WO2012039324A1 - Composition de résine thermoconductrice, feuille de résine, feuille métallique revêtue de résine, feuille de résine durcie et élément dissipateur de chaleur - Google Patents

Composition de résine thermoconductrice, feuille de résine, feuille métallique revêtue de résine, feuille de résine durcie et élément dissipateur de chaleur Download PDF

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Publication number
WO2012039324A1
WO2012039324A1 PCT/JP2011/070863 JP2011070863W WO2012039324A1 WO 2012039324 A1 WO2012039324 A1 WO 2012039324A1 JP 2011070863 W JP2011070863 W JP 2011070863W WO 2012039324 A1 WO2012039324 A1 WO 2012039324A1
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resin
resin composition
sheet
heat
structural unit
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PCT/JP2011/070863
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English (en)
Japanese (ja)
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士輝 宋
片木　秀行
竹澤　由高
山下　幸彦
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日立化成工業株式会社
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Priority to JP2012535005A priority Critical patent/JPWO2012039324A1/ja
Publication of WO2012039324A1 publication Critical patent/WO2012039324A1/fr

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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
    • B32B15/04—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

  • the present invention relates to a thermally conductive resin composition, a resin sheet, a metal foil with resin, a cured resin sheet, and a heat dissipation member.
  • thermally conductive resin compositions are widely used.
  • the thermal conductive resin composition is required to have excellent thermal conductivity. Therefore, in many cases, a method of adding an inorganic filler having a high thermal conductivity with a filling rate as high as possible is used for the preparation of the thermal conductive resin composition. For example, in Japanese Patent Application Laid-Open No.
  • a molded product having a thermal conductivity of 3 W / mK to 10 W / mK is obtained by setting the inorganic filler in the epoxy resin to a high filling rate of 80% by mass to 95% by mass. It is described that it can be obtained.
  • the resulting heat conductive resin composition is often hard and brittle, and therefore, it tends to break easily.
  • the ratio of the epoxy resin component which has the adhesive performance contained in a heat conductive resin composition decreases. Therefore, in general, when filler is added at a high filling rate, the adhesiveness of the resin to a metal surface such as aluminum or copper, that is, the adhesive strength at the resin-metal interface tends to be greatly reduced.
  • the resin composition As described above, it is possible to achieve a high thermal conductivity of the resin composition by adding an inorganic filler at a high filling rate, but on the other hand, the resin composition tends to lack flexibility and has an adhesive strength. It is a problem that the decline of
  • an object of the present invention is to provide a thermal conductive resin composition having excellent thermal conductivity and excellent flexibility and adhesiveness, and a molded product using the resin composition. It is to provide.
  • the present invention includes the following aspects.
  • the first aspect of the present invention is a thermally conductive resin composition containing an epoxy resin, an inorganic filler, and an elastomer having at least a structural unit represented by the following general formula (I) in the molecule.
  • R 1 , R 2 and R 3 are each independently a linear or branched alkyl group or a hydrogen atom, R 4 is a linear or branched alkyl group, and n Represents an arbitrary integer.
  • the elastomer is preferably an acrylic resin.
  • the acrylic resin preferably further has at least one of a carboxy group and a hydroxy group in the molecule.
  • the acrylic resin preferably further has an amino group in the molecule.
  • the acrylic resin is preferably a compound having a structure represented by the following general formula (II).
  • R 21 and R 22 are each independently a linear or branched alkyl group having a different carbon number
  • R 23 to R 26 are each independently a hydrogen atom or a methyl group
  • R 21 and R 22 are preferably each independently a linear or branched alkyl group having 4 to 12 carbon atoms, each having a different carbon number.
  • the heat conductive resin composition preferably further contains a phenolic curing agent.
  • the second aspect of the present invention is a resin sheet formed by molding the thermal conductive resin composition into a sheet shape.
  • a third aspect of the present invention is a metal foil with a resin having a metal foil and a semi-cured resin layer that is a semi-cured product of the thermally conductive resin composition disposed on the metal foil.
  • a fourth aspect of the present invention is a cured resin sheet that is a heat-treated product of the thermally conductive resin composition.
  • a fifth aspect of the present invention is a heat dissipating member having a metal work and the resin sheet or the cured resin sheet disposed on the metal work.
  • the heat conductive resin composition which was excellent also in the flexibility and the adhesiveness, and the molded article using this resin composition can be provided. .
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition in the present specification when there are a plurality of substances corresponding to each component in the composition, the plurality of the components present in the composition unless otherwise specified. It means the total amount of substance.
  • the thermally conductive resin composition of the present invention (hereinafter also simply referred to as “resin composition”) comprises an epoxy resin, an inorganic filler, and an elastomer having at least a structural unit represented by the following general formula (I) in the molecule. Containing.
  • resin composition comprises an epoxy resin, an inorganic filler, and an elastomer having at least a structural unit represented by the following general formula (I) in the molecule. Containing.
  • R 1 , R 2 and R 3 are each independently a linear or branched alkyl group or a hydrogen atom, R 4 is a linear or branched alkyl group, and n Represents an arbitrary integer.
  • Epoxy resin The epoxy resin used in the present invention is not particularly limited.
  • bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, cycloaliphatic epoxy resin and the like can be mentioned.
  • an epoxy resin having a mesogenic skeleton in the molecule which is a structure that is easily self-aligned, such as a biphenyl group.
  • An epoxy resin having such a mesogenic skeleton in the molecule is disclosed, for example, in JP-A-2005-206814.
  • Examples of the epoxy resin include 1- ⁇ (3-methyl-4-oxiranylmethoxy) phenyl ⁇ -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene, 1- ⁇ (2-methyl-4 -Oxiranylmethoxy) phenyl ⁇ -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene, 1- ⁇ (3-ethyl-4-oxiranylmethoxy) phenyl ⁇ -4- (4-oxira Nylmethoxyphenyl) -1-cyclohexene.
  • 1- ⁇ (3-methyl-4-oxiranylmethoxy) phenyl ⁇ -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene is preferable from the viewpoint of a low melting temperature.
  • a specific epoxy resin By using such a specific epoxy resin, it becomes possible to melt and mix with a curing agent described later at a curing temperature (preferably 120 ° C.) or lower, and it can be applied to a process requirement for low temperature curing.
  • the content of the epoxy resin in the resin composition is not particularly limited.
  • the solid content of the resin composition can be 1% by mass to 50% by mass, and preferably 1% by mass to 10% by mass. Adhesiveness and heat conductivity can be improved more because the content rate of an epoxy resin is the said range.
  • the solid content of the resin composition means a residue obtained by removing volatile components from the resin composition.
  • the inorganic filler used in the present invention is not particularly limited, and compounds well known in the art can be used. They may be non-conductive or conductive.
  • the non-conductive inorganic filler include aluminum oxide (alumina), magnesium oxide, aluminum nitride, boron nitride, silicon nitride, silicon oxide, aluminum hydroxide, and barium sulfate.
  • the conductive inorganic filler include gold, silver, nickel, and copper. When a conductive inorganic filler is used, the thermal conductivity can be improved, but the insulation tends to be lowered.
  • the inorganic filler may be used alone or in a mixed system of two or more.
  • inorganic fillers having different particle sizes may be used in combination.
  • an inorganic filler having a small particle diameter enters a gap between inorganic fillers having a large particle diameter, facilitating high filling of the inorganic filler, and high thermal conductivity efficiently. This is preferable because it can be realized.
  • it is preferable to use alumina as the inorganic filler it is more preferable to use a combination of alumina having different particle sizes.
  • the alumina when the 50% cumulative particle size from the small particle side of the weight cumulative particle size distribution is D50, the alumina has a D50 of 2 ⁇ m or more.
  • alumina (A) 100 ⁇ m or less of alumina (A)
  • D50 is alumina powder (B) of 1 ⁇ m or more and 10 ⁇ m or less
  • D50 is alumina powder (C) of 0.01 ⁇ m or more and 5 ⁇ m or less of alumina powder (A) with respect to the total volume of alumina powder
  • the ratio of (B) and (C) is (A) 50% by volume to 90% by volume, (B) 5% by volume to 40% by volume, and (C) 1% by volume to 30% by volume, respectively. Some embodiments may be mentioned (wherein the total volume% of alumina (A), (B) and (C) is 100 volume%).
  • alumina (A) is 60 volume% or more and 90 volume% or less
  • alumina (B) is 10 volume% or more and 40 volume% or less
  • alumina (C) is 5 volume% with respect to the total volume of alumina powder.
  • Alumina powder having a volume% of 30% or less is preferable (however, the total volume% of alumina (A), (B) and (C) is 100% by volume).
  • alumina (A) is 70 volume% or more and 90 volume% or less
  • alumina (B) is 10 volume% or more and 30 volume% or less
  • alumina (C) is 5 volume% or more and 20 volume% or less.
  • a certain alumina powder is mentioned (however, the total volume% of alumina (A), (B) and (C) is 100 volume%).
  • the alumina when the 50% cumulative particle size from the small particle side of the weight cumulative particle size distribution is D50, the alumina is D50 Is an alumina powder composed of alumina (A) having a diameter of 10 ⁇ m to 100 ⁇ m, alumina (B) having a D50 of 1 ⁇ m to less than 10 ⁇ m, and alumina (C) having a D50 of 0.01 ⁇ m to less than 1 ⁇ m,
  • the ratio of (A), (B) and (C) is (A) 55 volume% or more and 85 volume% or less, (B) 10 volume% or more and 30 volume% or less, and (C) 5 volume% or more and 15 volume%, respectively.
  • % Wherein the total volume% of alumina (A), (B) and (C) is 100% by volume.
  • alumina (A) is 55 volume% or more and 85 volume% or less
  • alumina (B) is 10 volume% or more and 40 volume% or less
  • alumina (C) is 5 volume% with respect to the total volume of alumina powder.
  • Alumina powder having a volume% of 30% or less is preferable (however, the total volume% of alumina (A), (B) and (C) is 100% by volume).
  • alumina (A) is 65 volume% or more and 80 volume% or less
  • alumina (B) is 10 volume% or more and 20 volume% or less
  • alumina (C) is 10 volume% or more and 15 volume% or less.
  • a certain alumina powder is mentioned (however, the total volume% of alumina (A), (B) and (C) is 100 volume%).
  • the above alumina (A), (B) and (C) can be obtained as commercial products. Further, it is also possible to produce transition alumina or alumina powder that becomes transition alumina by heat treatment in an atmosphere gas containing hydrogen chloride (for example, Japanese Patent Laid-Open Nos. 6-191833 and 6-6-1). No. 191836).
  • the alumina powder can be prepared by appropriately mixing alumina (A), (B) and (C) having a predetermined particle size distribution.
  • the alumina powder is preferably ⁇ -alumina powder.
  • the alumina (C) may be alumina made of ⁇ -alumina particles, or alumina made of transition alumina particles such as ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina.
  • Alumina made of ⁇ -alumina particles is preferred, and alumina made of ⁇ -alumina single crystal particles is more preferred.
  • the particle diameter D50 of the alumina particles is measured as a weight average particle diameter by a wet method using a laser diffraction / scattering particle size distribution analyzer.
  • the content of the entire filler in the resin composition is not particularly limited.
  • the total solid volume of the resin composition is preferably 30% by volume to 95% by volume, more preferably 45% by volume to 90% by volume from the viewpoint of improving thermal conductivity, and further heat conduction. From the viewpoint of improving the rate, it is more preferably 80 to 90% by volume. When it is 30% by volume or more, the thermal conductivity of the resin composition tends to be higher. Moreover, it exists in the tendency which the moldability of a resin composition improves more that it is 95 volume% or less.
  • the total solid content volume of a resin composition means the total volume of a non-volatile component among the components which comprise a resin composition.
  • the elastomer is a compound having at least a structural unit represented by the following general formula (I) in the molecule, and an acrylic resin is particularly preferable.
  • the acrylic resin is preferably a homopolymer or a copolymer derived from (meth) acrylic acid or (meth) acrylic acid ester.
  • R 1 , R 2 and R 3 each independently represent a linear or branched alkyl group or a hydrogen atom.
  • the number of carbons is preferably 1 to 12 from the viewpoint of imparting flexibility, and the number of carbons from the viewpoint of low Tg (glass transition temperature). Is more preferably 1-8.
  • R 1 and R 2 are each a hydrogen atom
  • R 3 is a hydrogen atom or a methyl group. More preferably, R 1 , R 2 and R 3 are hydrogen atoms.
  • R 4 is a linear or branched alkyl group.
  • the alkyl group in R 4 preferably has 2 to 16 carbon atoms from the viewpoint of imparting flexibility, and more preferably 3 to 14 carbon atoms from the viewpoint of small inhibition of the formation of the resin higher-order structure.
  • the number of carbon atoms is 4 to 12 from the viewpoints of availability and ease of synthesis.
  • the elastomer preferably has a structural unit number of carbon atoms in the alkyl group represented by R 4 is represented by two or more of the general formulas differ (I).
  • the carbon number of the alkyl group in one structural unit may be 2 to 8 from the viewpoint of low Tg.
  • the number of carbon atoms is 3-6.
  • the number of carbon atoms of the alkyl group in the other structural unit is preferably 8 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms from the viewpoint of imparting flexibility.
  • n is an arbitrary integer indicating the number of repeating units.
  • the number of repeating units represented by n means the total number of structural units represented by the general formula (I) contained in the elastomer molecule.
  • an acrylic resin mainly having a structural unit represented by the above general formula (I) it is possible to impart a soft structure (flexibility) to a thermally conductive resin composition containing an epoxy resin and an inorganic filler. Become. Therefore, it is possible to improve the problems such as a decrease in the flexibility of the sheet due to the high filling of the inorganic filler as seen in the conventional heat conductive sheet.
  • the acrylic resin having at least the structural unit represented by the general formula (I) in the molecule preferably further has at least one of a carboxy group and a hydroxy group in the molecule. It is more preferable to include a structural unit having at least one of hydroxy groups, and it is more preferable to include a structural unit having at least a carboxy group.
  • Examples of monomers that can form a structural unit having a carboxy group include acrylic acid, methacrylic acid, maleic acid, and itaconic acid. Among these, acrylic acid and methacrylic acid are preferable.
  • Examples of the monomer capable of forming a structural unit having a hydroxy group include (meth) acrylic acid esters containing a hydroxyalkyl group having 2 to 20 carbon atoms, including a hydroxyalkyl group having 2 to 6 carbon atoms.
  • a (meth) acrylic acid ester is preferred. Specific examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.
  • the effect of such surface treatment is that the wettability between the inorganic filler and the acrylic resin is improved, so that the viscosity of the varnish is lowered when the varnish is blended, and the coating tends to be easy. Furthermore, the improvement of wettability causes the inorganic filler to be more highly dispersed and contributes to the improvement of thermal conductivity.
  • the content of the structural unit having at least one of carboxy group and hydroxy group contained in the acrylic resin is not particularly limited.
  • the content of the structural unit having at least one of a carboxy group and a hydroxy group in the acrylic resin is preferably 10 mol% or more and 30 mol% or less, and 14 mol% or more and 28 mol% or less. More preferably.
  • the acrylic resin having at least the structural unit represented by the general formula (I) in the molecule preferably further includes at least one amino group in the molecule. It is preferable to include at least one kind of structural unit. Among these, from the viewpoint of preventing moisture absorption, a secondary amino group or a tertiary amino group is preferable. From the viewpoint of improving thermal conductivity, an N-methylpiperidino group is particularly preferable. When an N-methylpiperidino group is present in the acrylic resin, the compatibility is remarkably improved by the interaction with the phenol curing agent, which is preferable. Thus, when the acrylic resin excellent in compatibility is added to the system of a composition, the loss of heat conductivity becomes small. In addition, the interaction between the N-methylpiperidino group and the phenol-based curing agent exhibits a stress relaxation effect due to slippage between different types of molecules, and contributes to an improvement in adhesion.
  • the content of the amino group contained in the acrylic elastomer is not particularly limited.
  • the content of the structural unit having an amino group in the resin constituting the acrylic elastomer is preferably 0.5 mol% or more and 5 mol% or less, and 0.7 mol% or more and 3.5 mol% or less. More preferably, it is at most mol%.
  • R 21 and R 22 are each independently a linear or branched alkyl group having a different carbon number.
  • R 23 to R 26 each independently represents a hydrogen atom or a methyl group.
  • the structural unit present in the proportion of a (hereinafter also referred to as “structural unit a”) can impart flexibility to the sheet, and also has thermal conductivity. And compatibility with flexibility. Further, the structural unit present in the proportion of b (hereinafter also referred to as “structural unit b”) makes the sheet more flexible in combination with the structural unit a shown above.
  • the chain length of the alkyl group represented by R 21 and R 22 in the structural units a and b that imparts a flexible structure (flexibility) is not particularly limited.
  • the chain length of R 21 and R 22 are preferably in the range of 2 to 16 carbon atoms, more preferably in the range of 3 to 14 carbon atoms, and still more preferably in the range of 4 to 12 carbon atoms.
  • the alkyl groups represented by R 21 and R 22 have different carbon numbers.
  • the difference in carbon number between R 21 and R 22 is not particularly limited, but the difference in carbon number is preferably 4 to 10 and more preferably 6 to 8 from the viewpoint of the balance between flexibility and flexibility.
  • R 21 preferably has 2 to 6 carbon atoms
  • R 22 preferably has 8 to 16 carbon atoms
  • R 21 has 3 to 5 carbon atoms. More preferably, R 22 has 10 to 14 carbon atoms.
  • the range of mol% of the structural unit a and the structural unit b is not particularly limited. Further, the ratio between the structural unit a and the structural unit b may be arbitrary. It is preferable to use an acrylic resin including a combination of the structural unit a and the structural unit b, rather than any one of the structural unit a and the structural unit b being included alone.
  • the combination of the structural unit a and the structural unit b may increase the number of side chains and increase the flexibility of the acrylic resin, and may increase the Tg.
  • Tg can be controlled within a suitable range by appropriately adjusting the molar ratios a and b of the structural unit a and the structural unit b in the acrylic resin.
  • the content of the structural unit a is preferably 50 mol% to 85 mol%, more preferably 60 mol% to 80 mol%.
  • the content of the structural unit b is preferably 2 mol% to 20 mol%, more preferably 5 mol% to 15 mol%.
  • the content ratio of the structural unit a to the structural unit b is preferably 4 to 10, and more preferably 6 to 8.
  • the thermal conductivity is improved by the presence of a carboxy group in the acrylic resin derived from a structural unit present in the proportion of c (hereinafter also referred to as “structural unit c”).
  • structural unit c a carboxy group in the acrylic resin derived from a structural unit present in the proportion of c
  • structural unit d an N-methylpiperidino group in the acrylic resin derived from a structural unit present in the proportion of d
  • the N-methylpiperidino group can accept hydrogen ions from a carboxy group and then allows interaction with, for example, phenol contained as a curing agent.
  • the compatibility with the acrylic resin and the composition system is improved by the interaction with phenol.
  • the intramolecular interaction between the carboxy group and the N-methylpiperidino group contributes to the stress relaxation due to the low elasticity. This can be considered, for example, because the entire molecule of the acrylic resin has a curved structure instead of a linear structure. From such a viewpoint, in one embodiment of the acrylic resin represented by the general formula (II), the proportion of the structural unit c and the structural unit d is preferably in the range of 10 mol% to 28 mol%.
  • d is preferably in the range of 0.5 mol% to 5 mol%, more preferably 0.7 mol. % To 3.5 mol%, more preferably 0.7 mol to 1.4 mol%.
  • the content ratio of the structural unit c to the structural unit d is preferably 0.01 to 0.5, more preferably 0.03 to 0.3, and further preferably 0.035 to 0.25.
  • R 23 to R 26 are each independently a hydrogen atom or a methyl group, but it is preferable that at least one of R 23 and R 24 is a hydrogen atom and the other is a methyl group, and R 23 is a hydrogen atom and R 24 is More preferred is a methyl group. Moreover, it is preferable that at least one of R 25 and R 26 is a hydrogen atom and the other is a methyl group, and it is more preferable that R 25 is a hydrogen atom and R 26 is a methyl group.
  • the acrylic resin having the structure represented by the general formula (II) may further contain structural units other than the structural units a to d.
  • the structural unit other than the structural units a to d is not particularly limited.
  • the structural unit derived from the (meth) acrylic acid ester containing a hydroxyalkyl group and the structural unit derived from the (meth) acrylic acid ester containing a tertiary amino group can be mentioned.
  • the content of structural units other than the structural units a to d in the acrylic resin is 10 mol% or less, preferably 5 mol% or less, and more preferably 1 mol% or less.
  • the weight average molecular weight of the elastomer is not particularly limited. Among these, from the viewpoint of thermal conductivity and flexibility, it is preferably 10,000 to 100,000, more preferably 10,000 to 50,000, and preferably 10,000 to 30,000. Further preferred. Furthermore, when the weight average molecular weight of the elastomer is within the above range, the dispersibility of the inorganic filler is further improved and the viscosity of the resin composition tends to be further decreased. The weight average molecular weight of the elastomer is measured by a usual method using GPC.
  • the content of the elastomer is 0. 0 when the total mass of the epoxy resin-containing components (epoxy resin and a curing agent included as necessary) is 100 parts by mass. It can be in the range of 1 to 99 parts by mass, preferably in the range of 1 to 20 parts by mass, and more preferably in the range of 1 to 10 parts by mass.
  • the added amount of the acrylic resin is 0.1 parts by mass or more, a decrease in thermal conductivity tends to be suppressed and the adhesive force with the adherend tends to be improved.
  • the amount is 99 parts by mass or less of the acrylic resin, a decrease in adhesive strength with the adherend is suppressed, and the thermal conductivity tends to be improved. Therefore, it becomes easy to express various characteristics in a well-balanced manner by adjusting the amount of the acrylic resin added to the above range.
  • the resin composition preferably contains at least one curing agent.
  • curing agent there is no restriction
  • the curing agent can be appropriately selected from curing agents usually used as a curing agent for epoxy resins. Specific examples include amine curing agents such as dicyandiamide and aromatic diamine, and phenolic curing agents such as phenol novolac resin, cresol novolac resin, and catechol resorcinol novolak resin.
  • a phenolic curing agent is preferable, and a phenolic curing agent containing a bifunctional phenol such as catechol, resorcinol and p-hydroquinone is preferable.
  • the content of the curing agent in the resin composition is not particularly limited.
  • the epoxy resin it can be 0.1 to 2.0 on an equivalent basis, preferably 0.5 to 1.5 from the viewpoint of improving flexibility, and 0.8 from the viewpoint of high thermal conductivity. It is preferable that it is -1.1. Adhesiveness and heat conductivity can be improved more because the content rate of a hardening
  • curing agent is the said range.
  • the resin composition preferably contains at least one curing catalyst.
  • a curing catalyst there is no restriction
  • the curing catalyst include triphenylphosphine, 2-ethyl-4-methylimidazole, boron trifluoride amine complex, 1-benzyl-2-methylimidazole, and the like. Can be mentioned. Among them, it is preferable to use triphenylphosphine from the viewpoint of achieving high thermal conductivity.
  • the content rate of the curing catalyst in the resin composition is not particularly limited. For example, it can be 0.1% by mass to 2.0% by mass and preferably 0.5% by mass to 1.5% by mass with respect to the epoxy resin. Adhesiveness and heat conductivity can be improved more because the content rate of a curing catalyst is the said range.
  • the resin composition preferably contains at least one coupling agent in addition to the essential components, epoxy resin, elastomer and inorganic filler.
  • the coupling agent can be contained for the purpose of, for example, surface treatment of inorganic filler.
  • the coupling agent is not particularly limited, and can be appropriately selected from commonly used coupling agents. Specifically, for example, methyltrimethoxysilane (available from Shin-Etsu Chemical Co., Ltd., available as trade name “KBM-13”), 3-mercaptopropyltrimethoxysilane (available from Shin-Etsu Chemical Co., Ltd., trade name “KBM-”).
  • the content of the coupling agent in the resin composition is not particularly limited.
  • it can be 0.05% by mass to 1.0% by mass, and preferably 0.1% by mass to 0.5% by mass. Thermal conductivity can be improved more because the content rate of a coupling agent is the said range.
  • the thermally conductive resin composition may contain at least one solvent.
  • the solvent is not particularly limited as long as it does not inhibit the curing reaction of the resin composition, and can be appropriately selected from commonly used organic solvents. Specific examples include ketone solvents such as methyl ethyl ketone and cyclohexanone, and alcohol solvents such as cyclohexanol.
  • the content of the solvent in the heat conductive resin composition is not particularly limited, and can be appropriately selected according to the applicability of the heat conductive resin composition.
  • the resin sheet of the present invention is formed by molding the resin composition into a sheet shape.
  • the said resin sheet can be manufactured by apply
  • the said resin sheet is excellent in thermal conductivity, flexibility, and adhesiveness by being comprised from the said resin composition.
  • the resin sheet is formed from the resin composition into a sheet shape, and is preferably a B stage sheet that is further heat-treated until it is in a semi-cured state (B stage state).
  • the B-stage sheet is a resin sheet having a viscosity of 10 4 Pa ⁇ s to 10 5 Pa ⁇ s at room temperature (25 degrees), whereas it is 10 2 Pa ⁇ s to 10 3 Pa ⁇ s at 100 ° C.
  • the viscosity is reduced to s.
  • the cured resin sheet to be described later is not melted by heating.
  • the viscosity is measured by dynamic viscoelasticity measurement (frequency 1 Hz, load 40 g, temperature increase rate 3 ° C./min).
  • the resin sheet can be manufactured as follows.
  • a resin layer can be obtained by applying and drying a varnish-like resin composition to which a solvent such as methyl ethyl ketone or cyclohexanenon is added on a release film such as a PET film.
  • coating can be implemented by a well-known method. Specific examples of the coating method include comma coating, die coating, lip coating, and gravure coating.
  • a coating method for forming a resin layer with a predetermined thickness a comma coating method in which an object to be coated is passed between gaps, a die coating method in which a resin varnish whose flow rate is adjusted from a nozzle, or the like can be applied. .
  • the thickness of the resin layer before drying is 50 ⁇ m to 500 ⁇ m, it is preferable to use a comma coating method.
  • the conditions for heat-treating the obtained resin layer are not particularly limited as long as the resin composition can be semi-cured to the B stage state, and can be appropriately selected according to the configuration of the resin composition.
  • the heat treatment is preferably a heat treatment method selected from a hot vacuum press and a hot roll laminate.
  • void (void) in the resin layer produced in the case of coating can be reduced, and a flat B stage sheet
  • the resin composition can be semi-cured in a B-stage state by heat-pressing at a heating temperature of 80 ° C. to 130 ° C. for 1 to 30 seconds under reduced pressure (for example, 1 MPa).
  • the thickness of the resin sheet can be appropriately selected according to the purpose. For example, it can be 50 ⁇ m or more and 200 ⁇ m or less, and from the viewpoint of thermal conductivity and sheet flexibility, it is 60 ⁇ m or more and 150 ⁇ m or less. preferable.
  • the resin sheet can also be produced by hot pressing while laminating two or more resin layers.
  • the metal foil with resin of this invention has metal foil and the semi-hardened resin layer which is a semi-hardened material of the said heat conductive resin composition arrange
  • the semi-cured resin layer is obtained by heat-treating the resin composition so as to be in a B-stage state.
  • the metal foil is not particularly limited, such as a gold foil, a copper foil, and an aluminum foil, but generally a copper foil is used.
  • the thickness of the metal foil is not particularly limited as long as it is 1 ⁇ m to 35 ⁇ m, but flexibility is further improved by using a metal foil of 20 ⁇ m or less.
  • nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as the intermediate layers for the metal foil, and 0.5 ⁇ m to 15 ⁇ m copper layer and 10 ⁇ m to 300 ⁇ m on both sides.
  • a composite foil having a three-layer structure provided with a copper layer or a two-layer structure composite foil in which aluminum and copper foil are combined can also be used.
  • the metal foil with resin can be produced by forming a resin layer by applying and drying the thermally conductive resin composition on the metal foil, and the method for forming the resin layer is as described above.
  • the production conditions of the resin-coated metal foil are not particularly limited, but it is preferable that 80% by mass or more of the organic solvent used for the resin varnish is volatilized in the resin layer after drying.
  • the drying temperature is about 80 ° C. to 180 ° C., and the drying time can be determined in consideration of the gelling time of the varnish, and is not particularly limited.
  • the coating amount of the resin varnish is preferably applied so that the thickness of the resin layer after drying is 50 ⁇ m to 200 ⁇ m, and more preferably 60 ⁇ m to 150 ⁇ m.
  • the resin layer after drying becomes a B stage state by heat treatment.
  • the conditions for heat treatment of the thermally conductive resin composition are the same as the heat treatment conditions for the B-stage sheet.
  • the cured resin sheet of the present invention is obtained by heat-treating the thermally conductive resin composition.
  • the curing method for curing the thermally conductive resin composition can be appropriately selected according to the configuration of the thermally conductive resin composition, the purpose of the cured resin sheet, and the like, but is preferably a heat and pressure treatment.
  • the conditions for the heat and pressure treatment are, for example, that the heating temperature is 80 ° C. to 250 ° C., the pressure is preferably 0.5 MPa to 8.0 MPa, the heating temperature is 130 ° C. to 230 ° C., and the pressure is 1.5 MPa to More preferably, it is 5.0 MPa.
  • the treatment time for the heat and pressure treatment can be appropriately selected according to the heating temperature and the like. For example, it can be 2 to 8 hours, and preferably 4 to 6 hours. Further, the heat and pressure treatment may be performed once, or may be performed twice or more by changing the heating temperature or the like.
  • the heat radiating member of the present invention includes at least a metal workpiece and the B stage sheet or the cured resin sheet disposed on the metal workpiece so as to be in contact with the metal workpiece.
  • the “metal workpiece” means a molded product made of a metal material that can function as a heat dissipation member, including a substrate, fins, and the like.
  • the metal workpiece is preferably a substrate composed of various metals such as Al and Cu.
  • FIG. 1 a heat radiating member using a resin sheet obtained by molding the heat conductive resin composition into a sheet is illustrated in FIG.
  • the resin sheet may be a B stage sheet or a cured resin sheet.
  • the resin sheet 10 is located between a first metal workpiece 20 made of, for example, Al and a second metal workpiece 30 made of, for example, Cu, and one surface thereof is on the surface of the metal workpiece 20. The other surface is bonded to the surface of the metal work 30.
  • the resin sheet 10 is excellent in flexibility and can realize excellent adhesiveness with the contact surfaces of the first and second metal workpieces 20 and 30.
  • the resin sheet applied to the adhesion of the metal workpiece desirably has a shear strength of 5 MPa or more from the viewpoint of adhesion.
  • a resin sheet satisfying the above-described shear strength can be provided.
  • the resin sheet 10 has excellent thermal conductivity, for example, the heat generated from the second metal work 30 made of Cu is used as the first metal work made of Al through the resin sheet 10. It becomes possible to conduct efficiently to the 20 side and to dissipate heat to the outside.
  • catechol resorcinol novolak (CRN) resin had a number average molecular weight of 530 and a weight average molecular weight of 930.
  • the hydroxyl equivalent of the CRN resin was 65.
  • the catechol resorcinol novolak (CRN) resin obtained above was used in the following examples.
  • Example 1 The elastomer used in the following examples was synthesized with reference to Japanese Patent Application Laid-Open No. 2010-106220. According to the structure of the elastomer, an appropriate solvent was used, and the monomer components were mixed with a polymerization initiator and the like so as to have a desired ratio, stirred, heated and copolymerized.
  • Example 1 1.
  • the obtained resin sheet coating solution is applied to a release surface of a polyethylene terephthalate film (Fujimori Kogyo Co., Ltd., 75E-0010CTR-4, hereinafter abbreviated as PET film) to a thickness of about 300 ⁇ m. It was coated and allowed to stand for 15 minutes in a normal state, and then dried in a box oven at 100 ° C. for 30 minutes to form a resin composition layer on the PET film. Next, the upper surface of the resin composition layer that has been in contact with air is covered with a PET film, and flattened by hot pressing (upper hot plate 150 ° C., lower hot plate 80 ° C., pressure 1.5 MPa, treatment time 3 minutes). A B-stage sheet was obtained as an elastomer-containing resin sheet having a thickness of 200 ⁇ m. When the flexibility of the obtained B-stage sheet was evaluated as follows, it was good and was A.
  • FIG. 2 is a schematic cross-sectional view for explaining the state of the sheet in determining the flexibility of the sheet.
  • reference numeral 10 denotes a resin sheet
  • 40 denotes a support.
  • FIG. 2 (a) shows a state in which the elastomer is not added and the flexibility of the sheet is poor
  • FIG. 2 (b) shows a state in which the flexibility of the sheet is improved by adding an elastomer having a specific structure. .
  • the thermal diffusivity of the sheet was measured using a Nanoflash LFA447 Xe flash method thermal diffusivity measuring apparatus manufactured by NETZSCH.
  • the thermal conductivity (W / mK) was calculated by multiplying the numerical value of the obtained thermal diffusivity by the specific heat Cp (J / g ⁇ K) and the density d (g / cm 3 ). All measurements were performed at 25 ⁇ 1 ° C.
  • Example 2 An acrylic resin (REB124-6) was used in the same manner as in Example 1 except that “REB124-6” (weight average molecular weight 44000) having the following structural formula was used instead of “REB122-4” as the acrylic resin.
  • A) B-stage sheet was prepared. When the flexibility of the obtained B-stage sheet was evaluated in the same manner as in Example 1, it was good and the evaluation was A.
  • a cured B-stage sheet containing REB124-6 was produced in the same manner as in Example 1.
  • the thermal conductivity was 7.0 W / mK.
  • a metal workpiece on which a B stage sheet containing REB124-6 was attached was produced.
  • the shear adhesive strength of the obtained metal workpiece was measured in the same manner as in Example 1, it was 7.4 [MPa].
  • Example 3 An acrylic resin (REB58-5) was used in the same manner as in Example 1 except that “REB58-5” (weight average molecular weight 34000) having the following structural formula was used instead of “REB122-4” as the acrylic resin. A) B-stage sheet was prepared. The flexibility of the obtained B stage sheet was good.
  • a cured B-stage sheet containing REB58-5 was produced in the same manner as in Example 1.
  • the thermal conductivity was 6.8 W / mK.
  • a metal workpiece on which a B stage sheet containing REB58-5 was attached was produced.
  • the shear adhesive strength of the obtained metal workpiece was measured in the same manner as in Example 1, it was 7.6 [MPa].
  • Example 4 An acrylic resin (REB124-2) was used in the same manner as in Example 1 except that “REB124-2” (weight average molecular weight 39000) having the following structural formula was used instead of “REB122-4”. A) B-stage sheet was prepared. When the flexibility of the obtained B-stage sheet was evaluated in the same manner as in Example 1, it was good and the evaluation was A.
  • a cured B-stage sheet containing REB 124-2 was produced in the same manner as in Example 1.
  • the thermal conductivity was 5.5 W / mK.
  • a metal workpiece on which a B stage sheet containing REB 124-2 was attached was produced.
  • the shear adhesive strength of the obtained metal workpiece was measured in the same manner as in Example 1, it was 5.0 [MPa].
  • Example 5 An acrylic resin (REB 146-2) was used in the same manner as in Example 1 except that “REB 146-2” (weight average molecular weight 43081) having the following structural formula was used instead of “REB 122-4” as the acrylic resin.
  • A) B-stage sheet was prepared. When the flexibility of the obtained B-stage sheet was evaluated in the same manner as in Example 1, it was good and the evaluation was A.
  • Example 1 a cured product of a B stage sheet containing REB 146-2 was produced in the same manner as in Example 1.
  • the thermal conductivity was 6.0 W / mK.
  • a metal workpiece on which a B stage sheet containing REB 146-2 was attached was produced.
  • the shear adhesive strength of the obtained metal workpiece was measured in the same manner as in Example 1, it was 5.1 [MPa].
  • Example 6 An acrylic resin (REB100-5) was used in the same manner as in Example 1 except that “REB100-5” (weight average molecular weight 25000) having the following structural formula was used instead of “REB122-4” as the acrylic resin. A) B-stage sheet was prepared. When the flexibility of the obtained B-stage sheet was evaluated in the same manner as in Example 1, it was good and the evaluation was A.
  • Example 1 a cured B stage sheet containing REB 100-5 was produced.
  • the thermal conductivity was 7.0 W / mK.
  • a metal workpiece on which a B stage sheet containing REB 100-5 was attached was produced.
  • the shear adhesive strength of the obtained metal workpiece was measured in the same manner as in Example 1, it was 5.0 [MPa].
  • Comparative Example 1 Preparation of Elastomer-Free Resin Sheet
  • 0.0960 parts by mass of 3-glycidyloxypropyltrimethoxysilane (trade name “KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) was used in the same manner as in Example 1.
  • CRN catechol resorcinol novolak
  • the coating solution obtained above is adjusted to a thickness of about 300 ⁇ m on the release surface of a polyethylene terephthalate film (Fujimori Kogyo Co., Ltd., 75E-0010CTR-4, hereinafter abbreviated as PET film).
  • PET film polyethylene terephthalate film
  • the flexibility of the obtained B-stage sheet was evaluated in the same manner as in Example 1, the sheet was fragile and judged as B.
  • Example 2 a metal workpiece on which a B-stage sheet containing X-22-162C was attached was produced. However, since the cured product was brittle, it could not be bonded to the metal, and the shear strength could not be measured. It was.
  • Example 3 Comparative Example 3 Except that a nitrile resin (manufactured by ZEON Corporation, trade name “Nipol DN601”) was used instead of “REB122-4” (acrylic resin), B containing Nipol DN601 was the same as in Example 1. A stage sheet was prepared. When the flexibility of the obtained B-stage sheet was evaluated in the same manner as in Example 1, the sheet was fragile and judged as B.
  • a nitrile resin manufactured by ZEON Corporation, trade name “Nipol DN601”
  • REB122-4 acrylic resin
  • Table 1 summarizes the examination results of the thermal conductivity and flexibility of the heat conductive sheets prepared in Examples 1 to 5 and Comparative Examples 1 to 3, and the shear bond strength of the metal workpiece using the sheets.
  • the resin sheet composed of the heat conductive resin composition of the present invention is excellent in flexibility and adhesiveness. Moreover, it turns out that the resin sheet hardened

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne une composition de résine thermoconductrice qui comprend une résine époxy, une charge inorganique et un élastomère comprenant au moins une unité structurale représentée par la formule générale (I) dans la molécule. Dans la formule (I), R1, R2 et R3 représentent indépendamment un groupe alkyle linéaire ou ramifié ou un atome d'hydrogène ; R4 représente un groupe alkyle linéaire ou ramifié ; et n représente un entier arbitraire.
PCT/JP2011/070863 2010-09-22 2011-09-13 Composition de résine thermoconductrice, feuille de résine, feuille métallique revêtue de résine, feuille de résine durcie et élément dissipateur de chaleur WO2012039324A1 (fr)

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WO2022075227A1 (fr) * 2020-10-06 2022-04-14 デンカ株式会社 Composition, corps durci, et substrat de base en métal
CN114716953A (zh) * 2022-04-18 2022-07-08 上海燊量科技有限公司 一种钢丝绳索具浇注用树脂胶黏剂及其制备方法和应用
CN116234842A (zh) * 2020-10-06 2023-06-06 电化株式会社 组合物及其制造方法、固化体以及金属基底基板
WO2023189609A1 (fr) * 2022-03-31 2023-10-05 デンカ株式会社 Composition de résine, corps durci en résine isolante, stratifié et substrat de circuit
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JP2018021163A (ja) * 2016-08-05 2018-02-08 スリーエム イノベイティブ プロパティズ カンパニー 放熱用樹脂組成物、その硬化物、及びこれらの使用方法
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CN116234841A (zh) * 2020-10-06 2023-06-06 电化株式会社 组合物、固化体及金属基底基板
CN116234842A (zh) * 2020-10-06 2023-06-06 电化株式会社 组合物及其制造方法、固化体以及金属基底基板
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WO2023189609A1 (fr) * 2022-03-31 2023-10-05 デンカ株式会社 Composition de résine, corps durci en résine isolante, stratifié et substrat de circuit
WO2023189610A1 (fr) * 2022-03-31 2023-10-05 デンカ株式会社 Composition de résine, corps durci en résine isolante, stratifié et substrat de circuit
CN114716953A (zh) * 2022-04-18 2022-07-08 上海燊量科技有限公司 一种钢丝绳索具浇注用树脂胶黏剂及其制备方法和应用
CN114716953B (zh) * 2022-04-18 2024-01-05 上海燊量科技有限公司 一种钢丝绳索具浇注用树脂胶黏剂及其制备方法和应用

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