CN102337006B - Resin composition, B stage sheet, metal foil with resin, metal substrate, and LED substrate - Google Patents

Resin composition, B stage sheet, metal foil with resin, metal substrate, and LED substrate Download PDF

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Publication number
CN102337006B
CN102337006B CN201110189110.3A CN201110189110A CN102337006B CN 102337006 B CN102337006 B CN 102337006B CN 201110189110 A CN201110189110 A CN 201110189110A CN 102337006 B CN102337006 B CN 102337006B
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China
Prior art keywords
aluminum oxide
aforementioned
resin
epoxy resin
resol
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Expired - Fee Related
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CN201110189110.3A
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CN102337006A (en
Inventor
天沼真司
小林雄二
田仲裕之
原直树
吉原谦介
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Resonac Corp
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Hitachi Chemical Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention provides a resin composition, a B stage sheet, a metal foil with resin, a metal substrate, and an LED substrate. The resin composition includes 2-functional epoxy resin with a biphenyl structure, a phenolic resin, a first aluminium oxide group with a grain diameter D50 from 7mum to 25mum, from a small grain diameter side, corresponding to 50% accumulation, a second aluminium oxide group with the grain diameter D50 from 1mum to 7mum and a third aluminium oxide group with the grain diameter D50 smaller than 1mum. A ratio of the phenolic resin to the epoxy resin is from 1.00 to 1.25 in terms of a equivalent standard.

Description

Resin combination, B rank sheet material, tinsel, metal substrate and LED substrate
Technical field
The present invention relates to a kind of resin combination, B rank sheet material (B stage sheet), the tinsel with resin, metal substrate and LED substrate.
Background technology
Along with the densification of e-machine, the carrying out of densification, the heat release of the electronic units such as semi-conductor becomes large problem.Therefore, require to have the resin combination of high thermal conductivity coefficient and high electric insulation, and using it as heat conductivity sealing material, thermal conductive adhesive carries out actual use.
With above-mentioned relevant, in TOHKEMY 2008-13759 communique, disclose and shown the epoxy resin of liquid crystal liquid crystal property and the composition epoxy resin of alumina powder a kind of comprising, think that it has high thermal conductivity coefficient and excellent processibility.
Summary of the invention
The problem that invention will solve
Yet, for the composition epoxy resin of recording in TOHKEMY 2008-13759 communique, sometimes cannot obtain sufficient electrical insulating property.
The problem to be solved in the present invention is to provide a kind of resin combination that can form the resin cured matter with high thermal conductivity coefficient and high electric insulation, and uses the formed B of this resin combination rank sheet material, the tinsel with resin, metal substrate and LED substrate.
The method of dealing with problems
The present invention comprises following mode.
<1> resin combination, it contains 2 officials' energy epoxy resin with biphenyl backbone, resol, from the small particle size side of weight build-up size-grade distribution, accumulation 50% corresponding particle diameter D50 is more than 7 μ m the 1st aluminum oxide group below 25 μ m, aforementioned particle size D50 is that 1 μ m is above and less than the 2nd aluminum oxide group of 7 μ m, and aforementioned particle size D50 is the 3rd aluminum oxide group less than 1 μ m, aforementioned resol contains ratio (resol/epoxy resin) with respect to epoxy resin total content, in equivalent benchmark, be more than 1.00 below 1.25.
The resin combination of <2> as described in aforementioned <1>, wherein aforementioned resol has the represented structural unit of following general formula (I).
(in general formula (I), R 1represent alkyl, aryl or aralkyl, R 2and R 3represent independently of one another hydrogen atom, alkyl, aryl or aralkyl, m represents 0～2 integer, and n represents 1～7 integer)
The resin combination of <3> as described in aforementioned <1> or <2>, wherein aforementioned 2 officials with biphenyl backbone can comprise the represented compound of following general formula (III) by epoxy resin.
(in general formula (III), R 1～R 8represent that independently of one another hydrogen atom or carbonatoms are 1～10 alkyl, n represents 0～3 integer)
<4> resin combination, it contains 2 officials' energy epoxy resin with biphenyl backbone, resol, from the small particle size side of weight build-up size-grade distribution, accumulation 50% corresponding particle diameter D50 is more than 7 μ m the 1st aluminum oxide group below 25 μ m, aforementioned particle size D50 is that 1 μ m is above and less than the 2nd aluminum oxide group of 7 μ m, and aforementioned particle size D50 is the 3rd aluminum oxide group less than 1 μ m, aforementioned the 1st aluminum oxide group, in the 2nd aluminum oxide group and the 3rd aluminum oxide group's total mass, aforementioned the 1st aluminum oxide group's containing ratio is below the above 70 quality % of 60 quality %, aforementioned the 2nd aluminum oxide group's containing ratio is below the above 30 quality % of 15 quality %, aforementioned the 3rd aluminum oxide group's containing ratio is below the above 25 quality % of 1 quality %, aforementioned the 2nd aluminum oxide faciation contains ratio (the 2nd aluminum oxide group/3rd aluminum oxide group) for aforementioned the 3rd aluminum oxide group's, in quality criteria, be more than 1.2 below 1.7.
The resin combination of <5> as described in aforementioned <4>, wherein aforementioned the 1st aluminum oxide faciation contains ratio (the 1st aluminum oxide group/2nd aluminum oxide group) for aforementioned the 2nd aluminum oxide group, in quality criteria, be more than 2.0 below 5.0.
<6> is by the formed B of the semicure resin combination rank sheet material that comes from the resin combination described in aforementioned <1>～<5> any one.
<7> tinsel with resin, it has tinsel and is configured in the semicure resin layer that comes from the resin combination described in aforementioned <1>～<5> any one on aforementioned metal paper tinsel.
<8> metal substrate, it has metal support, be configured in the curing resin layer that comes from the resin combination described in aforementioned <1>～<5> any one on aforementioned metal support and be configured in the tinsel on aforementioned curing resin layer.
<9> LED substrate, it has metal support, be configured in the curing resin layer that comes from the resin combination described in aforementioned <1>～<5> any one on aforementioned metal support, be configured on aforementioned curing resin layer by the formed circuit layer of tinsel and be configured in the LED element on aforementioned circuit layer.
Invention effect
According to the present invention, a kind of resin combination that can form the resin cured matter with high thermal conductivity coefficient and high electric insulation can be provided, and use the formed B of this resin combination rank sheet material, the tinsel with resin, metal substrate and LED substrate.
Accompanying drawing explanation
[Fig. 1] means the general profile chart of an example of the LED substrate in the present invention.
[Fig. 2] means the stereographic map of an example of the LED substrate in the present invention.
Embodiment
In this manual, term " operation ", not only comprises independently operation, and in the time cannot clearly distinguishing with other operation, as long as reached the predictive role of this operation, is just included in this term.
In addition, in this manual, use "～" represented numerical range, represent to comprise the described numerical value in "～" front and back respectively as minimum value and peaked scope.
Further, in this manual, in mentioning composition during the amount of each composition, while there is a plurality of material that is equivalent to each composition in composition, unless otherwise specified, represent the total amount of the plurality of material that exists in composition.
< resin combination >
Resin combination of the present invention contain there are 2 officials of biphenyl backbone can epoxy resin, resol, from the small particle size side of weight build-up size-grade distribution, accumulation 50% corresponding particle diameter D50 is that more than 7 μ m the 1st aluminum oxide group, the aforementioned particle size D50 below 25 μ m is more than 1 μ m and is the 3rd aluminum oxide group less than 1 μ m less than the 2nd aluminum oxide group and the aforementioned particle size D50 of 7 μ m, aforementioned resol contains ratio (resol/epoxy resin) with respect to epoxy resin total content, in equivalent benchmark, be more than 1.00 below 1.25.
Further, resin combination of the present invention, except above-mentioned neccessary composition, can also contain as required except having other epoxy resin can epoxy resin of 2 officials of biphenyl backbone, other composition and form.
At least 3 kinds of aluminum oxide that differ from one another by containing particle diameter D50, and resol is specific scope with respect to the ratio that contains of epoxy resin total content, can realize high thermal conductivity coefficient and high electric insulation.In addition, aforementioned resin, when for example forming B rank sheet material, has demonstrated excellent sheet material flexible.
In the present invention, resol is with respect to the ratio that contains of epoxy resin total content, in equivalent benchmark, is more than 1.00 below 1.25, from the viewpoint of thermal conductivity and electrical insulating property, considers, is preferably more than 1.00 below 1.22.
In addition, the equivalent benchmark in the present invention represents to take epoxy radix contained in epoxy resin and the hydroxyl value of the resol that reacts at 1: 1 with this epoxy group(ing) is benchmark, regulation epoxy resin and resol contain ratio.
In addition, the total content of epoxy resin refers to that aforementioned 2 officials with biphenyl backbone can epoxy resin and the aforementioned total content with 2 officials' energy epoxy resin other epoxy resin in addition of biphenyl backbone.
In addition, above-mentioned equivalent benchmark contain ratio, specifically, by following formula, calculated.
Formula: contain ratio (resol/epoxy resin)=∑ (the phenol equivalent of resol amount/resol)/∑ (epoxy equivalent (weight) of amount of epoxy/epoxy resin)
In addition, resin combination of the present invention contains 2 officials' energy epoxy resin with biphenyl backbone, resol, from the small particle size side of weight build-up size-grade distribution, accumulation 50% corresponding particle diameter D50 is more than 7 μ m the 1st aluminum oxide group below 25 μ m, aforementioned particle size D50 is that 1 μ m is above and less than the 2nd aluminum oxide group of 7 μ m, and aforementioned particle size D50 is the 3rd aluminum oxide group less than 1 μ m, at aforementioned the 1st aluminum oxide, in the 2nd aluminum oxide group and the 3rd aluminum oxide group's total mass, aforementioned the 1st aluminum oxide group's containing ratio is below the above 70 quality % of 60 quality %, aforementioned the 2nd aluminum oxide group's containing ratio is below the above 30 quality % of 15 quality %, aforementioned the 3rd aluminum oxide group's containing ratio is below the above 25 quality % of 1 quality %, aforementioned the 2nd aluminum oxide faciation contains ratio (the 2nd aluminum oxide group/3rd aluminum oxide group) for aforementioned the 3rd aluminum oxide group's, in quality criteria, be more than 1.2 below 1.7.
Further, resin combination of the present invention, except above-mentioned neccessary composition, can also contain as required other composition and form.
Because the contained aluminum oxide of resin combination has specific size distribution, the aluminium oxide particles with different-grain diameter plugs the gap mutually each other, thereby has filled aluminum oxide to high-density.In addition, by containing 2 officials' energy epoxy resin and the resol with biphenyl backbone, can realize high thermal conductivity coefficient and high electric insulation.Further, aforementioned resin, when for example forming B rank sheet material, has demonstrated excellent sheet material flexible.
Further, aforementioned resin preferably contains 2 officials' energy epoxy resin with biphenyl backbone, resol, from the small particle size side of weight build-up size-grade distribution, accumulation 50% corresponding particle diameter D50 is more than 7 μ m the 1st aluminum oxide group below 25 μ m, aforementioned particle size D50 is that 1 μ m is above and less than the 2nd aluminum oxide group of 7 μ m, and aforementioned particle size D50 is the 3rd aluminum oxide group less than 1 μ m, at aforementioned the 1st aluminum oxide, in the 2nd aluminum oxide group and the 3rd aluminum oxide group's total mass, aforementioned the 1st aluminum oxide group's containing ratio is below the above 70 quality % of 60 quality %, aforementioned the 2nd aluminum oxide group's containing ratio is below the above 30 quality % of 15 quality %, aforementioned the 3rd aluminum oxide group's containing ratio is below the above 25 quality % of 1 quality %, aforementioned the 2nd aluminum oxide faciation contains ratio (the 2nd aluminum oxide group/3rd aluminum oxide group) for aforementioned the 3rd aluminum oxide group's, in quality criteria, be more than 1.2 below 1.7, aforementioned resol contains ratio (resol/epoxy resin) with respect to epoxy resin total content, in equivalent benchmark, be more than 1.00 below 1.25.
Because aluminum oxide contained in resin combination has specific size distribution, and resol is specific scope with respect to the ratio that contains of epoxy resin total content, can realize more excellent thermal conductivity and the electrical insulating property of Geng Gao.Further, aforementioned resin, when for example forming B rank sheet material, present excellent sheet material outward appearance, and it is flexible to have demonstrated excellent sheet material.
[epoxy resin]
Resin combination of the present invention contains and has at least a kind that 2 officials of biphenyl backbone can epoxy resin.Aforementioned epoxy resins so long as contain at least 1 biphenyl backbone and have the compound of 2 epoxy group(ing), is just not particularly limited.
Specifically, for example, can enumerate biphenyl type epoxy resin or biphenylene type epoxy resin.
As aforementioned biphenyl type epoxy resin, can enumerate the represented epoxy resin of following general formula (III) etc.
[changing 3]
In general formula (III), R 1～R 8represent that independently of one another hydrogen atom or carbonatoms are 1～10 replacement or unsubstituted alkyl, n represents 0～3 integer.
The replacement that is 1～10 as carbonatoms or unsubstituted alkyl, can enumerate methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-etc.
Wherein, from the viewpoint of heat conductivity, consider R 1～R 8be preferably hydrogen atom or methyl.
As the represented biphenyl type epoxy resin of above-mentioned general formula (III), can enumerate with 44 '-bis-(2,3-epoxy group(ing) propoxy-) biphenyl or 4,4 '-bis-(2,3-epoxy group(ing) propoxy-)-3,3 ', 5, the epoxy resin that 5 '-tetramethyl biphenyl is principal constituent, make Epicholorohydrin and 4,4 '-bis-phenol or 4,4 '-(3,3 ', 5,5 '-tetramethyl-) epoxy resin of bis-phenol reaction gained etc.Wherein, the viewpoint consideration declining from suppressing the second-order transition temperature of cured article, preferably with 4,4 '-bis-(2,3-epoxy group(ing) propoxy-)-3,3 ', 5, the epoxy resin that 5 '-tetramethyl biphenyl is principal constituent.As this compound, YX-4000 (japan epoxy resin Co., Ltd. system), YL-6121H (japan epoxy resin Co., Ltd. system), YSLV-80XY (Toto Kasei KK's system) etc. can obtain as commodity.
In addition,, as aforementioned biphenylene type epoxy resin, can enumerate the represented epoxy resin of following general formula (IV) etc.
In general formula (IV), R 1～R 9represent independently of one another the aralkyl that alkyl that hydrogen atom, carbonatoms are 1～10, alkoxyl group that carbonatoms is 1～10, aryl that carbonatoms is 6～10 or carbonatoms are 6～10, n represents 0～10 integer.
The alkyl that is 1～10 as aforementioned carbonatoms, can enumerate methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-etc.The alkoxyl group that is 1～10 as carbonatoms, can enumerate methoxyl group, oxyethyl group, propoxy-, butoxy etc.The aryl that is 6～10 as carbonatoms, can enumerate phenyl, tolyl, xylyl etc.In addition, the aralkyl that is 7～10 as carbonatoms, can enumerate benzyl, styroyl etc.
Wherein, from the viewpoint that B rank sheet material is flexible, consider R 1～R 9be preferably hydrogen atom or methyl.
As the represented biphenyl type epoxy resin of above-mentioned general formula (IV), for example, NC-3000 (Nippon Kayaku K. K's trade(brand)name processed) can obtain as commodity.
As the 2 officials' energy epoxy resin with biphenyl backbone in the present invention, from the viewpoint that thermal conductivity, electrical insulating property and B rank sheet material are flexible, consider, preferably contain at least a kind of the represented compound of aforementioned formula (III) or general formula (IV), from the viewpoint of heat conductivity, consider, more preferably contain at least a kind of the represented compound of general formula (III).
As the aforementioned containing ratio with 2 officials' energy epoxy resin of biphenyl backbone in the total solids composition of resin combination of the present invention, be not particularly limited, but consider from the viewpoint that thermal conductivity, electrical insulating property and B rank sheet material are flexible, be preferably below the above 10 quality % of 3 quality %, from the viewpoint of the physical property of aftermentioned cured article, consider, more preferably below the above 7 quality % of 4 quality %.
In addition, the solids component in resin combination refers to from the composition of formation resin combination and removes the remaining composition after volatile component.
For resin combination of the present invention, can epoxy resin except aforementioned 2 officials with biphenyl backbone, can also contain other epoxy resin.As other epoxy resin, only otherwise there is biphenyl backbone, can use without particular limitation known epoxy resin in the past.
Specifically, can enumerate with phenol novolak type epoxy resin, o-cresol phenolic epoxy varnish, take that to have the epoxy resin of triphenyl methane skeleton be representative, by phenol, cresols, xylenol, Resorcinol, catechol, dihydroxyphenyl propane, the phenols such as Bisphenol F and/or naphthyl alcohol, 2-Naphthol, the aphthols such as dihydroxy naphthlene and formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, the compound that salicylic aldehyde etc. have aldehyde radical novolac resin of condensation or cocondensation gained under an acidic catalyst carries out epoxidised resin, dihydroxyphenyl propane, Bisphenol F, bisphenol S, stilbene type epoxy resin, hydroquinone type epoxy resin, by phthalic acid (acid of Off タ Le), the glycidyl ester type epoxy resin that reacts gained of the polyprotonic acids such as dimeracid and Epicholorohydrin, by diaminodiphenyl-methane, the glycidyl amine type epoxy resin that reacts gained of the polyamine such as isocyanuric acid and Epicholorohydrin, the epoxide of the cocondensation resin of Dicyclopentadiene (DCPD) and phenols, the epoxy resin with naphthalene nucleus, phenol aralkyl resin, the phenol aralkyl resin that contains biphenylene skeleton, the epoxide of the aralkyl-type phenol resin such as naphthols aralkyl resin, trimethylolpropane type epoxy resin, terpene (テ Le ペ Application) modified epoxy, with peracid such as peracetic acid, alkene key is oxidized the wire aliphatic epoxy resin of gained, cycloaliphatic epoxy resin, the epoxy resin that contains sulphur atom etc., they can use separately, also can be by two or more combination use.
The flexible viewpoint of resin combination of the present invention when forming B rank sheet material considered, preferably further contains at least a kind that is selected from the epoxy resin with naphthalene nucleus.
As the aforementioned epoxy resin with naphthalene nucleus, so long as there is the compound of at least 1 naphthalene nucleus and at least 1 epoxy group(ing), be just not particularly limited.For example, can enumerate HP4032D (Dainippon Ink Chemicals's system).
When resin combination of the present invention contains other epoxy resin (epoxy resin preferably with naphthalene nucleus), its containing ratio is not particularly limited.For example, with respect to aforementioned 2 officials' energy epoxy resin with biphenyl backbone, can be made as below the above 15 quality % of 0.01 quality %, be preferably below the above 12 quality % of 0.01 quality %.By being this containing ratio, can more effectively improve the flexible of thermal conductivity, electrical insulating property and B rank sheet material.
In addition, in the present invention, while having added other epoxy resin in aforementioned 2 officials with biphenyl backbone can epoxy resin, aforementioned resol is with respect to the ratio that contains of epoxy resin total amount, in equivalent benchmark, is more than 1.00 below 1.25.
When resin combination of the present invention contains other epoxy resin (epoxy resin preferably with naphthalene nucleus), 2 officials' energy epoxy resin and the containing than (2 officials' energy epoxy resin/other epoxy resin with biphenyl backbone) of other epoxy resin with biphenyl backbone are not particularly limited.For example, from flexible viewpoint, consider, can be made as more than 80/20, be preferably more than 90/10, more preferably more than 95/5.
[resol]
At least a kind of containing resol of resin combination of the present invention.As aforementioned resol, be not particularly limited, but preferably contain the resol of at least a kind (following, be sometimes referred to as " novolac resin ") of the compound with the represented structural unit of following general formula (I).Aforementioned resol, for example, as the solidifying agent of epoxy resin.
By containing the resol with ad hoc structure, can effectively improve thermal conductivity, further, can also fully extend the work-ing life under state before solidifying.
[changing 5]
In above-mentioned general formula (I), R 1represent alkyl, aryl or aralkyl.R 1represented alkyl, aryl and aralkyl, as possible, just can further have substituting group, as this substituting group, can enumerate alkyl, aryl, halogen atom and hydroxyl etc.
M represents 0～2 integer, when m is 2, and 2 R 1can be identical, also can be different.In the present invention, from the viewpoint of heat conductivity, consider, m is preferably 0 or 1, and more preferably 0.
In addition, n represents 1～7 integer.
Resol in the present invention is preferably the compound with the represented structural unit of above-mentioned general formula (I), and can have the represented structural unit of above-mentioned general formula of more than two kinds (I).When the resol in the present invention has the represented structural unit of above-mentioned general formula of more than two kinds (I), for this structural unit of more than two kinds, as long as its R 1～R 3, m and n any one differ from one another.
Resol in the present invention preferably contains at least a kind of compound with the represented structural unit of above-mentioned general formula (I), and can contain the compound of more than two kinds with the represented structural unit of above-mentioned general formula (I).When the resol in the present invention contains the compound of more than two kinds with the represented structural unit of above-mentioned general formula (I), this compound of more than two kinds is so long as different any situations in different with molecular weight of structural unit beyond the structural unit that the represented structural unit of general formula (I) is different, general formula (I) is represented.
Resol in the present invention is considered from the viewpoint of heat conductivity, preferably contains the part-structure coming from as the Resorcinol of phenoloid, and can further contain at least a kind of part-structure that comes from the phenoloid beyond Resorcinol.As the phenoloid beyond Resorcinol, for example, can enumerate phenol, cresols, catechol, quinhydrones etc.Aforementioned resol can contain independent a kind of part-structure that comes from them, also can combine and contain two or more.
, come from the part-structure of phenoloid herein, refer to from the phenyl ring of phenoloid and partly remove 1 valency that 1 or 2 hydrogen atoms form or the group of divalent.In addition, remove the position of hydrogen atom, be not particularly limited.
In the present invention, as the part-structure that comes from Resorcinol phenoloid in addition, from the viewpoint of thermal conductivity, cementability, storage stability, consider, be preferably to come from and be selected from phenol, cresols, catechol, quinhydrones, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene and 1,3, the part-structure of at least a kind in 5-trihydroxybenzene, more preferably comes from the part-structure of at least a kind being selected from catechol and quinhydrones.
In addition, the ratio that contains that comes from the part-structure of Resorcinol in aforementioned resol is not particularly limited, but consider from the viewpoint of thermal conductivity and storage stability, the part-structure that preferably comes from Resorcinol is more than 55 quality % with respect to the ratio that contains of resol total mass, more preferably more than 80 quality %, more preferably more than 90 quality %.
In general formula (I), R 2and R 3represent independently of one another hydrogen atom, alkyl, aryl, phenyl or aralkyl.R 2and R 3represented alkyl, phenyl, aryl and aralkyl, as possible, just can further have substituting group, as this substituting group, can enumerate alkyl, aryl, halogen atom and hydroxyl etc.
As the R in the present invention 2and R 3, from the viewpoint of storage stability and thermal conductivity, consider, be preferably hydrogen atom, alkyl or aryl, more preferably hydrogen atom, carbonatoms are 1 to 4 alkyl or phenyl, more preferably hydrogen atom.
Further, from stable on heating viewpoint, consider R 2and R 3at least one aryl more preferably.
As the resol in the present invention, specifically, be preferably the resol that contains the compound with the represented part-structure of any one of general formula shown below (Ia)～general formula (If).
In general formula (Ia)～general formula (If), i, j represent to come from each phenoloid structural unit contain ratio (quality %), i is 5～30 quality %, j is 70～95 quality %, i and j add up to 100 quality %.
Resol in the present invention is considered from the viewpoint of thermal conductivity and storage stability, the represented structural unit of any one that preferably contains general formula (Ia), general formula (Ie), and i is 5～20 quality %, j is 80～95 quality %, more preferably contain the represented structural unit of general formula (Ia), and i is 2～10 quality %, j is 90～98 quality %.
Resol in the present invention preferably contains the compound with the represented structural unit of above-mentioned general formula (I), and more preferably contains at least a kind of the represented compound of following general formula (II).
In general formula (II), R 11represent hydrogen atom or come from 1 valency group of the represented phenoloid of following general formula (IIp), R 12represent to come from 1 valency group of phenoloid.In addition R, 1, R 2, R 3, m and n, respectively with general formula (I) in R 1, R 2, R 3, m and n synonym.
R 12the represented 1 valency group that comes from phenoloid, is partly to remove from the phenyl ring of phenoloid the 1 valency group that 1 hydrogen atom forms, and the position of removing hydrogen atom, is not particularly limited.
In general formula (IIp), p represents 1～3 integer.In addition R, 1, R 2and R 3respectively with general formula (I) in R 1, R 2and R 3synonym, m represents 0～2 integer.
R 11and R 12phenoloid, so long as there is the compound of phenol hydroxyl, be just not particularly limited.Specifically, for example, can enumerate phenol, cresols, catechol, Resorcinol, quinhydrones etc.Wherein, from the viewpoint of thermal conductivity and storage stability, consider, be preferably at least a kind that is selected from cresols, catechol, Resorcinol.
As the number-average molecular weight of aforementioned resol, from the viewpoint of thermal conductivity, consider, be preferably below 800, more preferably more than 300 below 700, more preferably more than 350 below 550.
In resin combination of the present invention, the resol that contains the compound with the represented structural unit of above-mentioned general formula (I), can contain as the monomer that forms the phenoloid of resol.As form resol phenoloid monomer contain ratio (following, to be sometimes referred to as " monomer contains ratio "), be not particularly limited, be preferably 5～80 quality %, more preferably 15～60 quality %, more preferably 20～50 quality %.
By making monomer contain ratio, be more than 20 quality %, suppressed the viscosity rise of resol, and further improved the binding property of inorganic filler.In addition,, by being below 50 quality %, the crosslinking reaction in the time of can passing through to solidify, forms more highdensity higher-dimension structure, realizes excellent thermal conductivity and thermotolerance.
In addition,, as the monomer that forms the phenoloid of resol, can enumerate Resorcinol, catechol, quinhydrones, and preferably at least contain Resorcinol as monomer.
In addition, as the ratio that contains of aforementioned resol in resin combination of the present invention, as long as aforementioned resol is with respect to the ratio that contains of epoxy resin total amount, in equivalent benchmark, be more than 1.00 below 1.25, be just not particularly limited.From the viewpoint in flexible and work-ing life of thermal conductivity, electrical insulating property, B rank sheet material, consider, be preferably more than 1.00 below 1.22 that the consideration of the viewpoint of the insulativity during from moisture absorption more preferably more than 1.00 below 1.20, is particularly preferably more than 1.00 below 1.10.
Resin combination of the present invention is considered from the viewpoint of thermal conductivity and electrical insulating property, the resol of the compound that preferably contains the epoxy resin that comprises aforementioned formula (III) or the represented compound of general formula (IV) and comprise (I) the represented structural unit that there is aforementioned formula, and aforementioned resol is with respect to the ratio that contains of epoxy resin total content, in equivalent benchmark, be more than 1.00 below 1.22, the resol of the compound that more preferably contains the epoxy resin that comprises the represented compound of aforementioned formula (III) and comprise (I) the represented structural unit that there is aforementioned formula, and aforementioned resol is with respect to the ratio that contains of epoxy resin total content, in equivalent benchmark, be more than 1.00 below 1.22.
Resin combination of the present invention, except aforementioned resol, can also contain resol other solidifying agent in addition as required.As other solidifying agent, can use without particular limitation known solidifying agent in the past.Specifically, for example, can use amine is that solidifying agent, mercaptan are the potentiality solidifying agent such as the polyaddition type solidifying agent such as solidifying agent or imidazoles etc.
[aluminum oxide]
It is that more than 7 μ m the 1st aluminum oxide group, the aforementioned particle size D50 below 25 μ m is more than 1 μ m and is at least 3 kinds of aluminum oxide groups less than the 3rd aluminum oxide of 1 μ m less than the 2nd aluminum oxide group and the aforementioned particle size D50 of 7 μ m that resin combination of the present invention contains from the small particle size side of weight build-up size-grade distribution accumulation 50% corresponding particle diameter D50.Therefore, in aforementioned resin, the size distribution of contained aluminum oxide has at least 3 peaks that correspond respectively to the 1st to the 3rd aluminum oxide group.In addition, the peak area at each peak, corresponding to each aluminum oxide group's containing ratio.
In the present invention, the particle diameter D50 of aluminum oxide is used laser diffractometry to measure, and when describing weight build-up size distribution curve from small particle size side, its particle diameter that is 50% corresponding to weight build-up.
The particle size distribution that uses laser diffractometry, (for example, Beckmancoulter society system, LS230) carries out can to use laser diffraction and scattering particle size distribution device.
For aforementioned the 1st aluminum oxide group, it accumulates 50% corresponding particle diameter D50 from the small particle size side of weight build-up size-grade distribution is more than 7 μ m below 25 μ m.From the viewpoint of thermal conductivity and electrical insulating property, consider, be preferably below the above 25 μ m of 10 μ m, from keeping the viewpoint of sheet material flatness to consider, more preferably below the above 25 μ m of 15 μ m.
In addition, in aforementioned resin in the total mass of contained aluminum oxide, the 1st aluminum oxide group's containing ratio is preferably below the above 70 quality % of 60 quality %, considers, more preferably below the above 70 quality % of 62 quality % from the viewpoint of thermal conductivity and electrical insulating property.
In addition,, for aforementioned the 2nd aluminum oxide group, it accumulates 50% corresponding particle diameter D50 from the small particle size side of weight build-up size-grade distribution is more than 1 μ m and less than 7 μ m.From the viewpoint of thermal conductivity and electrical insulating property, consider, be preferably below the above 6 μ m of 2 μ m, from reduce sheet material, the viewpoint in space is considered, more preferably below the above 5 μ m of 3 μ m.
In aforementioned resin in the total mass of contained aluminum oxide, the 2nd aluminum oxide group's containing ratio is preferably below the above 30 quality % of 15 quality %, from the viewpoint of thermal conductivity and electrical insulating property, consider, more preferably below the above 27 quality % of 18 quality %, more preferably below the above 25 quality % of 18.5 quality %.
For aforementioned the 3rd aluminum oxide group, it accumulates 50% corresponding particle diameter D50 from the small particle size side of weight build-up size-grade distribution is less than 1 μ m.From the viewpoint of thermal conductivity and electrical insulating property, consider, be preferably below the above 0.8 μ m of 0.1 μ m, from reduce sheet material, the viewpoint in space is considered, more preferably below the above 0.6 μ m of 0.2 μ m.
In addition, in aforementioned resin in contained aluminum oxide total mass, the 3rd aluminum oxide group's containing ratio is preferably below the above 25 quality % of 1 quality %, from the viewpoint of thermal conductivity and electrical insulating property, consider, more preferably below the above 20 quality % of 5 quality %, more preferably below the above 18 quality % of 10 quality %.
In addition,, in the present invention, aforementioned the 2nd aluminum oxide faciation contains ratio (the 2nd aluminum oxide group/3rd aluminum oxide group) for aforementioned the 3rd aluminum oxide group's, is not particularly limited.From the viewpoint of thermal conductivity and electrical insulating property, consider, be preferably more than 1.2 below 1.7, more preferably more than 1.25 below 1.65, the viewpoint consideration in space from minimizing sheet material, more preferably more than 1.3 below 1.6.
On the other hand, aforementioned the 1st aluminum oxide faciation contains ratio (the 1st aluminum oxide group/2nd aluminum oxide group) for aforementioned the 2nd aluminum oxide group's, be not particularly limited, but consider from the viewpoint of thermal conductivity and electrical insulating property, be preferably more than 2.0 below 5.0, from reduce sheet material, the viewpoint in space is considered, more preferably more than 2.5 below 4.0.
Aluminum oxide in resin combination of the present invention is considered from the flexible viewpoint of thermal conductivity, electrical insulating property and sheet material, preferably containing the above following particle diameter D50 of 68 quality % of 60 quality % is the 1st aluminum oxide group below the above 22 μ m of 10 μ m, the above following particle diameter D50 of 27 quality % of 18 quality % is the 2nd aluminum oxide group below the above 6 μ m of 2 μ m, and 5 quality % take 20% following particle diameter D50 the 3rd aluminum oxide group below 0.8 μ m more than 0.1 μ m that improves quality, and aforementioned the 2nd aluminum oxide faciation is more than 1.25 below 1.65 for aforementioned the 3rd aluminum oxide group's the ratio that contains.
More preferably containing the above following particle diameter D50 of 65 quality % of 62 quality % is the 1st aluminum oxide group below the above 20 μ m of 15 μ m, the above following particle diameter D50 of 25 quality % of 20 quality % is the 2nd aluminum oxide group below the above 5 μ m of 3 μ m, and the above following particle diameter D50 of 15 quality % of 10 quality % is 0.2 μ m the 3rd aluminum oxide group below 0.6 μ m above, and aforementioned the 2nd aluminum oxide faciation is more than 1.3 below 1.6 for aforementioned the 3rd aluminum oxide group's the ratio that contains.
As long as the aluminum oxide in the present invention has aforesaid size distribution, its crystalline structure etc. is just not particularly limited, can be any in Alpha-alumina, beta-alumina, gama-alumina, δ-aluminum oxide, θ-aluminum oxide etc., and the aforementioned the 1st is preferably Alpha-alumina at least a kind of the 3rd aluminum oxide group, and consider from the viewpoint of heat conductivity, more preferably only by Alpha-alumina, formed.
In addition, aforementioned the 1st aluminum oxide group and the 2nd aluminum oxide group consider from the viewpoint of heat conductivity, more preferably by the formed aluminum oxide of monocrystal particle of Alpha-alumina.
On the other hand, aforementioned the 3rd aluminum oxide group is preferably Alpha-alumina, gama-alumina, δ-aluminum oxide or θ-aluminum oxide, Alpha-alumina more preferably, considers from the viewpoint of heat conductivity, more preferably by the formed aluminum oxide of monocrystal particle of Alpha-alumina.
As aforementioned the 1st to the 3rd aluminum oxide group, can from commercial goods, suitably select.In addition, can also be by by transitional alumina or form the alumina powder of transitional alumina through Overheating Treatment, in the atmosphere gas that contains hydrogenchloride, burn till (for example,, with reference to Japanese kokai publication hei 6-191833 communique, Japanese kokai publication hei 6-191836 communique etc.) and manufacture.
In resin combination of the present invention, the containing ratio of contained aluminum oxide is not particularly limited, and in forming the solids component of resin combination, can be made as below the above 95 quality % of 85 quality %, from the viewpoint that thermal conductivity, electrical insulating property and sheet material are flexible, consider, more preferably below the above 92 quality % of 88 quality %.
In addition, the solids component in resin combination refers to from the composition of formation resin combination and removes the remaining composition after volatile component.
For resin combination of the present invention, except aforementioned the 1st to the 3rd aluminum oxide group, can also contain and take aluminum oxide as principal constituent, and the equal Fibre diameter of its number is the inorganic fibre of 1 μ m～50 μ m.In the present invention, " inorganic fibre that the aluminum oxide of take is principal constituent ", refers to the inorganic fibre that contains the above aluminum oxide of 50 quality %.Wherein, be preferably the inorganic fibre that contains the above aluminum oxide of 70 quality %, more preferably contain the inorganic fibre of the above aluminum oxide of 90 quality %.The equal Fibre diameter of number of this inorganic fibre is 1 μ m～50 μ m, is preferably 1 μ m～30 μ m, more preferably 1 μ m～20 μ m.In addition, the staple length of this inorganic fibre, is generally 0.1mm～100mm.
As this inorganic fibre, conventionally use commercial goods, specifically, can enumerate Altex (ア Le テ Star Network ス) (Sumitomo Chemical Co's system), Denka alcen (デ Application カ ア Le セ Application) (Deuki Kagaku Kogyo Co., Ltd's system), Maftec bulk fiber (マ Off テ Star Network バ Le Network Off ア イ バ mono-) (Mitsubishi Chemical property Co., Ltd's system) etc.
When using this inorganic fibre, its usage quantity, with respect to aforementioned the 1st quality to the 3rd aluminum oxide group, be generally 5 quality %～70 quality %, be preferably 5 quality %～50 quality %, and the total quality of aluminum oxide and inorganic fibre, in the solids component of resin combination, is used the amount of 30 quality %～95 quality % conventionally.
For resin combination of the present invention, except aforementioned aluminum oxide, can also further contain as required aluminum oxide inorganic filling material in addition.As inorganic filling material, for example, as dielectric inorganic filling material, can enumerate magnesium oxide, aluminium nitride, boron nitride, silicon nitride, silicon oxide, aluminium hydroxide, barium sulfate etc.In addition, as the inorganic filling material of electroconductibility, can enumerate gold and silver, nickel, copper etc.These inorganic filling materials can be used separately a kind, also can use mixed system of more than two kinds.
For resin combination of the present invention, except above-mentioned neccessary composition, can also contain as required other composition.As other composition, for example, can enumerate solvent, silane coupling agent, dispersion agent, anti-sedimentation agent etc.
As aforementioned solvents, only otherwise can hinder the curing reaction of resin combination, be just not particularly limited, can suitably select organic solvent used conventionally.
Resin combination of the present invention preferably contains silane coupling agent.By containing silane coupling agent, and realized the effect (being equivalent to binding agent) that forms covalent linkage between the surface of alumina material and organic resin around thereof surrounding, thereby there is the effect of effective heat by conduction, further, owing to having prevented the intrusion of moisture, therefore also contribute to the raising of insulating reliability.
As silane coupling agent, conventionally can use commercial goods, but consider the consistency with epoxy resin or resol, and reduce the heat conduction loss on resin layer and aluminum oxide interface, be applicable to the silane coupling agent that use has epoxy group(ing), amino, sulfydryl, uride base or hydroxyl endways.
Specifically, can enumerate 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, APTES, 3-(2-amino-ethyl) TSL 8330, 3-(2-amino-ethyl) TSL 8330, 3-TSL 8330, 3-phenyl amino propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl triethoxyl silane, 3-uride base propyl-triethoxysilicane etc., and can enumerate and take silane coupling agent oligopolymer (Hitachi changes into Coated-sand Co., Ltd. system) that SC-6000KS2 is representative etc.
These silane coupling agents, can be used separately a kind, also can two or more are used.
In resin combination of the present invention, can add dispersion agent.As dispersion agent, can use without particular limitation the effectively dispersion agent of dispersed alumina.As dispersion agent, for example, can enumerate the Ajisper processed of aginomoto Finetech Co., Ltd. series, nanmu and originally change into Co., Ltd.'s HIPLAAD series processed, Co., Ltd. and spend king Homogenol processed (ホ モ ゲ ノ mono-Le) serial etc.These dispersion agents, can be used separately a kind, also can two or more are used.
<B rank sheet material >
B of the present invention rank sheet material, is formed by the semicure resin combination that comes from aforementioned resin, and has flake shape.
B rank sheet material, for example, can be manufactured by the following method and manufacture, and the method comprises and aforementioned resin is coated in mold release film and dry, forms the operation of resin molding, and by aforementioned resin film heat treated the operation to B scalariform state.
Due to aforementioned resin heat treated is formed, its thermal conductivity and electrical insulating property are excellent, and also excellent as the flexible and work-ing life of B rank sheet material.
B of the present invention rank sheet material refers to, as the viscosity of resin sheet, with respect to being 10 under normal temperature (25 degree) 4pas～10 5pas, its viscosity is reduced to 10 at 100 ℃ 2pas～10 3the sheet material of Pas.In addition, the curing resin layer after aftermentioned is solidified, even by heating, can melting yet.In addition, above-mentioned viscosity, measures by Measurement of Dynamic Viscoelasticity (frequency is 1Hz, and loading is 40g, and heat-up rate is 3 ℃/min).
Specifically, for example, can be by the mold release film such as PET film, the varnish shape resin combination of methylethylketone or pimelinketone equal solvent has been added in coating, is then dried and obtains resin molding.
Coating can be implemented by known method.As coating process, specifically, can enumerate the methods such as the coating of unfilled corner wheel (comma coat), mould painting, lip painting, intaglio plate coating.As resin layer being formed to the coating process of specific thickness, can being suitable for, make applied thing take turns coating method, by nozzle, be coated with the mould Tu Fa of the resinous varnish of having adjusted flow etc. by the unfilled corner between gap.For example, when dry front resin layer thickness is 50 μ m～500 μ m, preferably use unfilled corner wheel coating method.
Although the resin layer after coating is owing to substantially can not being cured reaction, and have flexiblely, its flexibility as sheet material is not enough, and under the state of removing as the aforementioned PET film of support, sheet material independence is not enough, is difficult to process.Therefore,, in the present invention, by heat treated described later, make resin combination B rank.
In the present invention, the resin molding of gained is carried out to the condition of heat treated, as long as can make resin combination semicure to B scalariform state, be just not particularly limited, and can suitably select according to the formation of resin combination.In the present invention, the object consideration in the space (hollow) the resin layer producing while being coated with from eliminating, heat treated is preferably the heating treatment method that is selected from thermovacuum pressurization and hot-roll lamination etc.Thus, can effectively manufacture smooth B rank sheet material.
Specifically, for example, can by take Heating temperature as 80 ℃～130 ℃, 1～30 second, (for example, condition 1MPa) is carried out hot-pressing processing to vacuum, and makes resin combination semicure to B scalariform state.
The thickness of aforementioned B rank sheet material, can suitably select according to object, for example, can be made as below the above 200 μ m of 50 μ m, and consider from the flexible viewpoint of thermal conductivity, electrical insulating property and sheet material, is preferably below the above 150 μ m of 60 μ m.In addition, can also be by 2 layers of above resin molding of one side lamination, one side makes by carrying out hot pressing.
< is with the tinsel > of resin
Tinsel with resin of the present invention has tinsel and is configured in the semicure resin layer that comes from aforementioned resin on aforementioned metal paper tinsel.By thering is the semicure resin layer that comes from aforementioned resin, so thermal conductivity, electrical insulating property and flexible excellence.
Aforementioned semicure resin layer can obtain its formation B scalariform state by aforementioned resin being carried out to heat treated.
As aforementioned metal paper tinsel, be not specially limited as goldleaf, Copper Foil, aluminium foil etc., but conventionally use Copper Foil.
As the thickness of aforementioned metal paper tinsel, as long as be 1 μ m～200 μ m, be just not particularly limited, but by using the tinsel below the above 150 μ m of 10 μ m, can further improve flexible.
In addition, as tinsel, can also use that to take nickel, nickel-phosphorus, nickel-tin alloy, nickel-ferro alloy, lead, Lead-tin alloy etc. be middle layer, and on its two sides, arrange the copper layer of 0.5 μ m～15 μ m and the copper layer of 10 μ m～300 μ m 3-tier architecture composite foil or by aluminium and 2 layers of compound structure composite paper tinsel of Copper Foil.
With the tinsel of resin, can form resin layer (resin molding) by aforementioned resin being coated in tinsel and dry, and aforementioned resin layer is carried out to heat treated make it form B scalariform state (semi-cured state) and manufacture.
Creating conditions of tinsel with resin is not particularly limited, the electrical insulating property during still from making metal substrate and the viewpoint consideration of outward appearance, and in dried resin layer, the organic solvent using in preferred resin varnish has volatilized more than 80 quality %.Drying temperature is 80 ℃～180 ℃ left and right, and can take into account the gelation time of varnish and determine time of drying, and it is not particularly limited.For the glue spread of resinous varnish, the mode that the dried resin layer thickness of preferably take is 50 μ m～200 μ m is coated with, more preferably 60 μ m～150 μ m.
In addition, the formation method of resin layer, heat treated condition, as previously mentioned.
< metal substrate >
Metal substrate of the present invention has metal support, is configured in the resin layer that comes from aforementioned resin on aforementioned metal support and is configured in the tinsel on aforementioned resin layer.Owing to being configured in the resin layer that comes from aforementioned resin between metal support and tinsel for being solid state and forming by carrying out heat treated, so cementability, thermal conductivity, electrical insulating property are excellent.
For aforementioned metal support, according to object, suitably select its material and thickness etc.Specifically, for example, use the metals such as aluminium, iron, from the viewpoint of processibility, consider, preferably making thickness is below the above 5mm of 0.5mm.
In addition, be configured in tinsel on resin layer and aforementioned with the tinsel synonym in the tinsel of resin, and optimal way is also identical.
Metal substrate of the present invention, for example, can manufacture as follows.Can be by the metal supports such as aluminium, and the above-mentioned aforementioned resin dry that is similarly coated with, form resin layer, and further on resin layer, configure tinsel, to its heat, pressure treatment, make resin layer solidify and manufacture.In addition, can also be by paste the aforementioned tinsel with resin on metal support, and make resin layer relative with metal support to, then to its heat, pressure treatment, make resin layer solidify and manufacture.
Make the condition of the curing heating of aforementioned resin layer, pressure treatment, can suitably select according to the formation of resin combination.For example, preferably Heating temperature is 80 ℃～250 ℃, and pressure is 0.5MPa～8.0MPa, and more preferably Heating temperature is 130 ℃～230 ℃, and pressure is 1.5MPa～5.0MPa.
<LED substrate >
LED substrate 100 of the present invention as shown in Fig. 1 and Fig. 2 summary, there is metal support 14, be configured in the curing resin layer that comes from aforementioned resin 12 on aforementioned metal support, be configured on aforementioned curing resin layer 12 by the formed circuit layer 10 of tinsel and be configured in the LED element 20 on aforementioned circuit layer.
By form the aforementioned resin layer of cementability, thermal conductivity and electrical insulating property excellence on metal support, the heat that can effectively emit LED element is dispelled the heat.
LED substrate of the present invention, for example, can be manufactured by the following method and manufacture, and the method comprises carries out circuit fabrication to the tinsel on the metal substrate of above-mentioned gained, forms the operation of circuit layer and the operation that configures LED element on the circuit layer forming.
Tinsel on metal substrate is carried out to the operation of circuit fabrication, can be suitable for the common methods used such as photolithography.In addition, on circuit layer, configure the operation of LED element, also can be suitable for without particular limitation method used conventionally.
Embodiment
Below, by embodiment, be described more specifically the present invention, but the present invention is not limited to these embodiment.In addition, unless otherwise specified, " portion " and " % " is quality criteria.
< resin synthesis example 1>
In the detachable flask of the 3L with stirrer, water cooler, thermometer, add Resorcinol 594g, catechol 66g, 37% formalin 316.2g, oxalic acid 15g, water 100g, in oil bath, heat, and be warming up to 100 ℃.Under reflux temperature, continue reaction 4 hours.
Then, Yi Bian heat up in a steamer, anhydrate, Yi Bian make the temperature in flask be warming up to 170 ℃.Remain on 170 ℃ on one side, continue to react 8 hour on one side.Then, under reduced pressure, carry out 20 minutes concentrated, remove water in system etc., and take out the resol with the represented structural unit of general formula (I).The number-average molecular weight of the resol of gained is 530, and weight-average molecular weight is 930.In addition, the phenol equivalent of resol is 65g/eq..
< embodiment 1>
In the 1L of polypropylene system lidded container, weighing 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 18 μ m, Sumicorundum (ス ミ コ ラ Application ダ system) AA18), 20.29g (22.5% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), 13.07g (14.5% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and add 0.099g silane coupling agent (Shin-Etsu Chemial Co., Ltd's system, KBM403), 12.18g is as the 2-butanone (He Guangchun medicine Co., Ltd. system) of solvent, (nanmu originally changes into Co., Ltd.'s system to 0.180g dispersion agent, ED-113), the resol of gained in 2.98g (solids component) resin synthesis example 1, and stir.Add again 5.914g to there are 2 officials' energy epoxy resin (Mitsubishi chemical Co., Ltd's systems of biphenyl backbone, YL6121H, epoxy equivalent (weight) are 172g/eq.), 0.657g naphthalene is epoxy resin (Dainippon Ink Chemicals's system, HP4032D, epoxy equivalent (weight) are 140g/eq.), 0.012g imidazolium compounds (Shikoku Chem's system, 2PHZ).Further, drop into the zirconia ball that 500g diameter is 5mm, and with 100rpm, stir 48 hours on ball mill pallet, then filter out zirconia ball, obtain the resin combination 1 of varnish shape.
In addition, in resin combination 1, resol is 1.18 with respect to the ratio that contains of epoxy resin total content.
Use has spreader and the desk-top coating machine (Tester Industry Co., Ltd system) in 250 μ m gaps, and the resin combination of above-mentioned gained 1 is coated on to PET film, and (Di Ren Du Pont membrane society system A53) above, and is dried 20 minutes at 100 ℃.Dried thickness is 100 μ m.On dried resin layer, place PET film (Di Ren Du Pont membrane society system, A53), then use vacuum laminator (name machine-processed Zuo Suo society system), under 130 ℃, vacuum tightness 1MPa, carry out 15 second vacuum pressed, obtain sheet forming thing (B rank sheet material).
The flexible excellence of the sheet forming thing of gained.
[evaluation]
The sheet forming thing of above-mentioned gained is clipped between the stainless steel plate that 2mm is thick, in box like dryer, at 140 ℃, processes 2 hours, then at 190 ℃, process 2 hours, obtain sheet material cured article.Sheet material cured article to gained, carries out following evaluation.Evaluation result is shown in table 1.
(thermal conductivity)
Use thermal diffusivity heat conducting coefficient measurement device (ai-Phase-Mobile, ai-Phase society system), and by temperature wave thermal analysis system, measure the thermal conductivity of the sheet material cured article of gained.Measurement result is shown in table 1.
(electrical insulating property)
The sheet material cured article of gained is clipped between the electrode that diameter is 25mm, uses HAT-300-100RHO type insulation breakdown voltage measuring device (Shan Qi industry society system), applying under the alternating-current condition of (500V/ second), measure minimum dielectric voltage withstand value.Measurement result is shown in table 1.
(sheet material gloss)
The gloss of the sheet material cured article by visual observation gained, and evaluate based on following metewand.
～metewand～
A: there is uniform gloss on whole of sheet material.
B: there is gloss on whole of sheet material, but have micro concavo-convex.
C: find out a little glossy on whole of sheet material.
D: all lackluster on whole of sheet material.
(aluminum oxide particle diameter)
Resin combination 1 for varnish shape, its 0.5g is dispersed in the methyl alcohol of 50g, and will put in right amount laser diffraction and scattering particle size distribution device (beckmancoulter society system, LS230) in, carry out the particle size distribution of aluminum oxide in resin combination.Measurement result is shown in table 1.
< embodiment 2>
Except in embodiment 1, as aluminum oxide, using 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Showa Denko K. K's system of 20 μ m, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, SumicorundumAA04) in addition, similarly operate with embodiment 1, the resin combination 2 of modulation varnish shape.The resin combination 2 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.Evaluation result is shown in table 1.
In addition, in resin combination 2, resol is 1.18 with respect to the ratio that contains of epoxy resin total content.
The flexible excellence of the sheet forming thing of gained.
< embodiment 3>
Except in embodiment 1, respectively the addition of resol is changed into 2.805g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.072g, the addition that is epoxy resin by naphthalene is changed into beyond 0.675g, with embodiment 1 similarly, the resin combination 3 of modulation varnish shape.The resin combination 3 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.Evaluation result is shown in table 1.
In addition, in resin combination 3, resol is 1.08 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 4>
Except in embodiment 1, respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.154g, the addition that is epoxy resin by naphthalene is changed into beyond 0.683g, similarly operate the resin combination 4 of modulation varnish shape with embodiment 1.The resin combination 4 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 4, resol is 1.03 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 5>
Except in embodiment 1, respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 5.991g, the addition that is epoxy resin by naphthalene is changed into beyond 0.666g, similarly operate the resin combination 5 of modulation varnish shape with embodiment 1.The resin combination 5 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 5, resol is 1.16 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 6>
Except in embodiment 1, respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 5.914g, the addition that is epoxy resin by naphthalene is changed into beyond 0.657g, similarly operate the resin combination 6 of modulation varnish shape with embodiment 1.The resin combination 6 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 6, resol is 1.20 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 7>
Except in embodiment 1, respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.495g, the addition that is epoxy resin by naphthalene is changed into beyond 0.342g, similarly operate the resin combination 7 of modulation varnish shape with embodiment 1.The resin combination 7 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 7, resol is 1.05 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 8>
Except in embodiment 1, respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.324g, the addition that is epoxy resin by naphthalene is changed into beyond 0.333g, similarly operate the resin combination 8 of modulation varnish shape with embodiment 1.The resin combination 8 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 8, resol is 1.15 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 9>
Except in embodiment 1, respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.242g, the addition that is epoxy resin by naphthalene is changed into beyond 0.329g, similarly operate the resin combination 9 of modulation varnish shape with embodiment 1.The resin combination 9 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 9, resol is 1.22 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 10>
Except in embodiment 1, respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.837g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate the resin combination 10 of modulation varnish shape with embodiment 1.The resin combination 10 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 10, resol is 1.04 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 11>
Except in embodiment 1, respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.657g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate the resin combination 11 of modulation varnish shape with embodiment 1.The resin combination 11 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 11, resol is 1.15 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 12>
Except in embodiment 1, respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.571g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate the resin combination 12 of modulation varnish shape with embodiment 1.The resin combination 12 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 12, resol is 1.22 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 13>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (the Sumitomo Chemical pillar commercial firm system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.154g, the addition that is epoxy resin by naphthalene is changed into beyond 0.683g, similarly operate with embodiment 1, the resin combination 13 of modulation varnish shape.The resin combination 13 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 13, resol is 1.06 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 14>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 5.991g, the addition that is epoxy resin by naphthalene is changed into beyond 0.666g, similarly operate with embodiment 1, the resin combination 14 of modulation varnish shape.The resin combination 14 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 14, resol is 1.15 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 15>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 5.914g, the addition that is epoxy resin by naphthalene is changed into beyond 0.657g, similarly operate with embodiment 1, the resin combination 15 of modulation varnish shape.The resin combination 15 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 15, resol is 1.21 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 16>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.495g, the addition that is epoxy resin by naphthalene is changed into beyond 0.342g, similarly operate with embodiment 1, the resin combination 16 of modulation varnish shape.The resin combination 16 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 16, resol is 1.06 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 17>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.324g, the addition that is epoxy resin by naphthalene is changed into beyond 0.333g, similarly operate with embodiment 1, the resin combination 17 of modulation varnish shape.The resin combination 17 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 17, resol is 1.16 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 18>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.242g, the addition that is epoxy resin by naphthalene is changed into beyond 0.329g, similarly operate with embodiment 1, the resin combination 18 of modulation varnish shape.The resin combination 18 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 18, resol is 1.18 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 19>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, SumicorundumAA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.837g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate with embodiment 1, the resin combination 19 of modulation varnish shape.The resin combination 19 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 19, resol is 1.05 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 20>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.657g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate with embodiment 1, the resin combination 20 of modulation varnish shape.The resin combination 20 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 20, resol is 1.14 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 21>
Except in embodiment 1, it is aluminum oxide (Showa Denko K. K's system of 20 μ m that aluminum oxide is changed into 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.571g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate with embodiment 1, the resin combination 21 of modulation varnish shape.The resin combination 21 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 21, resol is 1.03 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 22>
Except in embodiment 1, as aluminum oxide, change into the aluminum oxide that 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 the is 24 μ m (Materials of Nippon Steel (マ テ リ ア Le ズ) icron society of M Co., Ltd. system, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.154g, the addition that is epoxy resin by naphthalene is changed into beyond 0.683g, similarly operate with embodiment 1, the resin combination 22 of modulation varnish shape.The resin combination 22 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 22, resol is 1.05 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 23>
Except in embodiment 1, as aluminum oxide, changing into 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 24 μ m, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 5.991g, the addition that is epoxy resin by naphthalene is changed into beyond 0.666g, similarly operate with embodiment 1, the resin combination 23 of modulation varnish shape.The resin combination 23 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 23, resol is 1.16 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 24>
Except in embodiment 1, as aluminum oxide, changing into 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 24 μ m, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 5.914g, the addition that is epoxy resin by naphthalene is changed into beyond 0.657g, similarly operate with embodiment 1, the resin combination 24 of modulation varnish shape.The resin combination 24 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 24, resol is 1.20 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 25>
Except in embodiment 1, as aluminum oxide, using 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 24 μ m, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.495g, the addition that is epoxy resin by naphthalene is changed into beyond 0.342g, similarly operate with embodiment 1, the resin combination 25 of modulation varnish shape.The resin combination 25 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 25, resol is 1.06 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 26>
Except in embodiment 1, as aluminum oxide, changing into 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 24 μ m, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.324g, the addition that is epoxy resin by naphthalene is changed into beyond 0.333g, similarly operate with embodiment 1, the resin combination 26 of modulation varnish shape.The resin combination 26 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 26, resol is 1.13 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 27>
Except in embodiment 1, as aluminum oxide, changing into 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 24 μ m, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.242g, the addition that is epoxy resin by naphthalene is changed into beyond 0.329g, similarly operate with embodiment 1, the resin combination 27 of modulation varnish shape.The resin combination 27 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 27, resol is 1.22 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 28>
Except in embodiment 1, as aluminum oxide, changing into 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 24 μ m, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.713g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.837g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate with embodiment 1, the resin combination 28 of modulation varnish shape.The resin combination 28 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 28, resol is 1.05 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 29>
Except in embodiment 1, as aluminum oxide, changing into 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 24 μ m, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.893g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.657g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate with embodiment 1, the resin combination 29 of modulation varnish shape.The resin combination 29 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 29, resol is 1.15 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 30>
Except in embodiment 1, as aluminum oxide, changing into 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 24 μ m, AX-116), 18.93g (21.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 14.42g (16.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.979g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.571g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate with embodiment 1, the resin combination 30 of modulation varnish shape.The resin combination 30 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 30, resol is 1.21 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 31>
Except in embodiment 1, respectively the addition of resol is changed into 2.619g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.238g, the addition that is epoxy resin by naphthalene is changed into beyond 0.693g, similarly operate the resin combination 31 of modulation varnish shape with embodiment 1.The resin combination 31 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 31, resol is 1.00 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 32>
Except in embodiment 1, respectively the addition of resol is changed into 2.619g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.931g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate the resin combination 32 of modulation varnish shape with embodiment 1.The resin combination 32 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination 32, resol is 1.00 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< embodiment 33>
In the 1L of polypropylene system lidded container, weighing 56.80g (63.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 18 μ m, Sumicorundum AA18), 20.29g (22.5% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 13.07g (14.5% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and add 0.099g silane coupling agent (Shin-Etsu Chemial Co., Ltd's system, KBM403), 12.18g is as the 2-butanone (He Guangchun medicine Co., Ltd. system) of solvent, (nanmu originally changes into Co., Ltd.'s system to 0.180g dispersion agent, ED-113), 2.98g (solids component) resol (Hitachi Chemical Co., Ltd.'s system, Hitanol (ヒ タ ノ mono-Le), the novolac resin with the represented structural unit of general formula (I), phenol equivalent is 65g/eq.), and stir.Add again 5.914g to there are 2 officials' energy epoxy resin (Mitsubishi chemical Co., Ltd's systems of biphenyl backbone, YL6121H, epoxy equivalent (weight) are 172g/eq.), 0.657g naphthalene is epoxy resin (Dainippon Ink Chemicals's system, HP4032D, epoxy equivalent (weight) are 140g/eq.), 0.012g imidazolium compounds (Shikoku Chem's system, 2PHZ).Further, drop into the zirconia ball that 500g diameter is 5mm, and with 100rpm, stir 48 hours on ball mill pallet, then filter zirconia ball, obtain the resin combination 33 of varnish shape.The resin combination 33 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.Evaluation result is shown in table 1.
In addition, in resin combination 33, resol is 1.18 with respect to the ratio that contains of epoxy resin total content.
The flexible excellence of the sheet forming thing of gained.
< embodiment 34>
Except in embodiment 33, as aluminum oxide, using 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Showa Denko K. K's system of 20 μ m, AS-20), 16.77g (18.6% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 10.73g (11.9% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04) in addition, similarly operate with embodiment 1, the resin combination 34 of modulation varnish shape.The resin combination 34 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.Evaluation result is shown in table 1.
In addition, in resin combination 34, resol is 1.18 with respect to the ratio that contains of epoxy resin total content.
The flexible excellence of the sheet forming thing of gained.
< comparative example 1>
Except in embodiment 1, as aluminum oxide, change into the aluminum oxide that 62.66g (69.5% (with respect to aluminum oxide total mass)) particle diameter D50 is 20 μ m (clear and electrician's system, AS-20), 18.39g (20.4% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (icron society of Materials M Co., Ltd. of the Nippon Steel system of 4.5 μ m, AX3-32), and 9.10g (10.1% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Nippon Light Metal Co., Ltd's system of 0.5 μ m, LS235), and respectively the addition of resol is changed into 2.322g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.506g, the addition that is epoxy resin by naphthalene is changed into beyond 0.723g, similarly operate with embodiment 1, the resin combination C1 of modulation varnish shape.The resin combination C1 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination C1, resol is 0.85 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< comparative example 2>
Except in comparative example 1, respectively the addition of resol is changed into 3.226g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 5.692g, the addition that is epoxy resin by naphthalene is changed into beyond 0.632g, similarly operate the resin combination C2 of modulation varnish shape with comparative example 1.The resin combination C2 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination C2, resol is 1.36 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< comparative example 3>
Except in comparative example 1, respectively the addition of resol is changed into 2.523g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 7.027g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate the resin combination C3 of modulation varnish shape with comparative example 1.The resin combination C3 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination C3, resol is 0.95 with respect to the ratio that contains of epoxy resin total content.
And, the flexible excellence of the sheet forming thing of gained.
< comparative example 4>
Except in comparative example 1, as aluminum oxide, changing into 63.11g (70.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Showa Denko K. K's system of 39 μ m, AS-10), 13.52g (15.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 3 μ m, Sumicorundum AA3), and 13.52g (15.0% (with respect to aluminum oxide total mass)) particle diameter D50 is aluminum oxide (Sumitomo Chemical Co's system of 0.4 μ m, Sumicorundum AA04), and respectively the addition of resol is changed into 2.523g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 6.325g, the addition that is epoxy resin by naphthalene is changed into beyond 0.702g, similarly operate with comparative example 1, the resin combination C4 of modulation varnish shape.The resin combination C4 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination C4, resol is 0.94 with respect to the ratio that contains of epoxy resin total content.
The flexible excellence of the sheet forming thing of gained.
< comparative example 5>
Except in comparative example 4, respectively the addition of resol is changed into 3.146g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 5.764g, the addition that is epoxy resin by naphthalene is changed into beyond 0.640g, similarly operate the resin combination C5 of modulation varnish shape with comparative example 4.The resin combination C5 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination C5, resol is 1.29 with respect to the ratio that contains of epoxy resin total content.
The flexible excellence of the sheet forming thing of gained.
< comparative example 6>
Except in comparative example 4, respectively the addition of resol is changed into 2.424g, the addition with 2 officials' energy epoxy resin of biphenyl backbone is changed into 7.126g, the addition that is epoxy resin by naphthalene is changed into beyond 0g, similarly operate the resin combination C6 of modulation varnish shape with comparative example 4.The resin combination C6 that uses the varnish shape of gained, obtains sheet forming thing, similarly evaluates.
In addition, in resin combination C6, resol is 0.88 with respect to the ratio that contains of epoxy resin total content.
The flexible excellence of the sheet forming thing of gained.
Table 1
As shown in Table 1, resin combination of the present invention is being solidified in the sheet material cured article of gained, can be with excellent level with thermal conductivity and electrical insulating property.
No. 2010-152346, Japanese publication, No. 2010-152347 disclosed full content of Japanese publication, be incorporated in this specification sheets by reference.
For whole documents, patent application and the technological standard recorded in this specification sheets, each document, patent application and technological standard be by with reference to situation about introducing, with specifically and the situation same degree of recording respectively by reference, be incorporated in this specification sheets.

Claims (8)

1. a resin combination, its contain there are 2 officials of biphenyl backbone can epoxy resin, resol, from the small particle size side of weight build-up size-grade distribution, accumulation 50% corresponding particle diameter D50 is that more than 7 μ m the 1st aluminum oxide group, the aforementioned particle size D50 below 25 μ m is more than 1 μ m and is the 3rd aluminum oxide group less than 1 μ m less than the 2nd aluminum oxide group and the aforementioned particle size D50 of 7 μ m
Aforementioned resol with respect to epoxy resin total content contain ratio, be resol/epoxy resin, in equivalent benchmark, be more than 1.00 below 1.25,
In aforementioned the 1st aluminum oxide group, the 2nd aluminum oxide group and the 3rd aluminum oxide group's total mass, aforementioned the 1st aluminum oxide group's containing ratio is below the above 70 quality % of 60 quality %, aforementioned the 2nd aluminum oxide group's containing ratio is below the above 30 quality % of 15 quality %, aforementioned the 3rd aluminum oxide group's containing ratio is below the above 25 quality % of 1 quality %
Aforementioned the 1st aluminum oxide faciation contains ratio, i.e. the 1st aluminum oxide group/2nd aluminum oxide group for aforementioned the 2nd aluminum oxide group's, in quality criteria, is more than 2.0 below 5.0,
Aforementioned the 2nd aluminum oxide faciation contains ratio, i.e. the 2nd aluminum oxide group/3rd aluminum oxide group for aforementioned the 3rd aluminum oxide group's, in quality criteria, is more than 1.3 below 1.6.
2. resin combination as claimed in claim 1, wherein aforementioned resol comprises the resol with the represented structural unit of following general formula (I);
In general formula (I), R 1represent alkyl, aryl or aralkyl, R 2and R 3represent independently of one another hydrogen atom, alkyl, aryl or aralkyl, m represents 0～2 integer, and n represents 1～7 integer.
3. resin combination as claimed in claim 1, wherein aforementioned 2 officials with biphenyl backbone can comprise the represented compound of following general formula (III) by epoxy resin;
In general formula (III), R 1～R 8represent that independently of one another hydrogen atom or carbonatoms are 1～10 alkyl, n represents 0～3 integer.
4. resin combination as claimed in claim 2, wherein aforementioned 2 officials with biphenyl backbone can comprise the represented compound of following general formula (III) by epoxy resin;
In general formula (III), R 1～R 8represent that independently of one another hydrogen atom or carbonatoms are 1～10 alkyl, n represents 0～3 integer.
5. one kind by the formed B of the semicure resin combination rank sheet material that comes from the resin combination described in claim 1～4 any one.
6. with the tinsel of resin, it has tinsel and is configured in the semicure resin layer that comes from the resin combination described in claim 1～4 any one on aforementioned metal paper tinsel.
7. a metal substrate, it has metal support, be configured in the curing resin layer that comes from the resin combination described in claim 1～4 any one on aforementioned metal support and be configured in the tinsel on aforementioned curing resin layer.
8. a LED substrate, it has metal support, be configured in the curing resin layer that comes from the resin combination described in claim 1～4 any one on aforementioned metal support, be configured on aforementioned curing resin layer by the formed circuit layer of tinsel and be configured in the LED element on aforementioned circuit layer.
CN201110189110.3A 2010-07-02 2011-07-01 Resin composition, B stage sheet, metal foil with resin, metal substrate, and LED substrate Expired - Fee Related CN102337006B (en)

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