency, solvent cost, energy cost, and the like.
- a stabilizer may be added for easy handling.
- known ones can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol and 3,5-di-t-butyl-4-hydroxytoluene (BHT).
- BHT 3,5-di-t-butyl-4-hydroxytoluene
- you may add an additive (oxide etc.) in order to adjust the viscosity and color of the composition for heat radiating members.
- titanium oxide for making white, carbon black for making black, and silica fine powder for adjusting viscosity can be mentioned.
- an additive may be added to further increase the mechanical strength.
- fibers or long molecules such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, and polyimide can be used as inorganic fibers and cloth such as glass and carbon fiber, or polymer additives.
- the heat radiating member according to the second embodiment of the present invention is formed by molding a cured product (polymer (1)) obtained by curing the composition for heat radiating member according to the first embodiment according to the application. It is.
- the polymer (1) is obtained by polymerizing the composition (1) for a heat radiating member containing at least one compound (1) while controlling the orientation.
- This polymer (1) has high thermal conductivity, low water permeability, water absorption and gas permeability, and is excellent in chemical stability, heat resistance, hardness, mechanical strength and the like.
- the mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, bending elastic modulus, impact strength, and the like.
- FIG. 1 is an image diagram of a heat dissipation member when boron nitride is used as a filler.
- the polymer (1) is a thermosetting resin.
- a thermosetting resin is easily obtained.
- the thermosetting resin has a three-dimensional crosslinked structure. Since such a polymer (1) is insoluble in a solvent, the molecular weight cannot be measured. However, in the case of obtaining the heat dissipation member by applying the composition (1) for heat dissipation member on the substrate and polymerizing with the molecular orientation fixed, there is no further processing, so the size of the molecular weight is a problem. However, it is only necessary to satisfy the conditions in the use environment. In order to further increase the molecular weight, a crosslinking agent may be added. Thereby, the polymer (1) extremely excellent in chemical resistance and heat resistance can be obtained.
- a cross-linking agent known ones can be used without limitation, and examples thereof include tris (3-mercaptopropionate).
- the polymer (1) can have a feature that the molecular orientation is fixed in an arbitrary direction.
- the polymer (1) to which high thermal conductivity is imparted in the certain direction can be obtained by fixing the mesogenic portion of the liquid crystal molecule by aligning it as uniformly as possible in the certain direction. This direction can be arbitrarily controlled by aligning liquid crystal molecules before polymerization.
- thermal conductivity in all directions can be achieved by laminating films arranged in a certain direction in each direction.
- Such a laminated structure can also be formed by repeating the process of “application of composition for heat dissipation member ⁇ polymerization ⁇ application of composition for heat dissipation member ⁇ polymerization”. Forming a laminated structure in this way is also useful in reducing the anisotropy of the mechanical strength of the resulting heat dissipation member.
- the film arranged in a fixed direction may be cut out, and the film may be rearranged so that the orientation becomes vertical, thereby improving the thermal conductivity in the thickness direction of the film.
- a method for controlling the orientation of the mesogenic portion of the liquid crystal molecules in the heat radiating member composition (1) a method using an alignment film, a method of adding an alignment control agent to the composition (1), a rubbing treatment method, Examples thereof include a method of aligning by the self-alignment regulating force possessed by the composition (1) itself. These methods may be performed singly or in combination of two or more. Examples of the alignment state controlled by such an alignment control method include homogeneous, twist, homeotropic, hybrid, bend, and spray alignment, and can be appropriately determined according to the application and the alignment control method.
- the heat treatment of the composition (1) is performed at or above the clearing point of the composition (1).
- the heat treatment method there is a method in which the composition (1) is heated to a temperature at which a liquid crystal phase is exhibited to form an orientation in the composition (1).
- the alignment may be formed by changing the temperature within a temperature range in which the composition (1) exhibits a liquid crystal phase. This method was more orderly by substantially completing the orientation of the composition (1) by heating the composition (1) to a high temperature range that exhibits the liquid crystal phase, and then lowering the temperature. It is to be oriented.
- the liquid crystal phase expressed by the heat radiating member composition (1) may be a nematic, smectic, or cholesteric phase.
- the heat treatment temperature is in the range of room temperature to 150 ° C., preferably room temperature to 100 ° C., more preferably room temperature to 70 ° C.
- the heat treatment time ranges from 5 seconds to 2 hours, preferably from 10 seconds to 60 minutes, more preferably from 20 seconds to 30 minutes.
- the temperature of the layer made of the composition for heat radiating member (1) may not be raised to a predetermined temperature, and when it is longer than the above range, the productivity may be lowered.
- the said heat processing conditions change with the kind and composition ratio of a compound used for this composition (1), the presence or absence, content of a polymerization initiator, etc., they show an approximate range to the last.
- Examples of the polymerization method of the heat radiating member composition (1) include radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization.
- Thermal polymerization or photopolymerization using light or heat such as electron beam, ultraviolet ray, visible ray or infrared ray (heat ray) is suitable.
- the thermal polymerization is preferably performed in the presence of a radical polymerization initiator, and the photopolymerization is preferably performed in the presence of a radical photopolymerization initiator.
- thermal polymerization by heat is preferred.
- the obtained polymer (1) may be any of a homopolymer, a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer, and may be appropriately selected depending on the use. .
- the thermosetting temperature is in the range of room temperature to 350 ° C., preferably room temperature to 250 ° C., more preferably 50 ° C. to 200 ° C.
- the curing time ranges from 5 seconds to 10 hours, preferably from 1 minute to 5 hours, more preferably from 5 minutes to 1 hour.
- After the polymerization it is preferable to slowly cool in order to suppress stress strain and the like.
- reheating treatment may be performed to reduce strain and the like.
- the polymer whose orientation is controlled as described above or the polymer in the polymerization process may be further controlled in an arbitrary direction by a mechanical operation such as stretching.
- the isolated polymer (1) may be dissolved in a solvent and oriented on an orientation-treated substrate and processed into a film or the like, or two polymers may be mixed and processed, or a plurality of polymers may be laminated. You may let them.
- the solvent include N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide dimethyl acetal, tetrahydrofuran, chloroform, 1,4-dioxane.
- Bis (methoxyethyl) ether, ⁇ -butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, 2-methoxyethyl acetate, methyl ethyl ketone, cyclopentanone, cyclohexanone and the like are preferable. These may be used by mixing with common organic solvents such as acetone, benzene, toluene, heptane, methylene chloride.
- the heat dissipating member of the present application is made of the polymer (1), and is used in the form of a sheet, a film, a thin film, a fiber, a molded body and the like.
- Preferred shapes are films and thin films. These are preferably cured in an oriented state by performing an orientation treatment utilizing flow.
- a film and a thin film are obtained by polymerizing the composition (1) for heat radiating member applied to the substrate or sandwiched between the substrates. It can also be obtained by applying the composition (1) containing a solvent to an alignment-treated substrate and removing the solvent. Further, the film can be obtained by press-molding a polymer.
- the thickness of the sheet is 1 mm or more
- the thickness of the film is 5 ⁇ m or more, preferably 10 to 500 ⁇ m, more preferably 20 to 300 ⁇ m
- the thickness of the thin film is less than 5 ⁇ m. What is necessary is just to change a film thickness suitably according to a use.
- the composition for heat radiating members (1) which does not contain a solvent can be obtained.
- a method for producing a film as a heat radiating member using the composition (1) for a heat radiating member not containing a solvent will be specifically described.
- the composition for heat radiating members (1) containing no solvent is sandwiched between hot plates using a compression molding machine, and orientation molding is performed by compression molding.
- the polymerizable liquid crystal compound is polymerized at a temperature range above the liquid crystal phase to form a polymer. Further, post-curing may be performed at an appropriate time and temperature.
- the pressure at the time of compression molding is preferably 50 ⁇ 200kgf / cm 2, more preferably 70 ⁇ 180kgf / cm 2. Basically, the pressure during curing is preferably high. However, it is preferable that the pressure is appropriately changed depending on the fluidity of the mold and the target physical properties (which direction of thermal conductivity is important) and an appropriate pressure is applied.
- the method of manufacturing the film as a heat radiating member using the composition for heat radiating members (1) containing a solvent is demonstrated concretely.
- the composition (1) is applied onto a substrate, and the solvent is removed by drying to form a coating film layer having a uniform film thickness.
- the coating method include spin coating, roll coating, caten coating, flow coating, printing, micro gravure coating, gravure coating, wire barcode, dip coating, spray coating, meniscus coating method, and the like.
- the solvent can be removed by drying, for example, by air drying at room temperature, drying on a hot plate, drying in a drying furnace, blowing hot air or hot air, and the like.
- the conditions for removing the solvent are not particularly limited, and it may be dried until the solvent is almost removed and the fluidity of the coating layer is lost.
- the molecular orientation of the liquid crystal molecules in the coating layer may be completed in the process of drying the coating layer.
- the coating layer that has undergone the drying step can be subjected to the polymerization step without going through the heat treatment step described above.
- an alignment film may be formed only on a substrate, or after an alignment film is formed on a substrate, a rubbing treatment with a rayon cloth or the like, or a substrate is directly rubbed with a rayon cloth or the like. And a method of oblique deposition of silicon oxide, a rubbing-free orientation method using a stretched film, a photo-alignment film, an ion beam, or the like.
- a desired alignment state can be formed without processing the substrate surface. For example, when homeotropic alignment is formed, surface treatment such as rubbing is often not performed, but rubbing may be performed in order to prevent alignment defects.
- the alignment film is not particularly limited as long as it can control the alignment of the heat radiating member composition (1), and a known alignment film can be used.
- a known alignment film can be used.
- polyimide, polyamide, polyvinyl alcohol, alkylsilane, Alkylamine or lecithin alignment films are preferred.
- a rubbing cloth made of materials such as rayon, cotton, and polyamide is applied to a metal roll or the like, and the roll is rotated while being in contact with the substrate or the alignment film.
- a method of moving the substrate while moving it, a method of moving the substrate side while fixing the roll, and the like are employed.
- an orientation control additive may be contained in the heat radiating member composition (1).
- alignment control additives include imidazoline, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl.
- Alignment such as homogeneous, homeotropic, twist, spray, hybrid, etc. can be obtained by appropriately selecting the substrate subjected to the alignment treatment as described above and sandwiching the heat radiating member composition between the substrates.
- the orientation may be arbitrarily controlled by applying an electric field or a magnetic field.
- the substrate examples include glass substrates such as alkali glass, borosilicate glass and flint glass; metal substrates such as aluminum, iron and copper; inorganic substrates such as silicon; polyimide, polyamideimide, polyamide, polyetherimide and polyether Ether ketone, polyether ketone, polyketone sulfide, polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose , Triacetyl cellulose or partially saponified product thereof, epoxy resin, phenol resin, norbornene Such as a plastic film substrate such as fat.
- glass substrates such as alkali glass, borosilicate glass and flint glass
- metal substrates such as aluminum, iron and copper
- the film substrate may be a uniaxially stretched film or a biaxially stretched film.
- the film substrate may be subjected to surface treatment such as saponification treatment, corona treatment, or plasma treatment in advance.
- the material used as the protective layer include polyvinyl alcohol.
- an anchor coat layer may be formed in order to improve the adhesion between the protective layer and the substrate.
- Such an anchor coat layer may be any inorganic or organic material as long as it improves the adhesion between the protective layer and the substrate.
- the heat radiating member of the present invention is useful for a heat radiating plate, a heat radiating sheet, a heat radiating film, a heat radiating adhesive, a heat radiating molded product, and the like.
- An electronic apparatus includes the heat dissipating member according to the second embodiment and an electronic device having a heat generating portion.
- a heat radiating member is arrange
- the shape of the heat dissipation member may be any of a heat dissipation plate, a heat dissipation sheet, a heat dissipation film, a heat dissipation adhesive, a heat dissipation molded product, and the like.
- a semiconductor element can be given as an electronic device.
- the heat dissipating member of the present application has high heat resistance and high insulation in addition to high thermal conductivity.
- an IGBT is one of semiconductor elements and is a bipolar transistor in which a MOSFET is incorporated in a gate portion, and is used for power control.
- Electronic devices equipped with IGBTs include high-power inverter main conversion elements, uninterruptible power supply devices, AC motor variable voltage variable frequency control devices, railway vehicle control devices, electric vehicles such as hybrid cars and electric cars, IH A cooker can be mentioned.
- the component material which comprises the heat radiating member used for the Example of this invention is as follows. ⁇ Polymerizable liquid crystal compound> Liquid crystalline epoxy: Formula (4-1) below (manufactured by JNC Corporation) It can be synthesized by the method described in Japanese Patent No. 5084148.
- BN particles modified with the coupling agent were transferred to a sample tube, 50 mL of THF (manufactured by Nacalai Tesque) was added, and then pulverized by ultrasonic treatment (MODEL 450, manufactured by BRANSON). Further, this solution was separated and purified at 6000 rpm for 10 minutes using a centrifuge (CT6E manufactured by Hitachi Koki Co., Ltd.). After discarding the supernatant, 50 mL of acetone was added and the same operation was performed twice. The modified BN particles after purification were dried in an oven at 60 ° C. for 24 hours.
- the coupling agent-treated BN particles and the liquid crystalline epoxy were measured on 2 g and 4 g (BN mixing ratio: 19 vol%) on a medicine wrapping paper, mixed using a mortar, and then biaxial roll (Nitto Reactor Co., Ltd.) The mixture was kneaded at 120 ° C. for 10 minutes using HR-3). Thereafter, separation and purification were performed by sonication and centrifugation to obtain coupling agent-modified BN particles from which unreacted components were removed. The coating amount was calculated from the heat loss at 600 ° C. of the produced coupling agent-modified BN particles using a TG-DTA apparatus (EXSTAR TG / DTA5200 manufactured by Seiko Instruments Inc.).
- Thermal conductivity was measured in advance by specific heat of the heat radiating member (measured with DSC input compensation type differential scanning calorimeter EXSTAR6000 manufactured by Seiko Instruments Inc.) and specific gravity (Mettler Toledo). The thermal conductivity was determined by multiplying the value by the thermal diffusivity determined by ULTC Riko Co., Ltd. TC7000 thermal diffusivity measuring device. The thermal diffusivity in the thickness direction was measured using a standard sample holder after blackening the sample using carbon spray.
- the thermal diffusivity in the plane direction is determined from the distance from the time when the sample is irradiated with the laser and the infrared ray is emitted, and the distance between the spot that irradiates the laser and the spot that detects the infrared ray. Calculated.
- Example 1 a heat radiating member was prepared using unmodified BN particles (PTX25) in ⁇ Preparation of heat radiating member> above.
- the thermal conductivity is shown below.
- 3 and 4 are graphs showing the relationship between the volume fraction of unmodified BN particles and the thermal conductivity. 3 and 4, (a) is the thermal conductivity in the xy direction, and (b) is the thermal conductivity in the thickness direction. Further, in Example 1, the same evaluation was performed using bisphenol type epoxy (jER828) instead of liquid crystalline epoxy (Comparative Example 1), and the thermal conductivity in the xy direction was 14.5 W / mK. There was only.
- FIG. 3 is a graph showing the relationship between the volume fraction of BN particles and the thermal conductivity. In FIG. 3, (a) is the thermal conductivity in the xy direction, and (b) is the thermal conductivity in the thickness direction.
- FIG. 4 is a graph showing the relationship between the volume fraction of BN particles and the thermal conductivity. In FIG. 4, (a) is the thermal conductivity in the xy direction, and (b) is the thermal conductivity in the thickness direction.
- FIG. 4 is a graph showing the relationship between the volume fraction of BN particles and the thermal conductivity. In FIG. 4, (a) is the thermal conductivity in the xy direction, and (b) is the thermal conductivity in the thickness direction.
- the heat dissipation member using unmodified boron nitride particles and the heat dissipation member using silane coupling agent-treated boron nitride particles have higher thermal conductivity as the amount of boron nitride particles increases.
- the value was extremely high in both the xy (planar) direction and the thickness direction, as compared with a heat radiating member formed from polymerizable epoxy that did not exhibit liquid crystallinity and boron nitride particles.
- the thermal conductivity in the xy direction is only 14.5 W / mK
- Example 1 liquid crystalline epoxy
- the heat conductivity in the thickness direction is higher in the heat dissipation member using coupling-modified or surface-modified boron nitride particles than in the heat dissipation member using unmodified boron nitride particles. This is thought to be because the modifying molecules around the modified boron nitride particles obstructed the flow alignment of the liquid crystal polymer during high shear, and the force in the thickness direction acted on the modified boron nitride particles, improving the thermal conductivity in the thickness direction. It is done.
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Abstract
Description
特許文献1には、樹脂の熱伝導率を向上させる方法として、液晶組成物を配向制御添加剤やラビング処理法などにより配向制御して重合することにより得られる放熱部材が開示されている。
そこで本発明は、高熱伝導性を有する放熱部材を形成可能な組成物および放熱部材を提供することを課題とする。
このように構成すると、放熱部材用組成物は、重合性液晶化合物が液晶相および等方相を示す温度範囲内で硬化する。すなわち、流動性を持つ状態で重合を起こすことができ、さらに重合性液晶化合物が配向している状態(分子が一方向に揃った状態)で重合性液晶化合物を重合させて、無機フィラーとともに硬化させることができる組成物となる。重合温度が液晶相を示す温度領域よりも高くなり、等方相を示す温度領域になった場合でも、メソゲン部位は冷却時に高い配向性を発現する。したがって、放熱部材用組成物から形成された膜(放熱部材)は、重合した液晶化合物の熱伝導性と、窒化物で形成された無機フィラーの熱伝導性の相乗効果により、高い熱伝導性を有することができる。
Ra1-Z-(A-Z)m1-Ra1 ・・・(1-1)
[上記式(1-1)中、
Ra1は、それぞれ下記式(2-1)~(2-2)のいずれかで表される重合性基であり;
Aは、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、ナフタレン-2,6-ジイル、テトラヒドロナフタレン-2,6-ジイル、フルオレン-2,7-ジイル、ビシクロ[2.2.2]オクト-1,4-ジイル、またはビシクロ[3.1.0]ヘキス-3,6-ジイルであり、
これらの環において、任意の-CH2-は、-O-で置き換えられてもよく、任意の-CH=は、-N=で置き換えられてもよく、任意の水素は、ハロゲン、炭素数1~10のアルキル、または炭素数1~10のハロゲン化アルキルで置き換えられてもよく、
該アルキルにおいて、任意の-CH2-は、-O-、-CO-、-COO-、または-OCO-で置き換えられてもよく、任意の-CH2CH2-は、-CH=CH-、または-C≡C-で置き換えられてもよく;
Zは、それぞれ単結合、または炭素数1~20のアルキレンであり、
該アルキレンにおいて、任意の-CH2-は、-O-、-S-、-CO-、-COO-、または-OCO-で置き換えられてもよく、任意の-CH2CH2-は、-CH=CH-、-CF=CF-、-CH=N-、-N=CH-、-N=N-、-N(O)=N-、または-C≡C-で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく;
m1は、1~6の整数である。]
このように構成すると、放熱部材用組成物は、重合性液晶化合物としてより好ましい化合物を含有することができる。これらの化合物は、熱硬化性でありフィラーの量に影響を受けずに硬化させることができ、さらに耐熱性に優れる。また分子構造は、対称性、直線性を有するため、フォノンの伝導に有利であると考えられる。
このように構成すると、放熱部材用組成物は、重合性液晶化合物としてさらに好ましい化合物を含有することができる。これらの化合物は、分子の直線性がより高くなり、フォノンの伝導により有利であると考えられる。
このように構成すると、放熱部材用組成物は、重合性液晶化合物として特に好ましい化合物を含有することができる。これらの化合物は、物性、作り易さ、または扱い易さに優れるため好ましい。
このように構成すると、放熱部材用組成物は、無機フィラーとしてより好ましい化合物を含有することができる。
H2N-Z-(A-Z)m2-NH2 ・・・(3-1)
[上記式(3-1)中、
Aは、1,4-シクロヘキシレン、または1,4-フェニレンであり、これらの環の任意の水素は、ハロゲン、または炭素数1~10のアルキルで置き換えられてもよく;
Zは、それぞれ単結合、または炭素数1~10のアルキレンであり;
m2は1~7の整数である。]
このように構成すると、放熱部材用組成物は、硬化剤としてより好ましい化合物を含有することができる。特にm2が偶数の場合、ジアミン化合物は、重合性液晶化合物の液晶性を阻害することなく、硬化させることができるため好ましい。
このように構成すると、カップリング処理したフィラー、表面修飾したフィラーを用いた放熱部材で、厚み方向により高い熱伝導性を得られるため好ましい。
このように構成すると、放熱部材は、重合した液晶化合物の熱伝導性と窒化物で形成された無機フィラーの熱伝導性の相乗効果により、高い熱伝導性を有することができる。
このように構成すると、高熱伝導性を有する放熱部材により、電子デバイスに生じた熱を効率よく伝導させることができる。
「液晶化合物」「液晶性化合物」は、ネマチック相やスメクチック相などの液晶相を発現する化合物である。
本発明の第1の実施の形態に係る放熱部材用組成物は、オキシラニル基またはオキセタニル基を含む構造を両末端に有する重合性液晶化合物と;前記重合性液晶化合物を硬化させる硬化剤と;窒化物で形成された無機フィラーとを含む。放熱部材用組成物の硬化温度は、前記重合性液晶化合物が液晶相を示す温度範囲以上、等方相を示す温度範囲以下である。
重合性液晶化合物の液晶相を利用することにより、分子が秩序良くならんだ状態で重合(硬化)した樹脂相を形成させることが可能になる。熱は配向した分子および配向に沿って整列した無機フィラーを通じて流れ、高熱伝導な特性を得ることができる。
本発明で用いられる化合物(1-1)は、下記式(1-1)で表される液晶化合物を意味し、液晶骨格と重合性基を有し、高い重合反応性、広い液晶相温度範囲、良好な混和性などを有する。この化合物(1-1)は他の液晶性の化合物や重合性の化合物などと混合するとき、容易に均一になりやすい。
Ra1-Z-(A-Z)m1-Ra1 (1-1)
上記化合物(1-1)のRa1が直鎖状アルキルである場合、液晶相の温度範囲が広く、かつ粘度が小さい。一方、Ra1が分岐状アルキルである場合、他の液晶性の化合物との相溶性がよい。Ra1がシアノ、ハロゲン、-CF3、-OCF3である場合においても、良好な液晶相温度範囲を示し、誘電率異方性が高く、適度な相溶性を有する。
上記化合物(1-1)の環構造Aにおける少なくとも1つの環が1,4-フェニレンの場合、配向秩序パラメーター(orientationalorder parameter)および磁化異方性が大きい。また、少なくとも2つの環が1,4-フェニレンの場合、液晶相の温度範囲が広く、さらに透明点が高い。1,4-フェニレン環上の少なくとも1つの水素がシアノ、ハロゲン、-CF3または-OCF3に置換された場合、誘電率異方性が高い。また、少なくとも2つの環が1,4-シクロヘキシレンである場合、透明点が高く、かつ粘度が小さい。
上記化合物(1-1)の結合基Zが、単結合、-(CH2)2-、-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH=CH-、-CF=CF-または-(CH2)4-である場合、特に、単結合、-(CH2)2-、-CF2O-、-OCF2-、-CH=CH-または-(CH2)4-である場合、粘度が小さくなる。また、結合基Zが、-CH=CH-、-CH=N-、-N=CH-、-N=N-または-CF=CF-である場合、液晶相の温度範囲が広い。また、結合基Zが、炭素数4~10程度のアルキルの場合、融点が低下する。
以上のように、末端基Ra1、環構造Aおよび結合基Zの種類、環の数を適宜選択することにより、目的の物性を有する化合物を得ることができる。
化合物(1-1)は、下記式(1-a)または(1-b)のように表すこともできる。
P-Y-(A-Z)m-Ra (1-a)
P-Y-(A-Z)m-Y-P (1-b)
Z1は、単結合、-(CH2)2-、-(CF2)2-、-(CH2)4-、-CH2O-、-OCH2-、-(CH2)3O-、-O(CH2)3-、-COO-、-OCO-、-CH=CH-、-CF=CF-、-CH=CHCOO-、-OCOCH=CH-、-(CH2)2COO-、-OCO(CH2)2-、-C≡C-、-C≡C-COO-、-OCO-C≡C-、-C≡C-CH=CH-、-CH=CH-C≡C-、-CH=N-、-N=CH-、-N=N-、-OCF2-または-CF2O-である。なお、複数のZ1は同一でも異なっていてもよい。
P1-Y-(A-Z)m-Ra (1-c)
P1-Y-(A-Z)m-Y-P1 (1-d)
上記式中、A、Y、Z、Raおよびmはすでに定義したとおりであり、P1は下記式(2-1)~(2-2)で表される重合性基を示す。上記式(1-d)の場合、2つのP1は同一の重合性基(2-1)~(2-2)を示し、2つのYは同一の基を示し、2つのYは対称となるように結合する。
上記化合物(1-1)は、有機合成化学における公知の手法を組み合わせることにより合成できる。出発物質に目的の末端基、環構造および結合基を導入する方法は、たとえば、ホーベン-ワイル(Houben-Wyle,Methods of Organic Chemistry, GeorgThieme Verlag, Stuttgart)、オーガニック・シンセシーズ(OrganicSyntheses, John Wily &Sons, Inc.)、オーガニック・リアクションズ(OrganicReactions, John Wily & Sons Inc.)、コンプリヘンシブ・オーガニック・シンセシス(ComprehensiveOrganic Synthesis, Pergamon Press)、新実験化学講座(丸善)などの成書に記載されている。また、特開2006-265527号公報を参照してもよい。
好ましい硬化剤の例を以下に示す。
アミン系硬化剤として、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、o-キシレンジアミン、m-キシレンジアミン、p-キシレンジアミン、トリメチルヘキサメチレンジアミン、2-メチルペンタメチレンジアミン、ジエチルアミノプロピルアミン、イソホロンジアミン、1,3-ビスアミノメチルシクロヘキサン、ビス(4-アミノ-3-メチルシクロヘキシル)メタン、ビス(4-アミノシクロヘキシル)メタン、ノルボルネンジアミン、1,2-ジアミノシクロヘキサン、3,9-ジプロパンアミン-2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノ-1,2-ジフェニルエタン、o-フェニレンジアミン、m-フェニレンジアミン、p-フェニレンジアミン、4,4’-ジアミノジフェニルスルホン、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン、ポリシクロヘキシルポリアミン、N-アミノエチルピペラジンなどが挙げられる。
特にジアミンは、重合性液晶化合物の液晶性を阻害することなく重合性液晶化合物を硬化させることができるため好ましい。硬化剤の量は、エポキシ当量またはオキセタン当量により適宜選択すればよい。
高熱伝導性の充填材(無機フィラー)として、窒化アルミニウム、窒化ホウ素、窒化珪素などの窒化物が挙げられる。ダイアモンド、黒鉛、炭化珪素、珪素、ベリリア、酸化マグネシウム、酸化アルミニウム、酸化亜鉛、酸化珪素、酸化銅、酸化チタン、酸化セリウム、酸化イットリウム、酸化錫、酸化ホルミニウム、酸化ビスマス、酸化コバルト、酸化カルシウム、窒化アルミニウム、窒化ホウ素、窒化珪素、水酸化マグネシウム、水酸化アルミニウム、金、銀、銅、白金、鉄、錫、鉛、ニッケル、アルミニウム、マグネシウム、タングステン、モリブデン、ステンレスなどの無機充填材および金属充填材であってもよい。が挙げられる。充填材の形状としては、球状、無定形、繊維状、棒状、筒状、板状などが挙げられる。充填財の形状は、重合性液晶化合物が液晶相を発現した際の配向を妨げない形状のものが好ましい。充填材の種類、形状、大きさ、添加量などは、目的に応じて適宜選択できる。得られる放熱部材が絶縁性を必要とする場合、所望の絶縁性が保たれれば導電性を有する充填材であっても構わない。
例えば、板状結晶の窒化ホウ素を用いると、板状構造が液晶化合物の配向に沿って配置され易い、または液晶化合物が板状構造に沿って配向され易いため好ましい。
なお、本明細書において平均粒径とは、レーザー回折・散乱法による粒度分布測定に基づく。すなわち、フランホーファー回折理論およびミーの散乱理論による解析を利用して、湿式法により、粉体をある粒子径から2つに分けたとき、大きい側と小さい側が等量(体積基準)となる径をメジアン径とした。
充填材の量は、硬化後の放熱部材中が20~95重量%の充填材を含有するようにすることが好ましい。より好ましくは、50~95重量%である。20重量%以上であると熱伝導率が高くなり好ましい。95重量%以下であると放熱部材が脆くならず好ましい。
カップリング剤は、オキシラニル基等または硬化剤と反応することが好ましいので、アミン系もしくはオキシラニル基等を末端にもつものが好ましい。たとえば、JNC(株)製では、サイラエースS310,S320,S330,S360,S510,S530などが挙げられる。なお、カップリング剤による修飾は、多ければ多いほど結合が増えるため好ましい。
重合性液晶化合物は、上記式(1-1)で示す化合物が好ましい。しかし、それ以外の重合性液晶化合物であってもよく、液晶性の無い重合性化合物であってもよい。重合性液晶化合物等による表面修飾は、多ければ多いほど結合が増えるため好ましい。
本願の放熱部材用組成物(1)は、上記化合物(1-1)を少なくとも1種含み、高熱伝導無機充填材としての無機フィラーと複合させた物である。該組成物(1)は、2種以上の化合物(1-1)で構成されていてもよく、また、少なくとも1種の化合物(1-1)と、化合物(1-1)以外の少なくとも1種の化合物との組み合わせで構成されていてもよい。このような化合物(1-1)以外の構成要素としては、特に限定されないが、たとえば、化合物(1-1)以外の重合性化合物(以下「その他の重合性化合物」ともいう)、非重合性の液晶性化合物、重合開始剤、および溶媒などが挙げられる。
放熱部材用組成物(1)は、その他の重合性化合物を構成要素としてもよい。このような重合性化合物としては、膜形成性および機械的強度を低下させない化合物が好ましい。この重合性化合物は、液晶性を有しない化合物と液晶性を有する化合物とに分類される。液晶性を有しない重合性化合物としては、ビニル誘導体、スチレン誘導体、(メタ)アクリル酸誘導体、ソルビン酸誘導体、フマル酸誘導体、イタコン酸誘導体などが挙げられる。
放熱部材用組成物(1)は、重合性基を有しない液晶性化合物を構成要素としてもよい。このような非重合性の液晶性化合物の例は、液晶性化合物のデータベースであるリクリスト(LiqCryst, LCIPublisher GmbH, Hamburg, Germany)などに記載されている。非重合性の液晶性化合物を含有する該組成物(1)を重合させることによって、化合物(1-1)の重合体と液晶性化合物との複合材料(composite materials)を得ることができる。このような複合材料では、たとえば、高分子分散型液晶のような高分子網目中に非重合性の液晶性化合物が存在している。
放熱部材用組成物(1)は重合開始剤を構成要素としてもよい。重合開始剤は、該組成物(1)の重合方法に応じて、たとえば光ラジカル重合開始剤、光カチオン重合開始剤、熱ラジカル重合開始剤などを用いればよい。
放熱部材用組成物(1)は溶媒を含有してもよい。該組成物(1)の重合は溶媒中で行っても、無溶媒で行ってもよい。溶媒を含有する該組成物(1)を基板上に、たとえばスピンコート法などにより塗布した後、溶媒を除去してから光重合させてもよい。また、光硬化後適当な温度に加温して熱硬化により後処理を行ってもよい。
なお、重合時の溶媒の使用割合を限定することにはあまり意味がなく、重合効率、溶媒コスト、エネルギーコストなどを考慮して、個々のケースごとに決定すればよい。
上記化合物(1-1)および放熱部材用組成物(1)は高い重合性を有するので、取扱いを容易にするために、安定剤を添加してもよい。このような安定剤としては、公知のものを制限なく使用でき、たとえば、ハイドロキノン、4-エトキシフェノールおよび3,5-ジ-t-ブチル-4-ヒドロキシトルエン(BHT)などが挙げられる。
さらに、放熱部材用組成物の粘度や色を調整するために添加剤(酸化物等)を添加してもよい。例えば、白色にするための酸化チタン、黒色にするためのカーボンブラック、粘度を調整するためのシリカの微粉末を挙げることができる。また、機械的強度をさらに増すために添加剤を添加してもよい。例えば、ガラス、カーボンファイバーなどの無機繊維やクロス、または高分子添加剤として、ポリビニルホルマール、ポリビニルブチラール、ポリエステル、ポリアミド、ポリイミドなどの繊維または長分子を挙げることができる。
本発明の第2の実施の形態に係る放熱部材は、上記第1の実施の形態に係る放熱部材用組成物を硬化させた硬化物(重合体(1))を用途に応じて成形したものである。
重合体(1)は、少なくとも1種の化合物(1)を含む放熱部材用組成物(1)を、配向制御して重合させることによって得られる。この重合体(1)は、高い熱伝導性を有するとともに、透水性、吸水性およびガス透過度が低く、化学的安定性、耐熱性、硬度および機械的強度などに優れている。なお、前記機械的強度とは、ヤング率、引っ張り強度、引き裂き強度、曲げ強度、曲げ弾性率、衝撃強度などである。
図1は、充填材として窒化ホウ素を用いた場合の放熱部材のイメージ図である。
熱硬化性樹脂は三次元の架橋構造を有する。このような重合体(1)は溶媒に不溶であるので、分子量を測定することができない。しかし、基板上に放熱部材用組成物(1)を塗布し、分子の配向を固定して重合することにより放熱部材を得る場合においては、さらに加工を施すことがないので、分子量の大小は問題とならず、使用環境において条件を満足すればよい。また、より分子量を上げるために、架橋剤を添加してもよい。これにより、耐薬品性および耐熱性に極めて優れた重合体(1)を得ることができる。このような架橋剤としては、公知のものを制限なく使用できるが、たとえば、トリス(3-メルカプトプロピオネート)などが挙げられる。
単離した重合体(1)は、溶媒に溶かして配向処理基板上で配向させフィルムなどに加工してもよく、2つの重合体を混合して加工してもよく、複数の重合体を積層させてもよい。前記溶媒としては、たとえば、N-メチル-2-ピロリドン、ジメチルスルホキシド、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミドジメチルアセタール、テトラヒドロフラン、クロロホルム、1,4-ジオキサン、ビス(メトキシエチル)エーテル、γ-ブチロラクトン、テトラメチル尿素、トリフルオロ酢酸、トリフルオロ酢酸エチル、ヘキサフルオロ-2-プロパノール、2-メトキシエチルアセテート、メチルエチルケトン、シクロペンタノン、シクロヘキサノンなどが好ましい。これらは、アセトン、ベンゼン、トルエン、ヘプタン、塩化メチレンなど一般的な有機溶媒と混合して用いてもよい。
以下、放熱部材用組成物(1)および放熱部材を製造する方法について具体的に説明する。
<カップリング処理を施す場合>
カップリング剤で処理された充填材を用いる場合は、充填材にカップリング処理を施す。カップリング処理は、公知の方法を用いることができる。
一例として、まず充填材粒子とカップリング剤を溶媒に加える。スターラー等を用いて撹拌したのち、放置する。溶媒乾燥後に、真空乾燥機等を用いて、真空条件下で加熱処理をする。この充填材粒子に溶媒を加えて、超音波処理により粉砕する。遠心分離機を用いてこの溶液を分離精製する。上澄みを捨てたのち、溶媒を加えて同様の操作を数回行う。オーブンを用いて精製後の充填材粒子を乾燥させる。
次にカップリング処理された充填材粒子と重合性液晶化合物を、メノウ乳鉢等を用いて混合したのち、2軸ロール等を用いて混練する。その後、超音波処理および遠心分離によって分離精製する。
さらにアミン系硬化剤と、メノウ乳鉢等を用いて混合したのち、2軸ロール等を用いて混練する。これにより、溶媒を含有しない放熱部材用組成物(1)を得ることができる。
<放熱部材の製造>
一例として、溶媒を含有しない放熱部材用組成物(1)を用いて、放熱部材としてのフィルムを製造する方法について具体的に説明する。
溶媒を含有しない放熱部材用組成物(1)を、圧縮成形機を用いて加熱板中にはさみ、圧縮成形により配向成形する。重合性液晶化合物は、液晶相を示す温度範囲以上で重合させて、重合体を形成する。さらに適切な時間、温度で後硬化を施してもよい。なお、圧縮成形時の圧力は、50~200kgf/cm2が好ましく、より好ましくは70~180kgf/cm2である。硬化時の圧力は基本的には高い方が好ましい。しかし、金型の流動性や、目的とする物性(どちら向きの熱伝導率を重視するかなど)によって適宜変更し、適切な圧力を加えることが好ましい。
まず、基板上に該組成物(1)を塗布し、溶媒を乾燥除去して膜厚の均一な塗膜層を形成する。塗布方法としては、たとえば、スピンコート、ロールコート、カテンコート、フローコート、プリント、マイクログラビアコート、グラビアコート、ワイヤーバーコード、デップコート、スプレーコート、メニスカスコート法などが挙げられる。
本発明の放熱部材は、放熱板、放熱シート、放熱フィルム、放熱接着材、放熱成形品などに有用である。
本発明の第3の実施の形態に係る電子機器は、上記第2の実施の形態に係る放熱部材と、発熱部を有する電子デバイスとを備える。放熱部材は、前記発熱部に接触するように電子デバイスに配置される。放熱部材の形状は、放熱板、放熱シート、放熱フィルム、放熱接着材、放熱成形品などのいずれであってもよい。
例えば、電子デバイスとして、半導体素子を挙げることができる。本願の放熱部材は、高熱伝導性に加えて、高耐熱性、高絶縁性を有する。そのため、半導体素子の中でも高電力のためより効率的な放熱機構を必要とする絶縁ゲートバイポーラトランジスタ(Insulated Gate Bipolar Transistor、IGBT)に特に有効である。IGBTは半導体素子のひとつで、MOSFETをゲート部に組み込んだバイポーラトランジスタであり、電力制御の用途で使用される。IGBTを備えた電子機器には、大電力インバータの主変換素子、無停電電源装置、交流電動機の可変電圧可変周波数制御装置、鉄道車両の制御装置、ハイブリッドカー、エレクトリックカーなどの電動輸送機器、IH調理器などを挙げることができる。
<重合性液晶化合物>
・液晶性エポキシ:下記式(4-1)(JNC(株)製)
なお、特許第5084148号公報に記載の方法で合成することができる。
・エポキシ:jER828(三菱化学(株)製)
<硬化剤>
・アミン系硬化剤1:4,4’-ジアミノ-1,2-ジフェニルエタン(和光純薬工業(株)製
・アミン系硬化剤2:4,4’-ジアミノ-1,2-ジフェニルメタン(和光純薬工業(株)製)
・アミン系硬化剤3:jER113(三菱化学(株)製)
・アミン系硬化剤4:EDR148(三井化学ファイン(株)製)
<充填材>
・窒化ホウ素:h-BN粒子(モメンティブ・パフォーマンス・マテリアルズ・ジャパン(合)製、(商品名)PolarTherm PTX―25)
<シランカップリング剤>
・オクタデシルトリエトキシシラン(アヅマックス(株)製)
・3-アミノプロピルトリメトキシシラン(信越化学(株)製、(商品名)KBM-903)
以下に、放熱部材の調製例を示す(下記分量は実施例35、36に該当する)。
・カップリング剤処理窒化ホウ素粒子の準備
窒化ホウ素粒子(PTX25、以下BNと略記)5.0gと3-アミノプロピルトリメトキシシラン0.75gをトルエン(無水)50mLに加え、スターラーを用いて750rpmで1時間攪拌し、得られた混合物を40℃で5時間、室温で19時間乾燥した。さらに、溶媒乾燥後に125℃に設定した真空乾燥機を用いて真空条件下で5時間加熱処理した。
このカップリング剤で修飾したBN粒子をサンプル管に移してTHF(ナカライテスク(株)製)50mLを加えたのち、超音波処理(BRANSON(株)製MODEL450)により粉砕した。さらに、この溶液を遠心分離機(日立工機(株)製CT6E)を用いて6000rpmで10分間分離精製した。上澄み液を捨てたのち、アセトンを50mL加えて同様の操作を二回行った。精製後の修飾BN粒子を60℃のオーブン中で24時間乾燥した。
このカップリング剤処理BN粒子と液晶性エポキシを、それぞれ2gと4g(BNの配合比が19vol%)薬包紙上に測りとり、乳鉢を用いて混合したのち、2軸ロール(日東反応機(株)製HR-3)を用いて120℃で10分混練した。その後、超音波処理および遠心分離によって分離精製し、未反応成分を取り除いたカップリング剤修飾BN粒子を得た。また被覆量は、作製したカップリング剤修飾BN粒子をTG-DTA装置(セイコーインスツル(株)製EXSTAR TG/DTA5200)を用いて、その600℃における加熱減量から算出した。
作製したシランカップリング剤修飾BN粒子と液晶性エポキシと、アミン系硬化剤1(DDET)を、それぞれ4.38gと0.34gと0.1gをメノウ乳鉢で混合したのち、2軸ロールを用いて55℃で10分間混練した。
得られた混合物をステンレス製板中にはさみ、150℃に設定した圧縮成形機((株)神藤金属工業所製F-37)を用いて9.8MPaまで加圧し、15分間加熱状態を続けることで、配向処理と前硬化をおこなった。すなわちステンレス板の間を混合物が広がる際に、広がり方向に液晶性エポキシが配向する。また、試料の厚みは約200μmになるように、試料の量を調整した。さらに、オーブンを用いて80℃で1時間、150℃で3時間の後硬化をおこない目的とする、本発明の放熱部材とした。
熱伝導率は、予め放熱部材の比熱(セイコーインスツル(株)製DSC型入力補償型示差走査熱量測定装置EXSTAR6000で測定した。)と比重(メトラー・トレド製比重計AG204密度測定キットにより測定した。)を求めておき、その値をアルバック理工(株)製TC7000熱拡散率測定装置により求めた熱拡散率を掛け合わせることにより熱伝導率を求めた。なお、厚み方向の熱拡散率は、試料をカーボンスプレーを用いて黒化処理し、標準のサンプルホルダーを用いて測定した。また、平面方向の熱拡散率は、レーザーを照射するスポットと、赤外線を検出するスポットの間を5mm離すアダプターを作製し、試料にレーザーが照射されて赤外線が出るまでの時間と、その距離から算出した。
また、図3、4に未修飾のBN粒子の体積分率と熱伝導率の関係をグラフで示す。図3、4において、(a)はx-y方向の熱伝導率であり、(b)は厚み方向の熱伝導率である。
また、実施例1において液晶性エポキシの代わりにビスフェノール型エポキシ(jER828)を使用して、同様な評価をおこなったところ(比較例1)、x-y方向の熱伝導率は14.5W/mKしかなかった。
また、図3にBN粒子の体積分率と熱伝導率の関係をグラフで示す。図3において、(a)はx-y方向の熱伝導率であり、(b)は厚み方向の熱伝導率である。
また、図4にBN粒子の体積分率と熱伝導率の関係をグラフで示す。図4において、(a)はx-y方向の熱伝導率であり、(b)は厚み方向の熱伝導率である。
また、図4にBN粒子の体積分率と熱伝導率の関係をグラフで示す。図4において、(a)はx-y方向の熱伝導率であり、(b)は厚み方向の熱伝導率である。
図4(b)に示すとおり、厚み方向の熱伝導率は、未修飾窒化ホウ素粒子を用いた放熱部材よりも、カップリング修飾または表面修飾窒化ホウ素粒子を用いた放熱部材の方が高い。これは、高せん断時に修飾窒化ホウ素粒子の周囲の修飾分子が液晶高分子の流動配向を阻害し、修飾窒化ホウ素粒子に厚み方向の力が働き、厚み方向の熱伝導率を向上させたためと考えられる。
ジアミンをアミン系硬化剤1から、アミン系硬化剤2~4に変更して放熱部材を調製したところ、一部試料で気泡が入ってしまい、密度を測定できなかったので熱拡散率での評価とした(実施例51-53、比較例2)。硬化剤に式(3-1)で示すようなジアミンを用いるほうが、放熱性が高くなる結果となった。
2 無機フィラー、窒化ホウ素
Claims (9)
- オキシラニル基またはオキセタニル基を含む構造を両末端に有する重合性液晶化合物と;
前記重合性液晶化合物を硬化させる硬化剤と;
窒化物で形成された無機フィラーとを含み;
硬化温度は、前記重合性液晶化合物が液晶相を示す温度範囲以上、等方相を示す温度範囲以下である、
放熱部材用組成物。 - 前記重合性液晶化合物は、下記式(1-1)で表される少なくとも1種の化合物である、
請求項1に記載の放熱部材用組成物。
Ra1-Z-(A-Z)m1-Ra1 ・・・(1-1)
[上記式(1-1)中、
Ra1は、それぞれ下記式(2-1)~(2-2)のいずれかで表される重合性基であり;
Aは、1,4-シクロヘキシレン、1,4-シクロヘキセニレン、1,4-フェニレン、ナフタレン-2,6-ジイル、テトラヒドロナフタレン-2,6-ジイル、フルオレン-2,7-ジイル、ビシクロ[2.2.2]オクト-1,4-ジイル、またはビシクロ[3.1.0]ヘキス-3,6-ジイルであり、
これらの環において、任意の-CH2-は、-O-で置き換えられてもよく、任意の-CH=は、-N=で置き換えられてもよく、任意の水素は、ハロゲン、炭素数1~10のアルキル、または炭素数1~10のハロゲン化アルキルで置き換えられてもよく、
該アルキルにおいて、任意の-CH2-は、-O-、-CO-、-COO-、または-OCO-で置き換えられてもよく、任意の-CH2CH2-は、-CH=CH-、または-C≡C-で置き換えられてもよく;
Zは、それぞれ単結合、または炭素数1~20のアルキレンであり、
該アルキレンにおいて、任意の-CH2-は、-O-、-S-、-CO-、-COO-、または-OCO-で置き換えられてもよく、任意の-CH2CH2-は、-CH=CH-、-CF=CF-、-CH=N-、-N=CH-、-N=N-、-N(O)=N-、または-C≡C-で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく;
m1は、1~6の整数である。]
- 上記式(1-1)中、Aは、1,4-シクロヘキシレン、任意の水素がハロゲンで置き換えられた1,4-シクロヘキシレン、1,4-フェニレン、任意の水素がハロゲンもしくはメチル基で置き換えられた1,4-フェニレン、フルオレン-2,7-ジイル、または任意の水素がハロゲンもしくはメチル基で置き換えられたフルオレン-2,7-ジイルである、
請求項2に記載の放熱部材用組成物。 - 請求項2に記載の上記式(1-1)中、Zは、単結合、-(CH2)a-、-O(CH2)a-、-(CH2)aO-、-O(CH2)aO-、-CH=CH-、-C≡C-、-COO-、-OCO-、-CH=CH-COO-、-OCO-CH=CH-、-CH2CH2-COO-、-OCO-CH2CH2-、-CH=N-、-N=CH-、-N=N-、-OCF2-または-CF2O-であり、該aが1~20の整数である、
請求項3に記載の放熱部材用組成物。 - 前記無機フィラーは、窒化ホウ素、窒化アルミニウム、および窒化珪素から選ばれる少なくとも一つである、
請求項1~請求項4のいずれか1項に記載の放熱部材用組成物。 - 前記硬化剤は、下記式(3-1)で表される少なくとも1種のジアミン化合物である、
請求項1~請求項5のいずれか1項に記載の放熱部材用組成物。
H2N-Z-(A-Z)m2-NH2 ・・・(3-1)
[上記式(3-1)中、
Aは、1,4-シクロヘキシレン、または1,4-フェニレンであり、これらの環の任意の水素は、ハロゲン、または炭素数1~10のアルキルで置き換えられてもよく;
Zは、それぞれ単結合、または炭素数1~10のアルキレンであり;
m2は1~7の整数である。] - 前記無機フィラーは、カップリング剤により処理されたフィラー、または、カップリング処理された後、前記重合性液晶化合物により表面修飾されたフィラーである、
請求項1~請求項6のいずれか1項に記載の放熱部材用組成物。 - 請求項1~請求項7のいずれか1項に記載の放熱部材用組成物を、配向処理をおこなった後、硬化させて得られる、
前記無機フィラーを20~95重量%含有する、
放熱部材。 - 請求項8に記載の放熱部材と;
発熱部を有する電子デバイスとを備え;
前記放熱部材が前記発熱部に接触するように前記電子デバイスに配置された;
電子機器。
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Also Published As
Publication number | Publication date |
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CN106459736B (zh) | 2020-04-07 |
US9938371B2 (en) | 2018-04-10 |
EP3141589A1 (en) | 2017-03-15 |
EP3141589A4 (en) | 2018-05-02 |
JPWO2015170744A1 (ja) | 2017-04-20 |
US20170137561A1 (en) | 2017-05-18 |
CN106459736A (zh) | 2017-02-22 |
JP6653793B2 (ja) | 2020-02-26 |
TW201546166A (zh) | 2015-12-16 |
TWI658091B (zh) | 2019-05-01 |
KR20170008212A (ko) | 2017-01-23 |
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