WO2013161606A1 - Epoxy resin composition, resin sheet, cured article, and phenoxy resin - Google Patents
Epoxy resin composition, resin sheet, cured article, and phenoxy resin Download PDFInfo
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- WO2013161606A1 WO2013161606A1 PCT/JP2013/061178 JP2013061178W WO2013161606A1 WO 2013161606 A1 WO2013161606 A1 WO 2013161606A1 JP 2013061178 W JP2013061178 W JP 2013061178W WO 2013161606 A1 WO2013161606 A1 WO 2013161606A1
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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
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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Definitions
- the present invention relates to an epoxy resin composition used in the field of electronic materials, a resin sheet and a cured product using the epoxy resin composition, and a phenoxy resin used in the epoxy resin composition.
- Epoxy resins are widely used in electronic parts, electrical equipment, automobile parts, FRP, sports equipment and the like because they are excellent in adhesiveness, heat resistance and moldability. In particular, in recent years, it is one of materials that have attracted much attention in the field of electronic materials (for example, Non-Patent Document 1).
- an epoxy resin composition containing an epoxy resin monomer having a biphenyl group or a biphenyl derivative, a dihydric or higher phenol having a hydroxyl group disposed at least in the ortho position, and a curing accelerator has also been proposed (for example, Patent Document 1).
- the cured product using this epoxy resin composition has improved thermal conductivity, but no specific solution has been shown for the problem of crystal precipitation in the varnish state.
- an object of the present invention is to provide a resin composition having no thermal precipitation in the state of varnish dissolved in a solvent and having excellent thermal conductivity in the state of a cured product.
- the present inventors have intensively studied to increase the solubility of the epoxy resin in a varnish state, and as a result, by adding an amorphous phenoxy resin having a specific structure to the epoxy resin.
- the inventors have found that the precipitation of epoxy resin crystals in the varnish can be prevented.
- the above amorphous phenoxy resin has a highly symmetrical structure, it becomes a uniform resin solution without precipitating crystals in the varnish. It has also been found that phenoxy resin exhibits higher thermal conductivity than general-purpose phenoxy resin.
- the epoxy resin composition of the present invention comprises the following components (a) to (c): (A) epoxy resin, (B) a curing agent, and (c) an amorphous phenoxy resin having a weight average molecular weight represented by the following general formula (1) in the range of 10,000 to 200,000, Is an epoxy resin composition containing
- the component (a) contains a crystalline epoxy resin having a mesogenic group within a range of 5 to 100% by weight based on the total amount of the component (a).
- Component) is contained within a range of 5 to 90 parts by weight with respect to 100 parts by weight of the total solid content in the components (a) and (c).
- X means a biphenylene skeleton represented by the following formula (2) or a naphthalene skeleton represented by the following formula (3)
- Y represents a biphenylene represented by the following formula (2)
- Z means a hydrogen atom or a glycidyl group
- n means a number representing a repeating unit.
- R 1 to R 8 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
- the mesogenic group may be a biphenylene group.
- the mesogenic group may be a naphthalene group.
- the component (c) may be an amorphous phenoxy resin in which X and Y in the formula (1) have a biphenylene skeleton represented by the formula (2). .
- At least four of R 1 to R 8 in the formula (2) may be an alkyl group having 4 or less carbon atoms, and the rest May be a biphenylene skeleton in which is a hydrogen atom.
- Y may be an unsubstituted biphenylene skeleton in which all of R 1 to R 8 in the formula (2) are hydrogen atoms.
- X may be a tetraalkylbiphenylene group in which an alkyl group having 4 or less carbon atoms is substituted at the 3,3′-position and the 5,5′-position.
- Y may be an unsubstituted biphenylene group.
- the component (c) may be an amorphous phenoxy resin having a naphthalene skeleton in which X is represented by the formula (3) in the formula (1).
- X may be a naphthalene skeleton having a single bond at each of the 1-position and the 6-position, and Y is R 1 to R 1 in the formula (2).
- An unsubstituted biphenylene skeleton in which all of R 8 are hydrogen atoms may be used.
- the epoxy resin composition of the present invention further comprises the following components (d), (D) inorganic filler, May be contained.
- the epoxy resin composition of the present invention further comprises the following components (e), (E) solvent, May be contained.
- the resin sheet of the present invention is obtained by forming any of the above epoxy resin compositions into a film.
- the cured product of the present invention is obtained by curing any of the above epoxy resin compositions.
- the phenoxy resin of the present invention has a tetramethylbiphenylene group substituted with a methyl group at the 3,3′-position and the 5,5′-position, and an unsubstituted biphenylene group, and has a weight average molecular weight of 10,000 to 200,000. Is within the range.
- the molar ratio of the tetramethylbiphenylene group substituted with a methyl group at the 3,3′-position and the 5,5′-position to the unsubstituted biphenylene group may be approximately 1: 1.
- the epoxy resin composition of the present invention comprises a combination of a crystalline epoxy resin having a mesogenic group and an amorphous phenoxy resin represented by the formula (1), so that the epoxy resin is solubilized in a solvent and varnished. It is possible to impart excellent thermal conductivity to the cured product while preventing precipitation of crystals therein. That is, by blending the amorphous phenoxy resin represented by the formula (1), the crystalline epoxy resin having a mesogenic group is solubilized, and a uniform resin composition can be obtained in a varnish state. Further, by applying and drying, molding into a resin sheet or the like can be easily performed. Moreover, the hardened
- the epoxy resin composition of the present invention can provide molded products and cured products such as a curable resin sheet, a curable high heat dissipation resin sheet, an insulating sheet, a prepreg, and an adhesive film excellent in thermal conductivity.
- the epoxy resin composition of the present embodiment contains the above components (A) to (C). Hereinafter, each component will be described.
- Epoxy resin for example, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, o-cresol novolak Exemplified epoxy resins with two or more epoxy groups in the molecule such as epoxy resin, biphenyl novolac epoxy resin, triphenylmethane epoxy resin, dicyclopentadiene epoxy resin, alicyclic epoxy resin, brominated epoxy resin can do. These epoxy resins can be used alone or in combination of two or more.
- the component (a) preferably contains a crystalline epoxy resin having a mesogenic group within a range of 5 to 100% by weight with respect to the total amount of the component (a).
- the crystalline epoxy resin having a mesogenic group is a solid epoxy resin having a softening point of 40 ° C. or higher.
- the mesogenic group for example, a biphenylene group or a naphthalene group is preferable.
- the biphenyl type epoxy resin and the naphthalene type epoxy resin are preferable as the crystalline epoxy resin having a mesogenic group.
- the crystallinity means that an endothermic peak temperature based on the melting point can be confirmed in DSC (differential scanning calorimetry).
- Specific examples of crystalline epoxy resins having mesogenic groups include Nippon Steel & Sumikin Chemical Co., Ltd.
- GK-3007 (biphenol aralkyl type epoxy resin), Mitsubishi Chemical Corporation YX-4000 (tetramethylbiphenol type epoxy resin), Mitsubishi Chemical Examples include YL-6121H manufactured by Nippon Kayaku Co., Ltd., NC-3000 (biphenylene aralkylphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., EPPN-501H (triphenylmethane type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like.
- the content of the component (a) epoxy resin is preferably within the range of 10 to 95 parts by weight, for example, with respect to 100 parts by weight of the total solids in the components (a) and (c), and 30 to 90 parts. More preferably within the range of parts by weight.
- the content of the epoxy resin as the component (a) is more than 95 parts by weight with respect to 100 parts by weight of the solid content, the workability of the epoxy resin composition in the B-stage state is deteriorated or the cured product becomes brittle. In some cases, the adhesive strength, heat resistance, temperature cycle resistance, etc. may decrease.
- the component (a) is a crystalline epoxy resin and the above upper limit is exceeded, the solvent solubility is lowered, and it becomes difficult to form a film of the epoxy resin composition.
- the content of the epoxy resin of component (a) is less than 10 parts by weight with respect to 100 parts by weight of the solid content, the epoxy resin composition is insufficiently cured, resulting in a decrease in adhesive strength and a decrease in heat resistance. May occur.
- the component (b) is a crystalline epoxy resin, if the component is below the lower limit, the resin sheet in the B-stage state becomes hard and easily broken.
- the solid content in the components (A) and (C) is, for example, when the epoxy resin composition is a varnish containing a predetermined solvent, and uses this varnish to form a cured product such as an insulating adhesive layer.
- the solid content in the components (a) and (c) that remains after the solvent is removed by drying or curing is meant.
- the varnish is a solvent containing a solvent for the purpose of reducing the viscosity of the epoxy resin composition and improving the workability. By doing so, a B-stage resin sheet can be obtained. Moreover, after impregnating the obtained varnish in a glass cloth etc., it can obtain a prepreg by drying. The solvent is removed by these drying steps.
- the content rate of the component in the epoxy resin composition of this Embodiment was prescribed
- ⁇ (B) component curing agent>
- the component (b) curing agent is blended for the purpose of curing the epoxy resin.
- an insulating layer an adhesive layer or a resin film is produced from the epoxy resin composition, sufficient insulation and adhesion are obtained. , Impart heat resistance, mechanical strength, etc.
- an imidazole curing agent or a non-imidazole curing agent can be used as the (b) component curing agent used in the present embodiment.
- the imidazole curing agent is preferably composed only of an imidazole compound.
- the imidazole-based curing agent can suppress the increase in viscosity of the epoxy resin composition, and the handling of the epoxy resin composition after blending becomes relatively easy.
- Examples of the imidazole compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, and 2-phenyl. Examples include -4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
- 2-phenyl-4,5-dihydroxymethylimidazole is most preferably used.
- 2-Phenyl-4,5-dihydroxymethylimidazole is a high-potency curing agent, and does not proceed with the curing reaction in the drying process when preparing a B-stage resin sheet, and is stable during long-term storage. Has excellent characteristics.
- the imidazole compound is usually often blended as a curing accelerator in a resin composition mainly composed of an epoxy resin.
- a resin composition mainly composed of an epoxy resin.
- the epoxy resin composition of the present embodiment when an imidazole-based curing agent is used, since no curing agent component other than the imidazole compound is used, the epoxy resin composition is subjected to anionic polymerization that proceeds from the imidazole compound. Can be cured. From such reaction characteristics, in the epoxy resin composition of the present embodiment, the imidazole compound can function as a curing agent, and compared with a reaction system in which an addition type curing agent component is blended, the blending as a curing agent. The amount can be kept low.
- the imidazole compound is a catalyst type curing agent, for example, if an addition type curing agent component such as dicyandiamide or a novolac type phenol resin is present, the addition type curing agent component and the epoxy resin react preferentially. However, the condensation reaction with the epoxy resin alone is unlikely to occur.
- an addition type curing agent component such as dicyandiamide or a novolac type phenol resin
- the content when using an imidazole-based curing agent comprising an imidazole compound as the component (b) is, for example, 0.01 to 10 parts by weight relative to a total of 100 parts by weight of the solid content in the components (a) to (c). Is preferably within the range of 0.01 to 5 parts by weight.
- the content of the imidazole curing agent is more than 10 parts by weight, there is a risk of inducing a halogen element derived from the epoxy resin as a halogen ion.
- the content of the imidazole-based curing agent is less than 0.01 parts by weight, the curing reaction does not proceed sufficiently, the adhesive strength is reduced, or the curing time is prolonged and the usability is reduced. There is.
- non-imidazole curing agent examples include those known as epoxy resin curing agents such as novolak-type phenol resin, dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone.
- the non-imidazole curing agent is preferably blended so that the equivalent ratio ((b) / (b)) to the epoxy resin of component (b) is 0.5 to 1.5.
- the range when using a phenol resin-based curing agent, the range is preferably 0.8 to 1.2, and when using an amine-based curing agent, the range is preferably 0.5 to 1.0.
- a curing accelerator in addition to the components (a) to (c).
- a curing accelerator for example, organophosphorus compounds such as triphenylphosphine, imidazoles such as 2-phenylimidazole and 2-ethyl-4-methylimidazole, and the like can be used.
- the blending ratio is appropriately selected according to the required curing time, but is generally 0.01 to 3.0 with respect to 100 parts by weight of the total solids in the components (a) to (c). Within the range of parts by weight is preferred.
- the amorphous phenoxy resin as the component (c) has a biphenylene skeleton or a naphthalene skeleton.
- Amorphous phenoxy resin prevents precipitation of crystals when the epoxy resin composition is in a varnish state and maintains a dissolved state in an organic solvent, and from the epoxy resin composition to an insulating layer, an adhesive layer, and a resin film. It is a component which improves the flexibility at the time of producing.
- the amorphous phenoxy resin having a biphenylene skeleton or a naphthalene skeleton is represented, for example, by the following general formula (1).
- X means a biphenylene skeleton represented by the following formula (2) or a naphthalene skeleton represented by the following formula (3)
- Y represents a biphenylene skeleton represented by the following formula (2).
- Z represents a hydrogen atom or a glycidyl group, and n represents a number representing a repeating unit.
- R 1 to R 8 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
- the ratio of X and Y is about 1: 1, but there may be a slight difference in the contents of X and Y.
- the molecular weight of the component (c) amorphous phenoxy resin is designed by the molar ratio of the starting compounds, and the desired product is generally obtained while controlling the reaction temperature and reaction time. It can be designed so that the end of the main chain is an epoxy group or a phenolic hydroxyl group depending on the molar ratio of the raw materials used.
- the non-crystalline phenoxy resin represented by the general formula (1) is substantially the same compound as the epoxy resin, but is called because it has different properties due to a difference in molecular weight. That is, the epoxy resin refers to those having a small molecular weight, and the phenoxy resin refers to those having a large molecular weight. Although there is no clear boundary, generally those having a weight average molecular weight of 10,000 or more are called phenoxy resins.
- the phenoxy resin is distinguished from the epoxy resin because the characteristic as a thermoplastic resin appears more strongly than the characteristic as a thermosetting resin because there are few epoxy groups as reaction points with respect to the molecular size.
- Epoxy resins and phenoxy resins are produced in various molecular weights depending on the purpose. Since the average molecular weight of the epoxy resin described in Patent Document 1 is about 300 to 400, it corresponds to the epoxy resin according to the above classification.
- the weight average molecular weight of the amorphous phenoxy resin as component (c) is, for example, in the range of 10,000 to 200,000, and more preferably in the range of 20,000 to 100,000.
- the weight average molecular weight of the amorphous phenoxy resin is less than 10,000, the self-film forming property is poor, and the sheet or film becomes fragile and is difficult to handle.
- a weight average molecular weight exceeds 200,000, the problem that an amorphous phenoxy resin becomes difficult to melt
- the weight average molecular weight here is a value in terms of polystyrene by GPC (gel permeation chromatography) measurement.
- amorphous phenoxy resin of component (c) include those in which X and Y in formula (1) are both a biphenylene skeleton represented by formula (2).
- X and Y in formula (1) are both a biphenylene skeleton represented by formula (2).
- at least for X, in formula (2) at least four of R 1 to R 8 are preferably alkyl groups having 4 or less carbon atoms, and the rest are hydrogen atoms, and Y is the same as X Or an unsubstituted biphenyl skeleton in which R 1 to R 8 in formula (2) are all hydrogen atoms.
- X in the formula (1) is in the 3,3 ′ position and the 5,5 ′ position, or the 2,2 ′ position and the 6,6 ′ position.
- a phenoxy resin having a weight average molecular weight in the range of 10,000 to 200,000 is more preferable.
- X in the formula (1) may be 3,3 ′, 5,5′-tetramethylbiphenylene group, and Y may be an unsubstituted biphenylene group. Particularly preferred.
- X in the formula (1) is a naphthalene skeleton represented by the formula (3), and Y is represented by the formula (2). And those having a biphenylene skeleton.
- X is preferably an asymmetrical position of the single bond of the naphthalene skeleton in Formula (3), and Y is an unsubstituted group in which R 1 to R 8 in Formula (2) are all hydrogen atoms.
- the biphenyl skeleton is preferable.
- the position of the single bond of the naphthalene skeleton is asymmetric
- the formula (3) one having a single bond at the 1-position and 6-position, or the 1-position and the 7-position of the naphthalene skeleton is preferable.
- the position of the single bond of the naphthalene skeleton is asymmetric, the molecular chain is difficult to be oriented due to structural hindrance, so that a liquid phenoxy resin soluble in a solvent can be obtained.
- the non-crystalline phenoxy resin of component (c) is preferably one in which X in formula (1) is a naphthalene skeleton having a bond at an asymmetric position, and Y is an unsubstituted biphenylene skeleton.
- X in formula (1) is a naphthalene skeleton having a bond at an asymmetric position
- Y is an unsubstituted biphenylene skeleton.
- a phenoxy resin having a weight average molecular weight in the range of 10,000 to 200,000 is more preferable.
- the content of the amorphous phenoxy resin as the component (c) is preferably in the range of 5 to 90 parts by weight, for example, with respect to 100 parts by weight of the total solids in the components (a) and (c). A range of 10 to 70 parts by weight is more preferable.
- the content of the amorphous phenoxy resin is more than 90 parts by weight with respect to the total of 100 parts by weight of the solid content, the viscosity of the varnish increases, and the workability and adhesion as an insulating layer and an adhesive layer are increased. May deteriorate, the surface condition may deteriorate, and the heat resistance may be reduced.
- it when it is set as a resin sheet, it will become hard and it will be easy to break, and handling property will fall.
- the content of the amorphous phenoxy resin is less than 5 parts by weight with respect to the total solid content of 100 parts by weight, crystals of the epoxy resin of the component (a) precipitate in the varnish state, resulting in poor curing. Cause it to happen.
- the (a) component epoxy resin containing the crystalline epoxy resin having a mesogenic group is blended with the (c) component amorphous phenoxy resin, thereby combining the varnish. While effectively preventing crystal formation in this state, excellent thermal conductivity can be imparted to the cured product.
- the compounding ratio of the component (c) to the crystalline epoxy resin having a mesogenic group of the component (a) in the epoxy resin composition of the present embodiment [crystals having a mesogenic group at (ha) / (a) The epoxy resin] is preferably in the range of 0.35 to 10, for example.
- the amorphous phenoxy resin represented by the general formula (1) is represented by, for example, an epoxy compound having two epoxy groups in one molecule represented by the following general formula (4) and the following general formula (5).
- a method of reacting a compound having two aromatic hydroxyl groups in one molecule in the presence of a polymerization catalyst, or two aromatic hydroxyl groups in one molecule represented by the following general formula (5) It can be produced by a publicly known and commonly used method of reacting a compound having an epihalohydrin with an alkali metal hydroxide.
- an epihalohydrin with an alkali metal hydroxide.
- an alkali metal hydroxide For example, epichlorohydrin is preferable.
- X and Y in the above formulas (4) and (5) have the same meanings as described above.
- an epoxy compound having two epoxy groups in one molecule represented by the general formula (4) for example, YX-4000 (tetramethylbiphenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation, manufactured by Mitsubishi Chemical Corporation YL-6121H and the like.
- a solvent, a rubber component, a fluorine-based or silicone-based antifoaming agent, a leveling agent, and the like can be added to the epoxy resin composition of the present embodiment as necessary.
- an adhesion imparting agent such as a silane coupling agent or a thermoplastic oligomer can be added.
- the inorganic filler examples include alumina, silica, boron nitride, aluminum nitride, silicon nitride, calcium carbonate, magnesium carbonate and the like.
- the organic filler examples include silicon powder, nylon powder, acrylonitrile-butadiene-based crosslinked rubber, and the like. About these fillers, 1 type (s) or 2 or more types can be used.
- the epoxy resin composition of the present embodiment can be blended with a colorant such as phthalocyanine / green, phthalocyanine / blue, or carbon black, if necessary.
- examples of the alumina as the inorganic filler include crystalline alumina, fused alumina and the like, and among these, crystalline spherical alumina powder is particularly preferable.
- Crystalline alumina is excellent in the effect of increasing the thermal conductivity as compared with fused alumina.
- the use of spherical alumina also has an effect of lowering the viscosity when used as a varnish or the melt viscosity when used as a resin film as compared with crushed alumina. From the viewpoint of achieving high thermal conductivity by close packing, it is preferable that the sphericity of the spherical alumina powder is 95% or more.
- the maximum particle size of spherical alumina powder has a great influence on thermal conductivity and insulation.
- a conductive path when a voltage is applied is formed on the surface of the spherical alumina powder. Therefore, if the maximum particle diameter is set so that a plurality of spherical alumina particles can be arranged in the thickness direction of the cured product, the conductive path becomes longer and the number of insulation points between the particles increases, so that the withstand voltage increases, but heat dissipation Sex is reduced. Therefore, the maximum particle diameter of the spherical alumina powder is preferably determined in consideration of the balance between voltage resistance and heat dissipation.
- the content is preferably 50 to 95% by weight with respect to the solid content of the epoxy resin composition, and is preferably 75 to 94. More preferably, it is% by weight.
- the higher the content of the spherical alumina powder in the epoxy resin composition the higher the thermal conductivity and the lower the thermal expansion. If the content of the spherical alumina powder with respect to the solid content of the epoxy resin composition is less than 50% by weight, the effect of improving the thermal conductivity becomes insufficient, and sufficient heat dissipation may not be exhibited.
- the content of the spherical alumina powder with respect to the solid content of the epoxy resin composition is more than 95% by weight, the viscosity when used as a varnish increases or the melt viscosity when used as an adhesive film increases.
- the workability, withstand voltage characteristics, and adhesiveness of the adhesive layer may be deteriorated or the surface state may be deteriorated.
- the epoxy resin composition of the present embodiment can be prepared by mixing the above essential components and optional components. In this case, it is preferable to use a varnish containing a solvent. That is, the epoxy resin composition of the present embodiment may be dissolved or dispersed in a predetermined solvent to form a varnish.
- Solvents that can be used for the varnish include amide solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), 1-methoxy-2-propano- A mixture of one or more of ether solvents such as methyl ether, methyl ethyl ketone, methyl isobutyl ketone (MIBK), ketone solvents such as cyclohexanone and cyclopentanone, aromatic solvents such as toluene and xylene, etc. it can.
- amide solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), 1-methoxy-2-propano-
- ether solvents such as methyl ether, methyl ethyl ketone, methyl isobutyl ketone (MIBK), ketone solvents such as
- the varnish can be prepared, for example, according to the following procedure. First, the amorphous phenoxy resin of component (c) is dissolved in a suitable solvent while stirring in a container with a stirrer. Next, the varnish can be prepared by mixing the epoxy resin of the component (A), the curing agent of the component (B), and an optional component with this solution, stirring, and dissolving or uniformly dispersing. Depending on the type of component (a) epoxy resin, an epoxy resin may be separately prepared in a solvent and mixed. As described above, the epoxy resin composition of the present embodiment is a combination of a crystalline epoxy resin having a mesogenic group and a non-crystalline phenoxy resin, whereby a varnish of a crystalline epoxy resin having a mesogenic group is used. The precipitation of crystals can be suppressed. Therefore, it becomes possible to obtain a uniform epoxy resin composition in the state of varnish, and further, it is easy to mold the resin sheet or the like by coating and drying.
- the viscosity of the varnish is preferably in the range of 1000 to 20000 Pa ⁇ s, more preferably in the range of 2000 to 10000 Pa ⁇ s.
- the viscosity of the varnish is less than 1000 Pa ⁇ s, the spherical filler is liable to settle, and unevenness and repelling during coating are likely to occur.
- the viscosity of the varnish is larger than 20000 Pa ⁇ s, the coating property is lowered due to the decrease in fluidity, and it becomes difficult to produce a uniform coating film.
- the resin sheet of a B-stage state can be formed by apply
- the copper foil with a resin sheet can also be formed by apply
- the epoxy resin composition of the present embodiment is obtained by combining the crystalline epoxy resin having a mesogenic group and the amorphous phenoxy resin, thereby improving the flexibility of the resin sheet, and further varnishing. As a result of suppressing the precipitation of crystals therein, the generation of cracks can also be suppressed.
- the ratio of the solid resin component which occupies for an epoxy resin composition can be restrained low.
- the amount of the imidazole compound as a curing agent can be reduced as compared with, for example, a case where a phenol novolac-based curing agent component is blended. Therefore, it becomes possible to mix
- the higher the solvent residual rate the better the film supportability.
- the solvent residual ratio is preferably 5% by weight or less.
- a solvent residual rate is the value calculated
- the support material used when forming a resin sheet or a copper foil with a resin sheet examples include polyethylene terephthalate (PET), polyethylene, copper foil, aluminum foil, release paper, and the like.
- PET polyethylene terephthalate
- the thickness of the support material can be set to 10 to 100 ⁇ m, for example.
- metal foil such as copper foil and aluminum foil, as the support material
- the metal foil may be manufactured by, for example, an electrolytic method, a rolling method, or the like.
- the surface on the side in contact with the insulating layer is preferably roughened from the viewpoint of enhancing the adhesion to the insulating layer.
- the resin sheet or the copper foil with a resin sheet is laminated on a base film as a support material, and then the other surface that is not in contact with the copper foil is covered with a film as a protective material and wound into a roll.
- a protective material used at this time include polyethylene terephthalate, polyethylene, release paper, and the like.
- the thickness of the protective material can be in the range of 10 to 100 ⁇ m, for example.
- the cured product of this embodiment is prepared by, for example, preparing the B-stage resin sheet (or copper foil with a resin sheet) from the epoxy resin composition and then heating it to a temperature in the range of 150 ° C. to 250 ° C., for example. Can be produced by curing.
- the cured product thus obtained does not have crystallinity but has excellent thermal conductivity.
- the thermal conductivity of the cured product is preferably, for example, 10 W / mK or more, and more preferably 13 W / mK or more.
- the cured product has a thermal conductivity of 10 W / mK or more, it has excellent heat dissipation characteristics and can be applied to a circuit board or the like used in a high temperature environment.
- the thickness of the aluminum substrate is not particularly limited, but can generally be set to 0.5 to 3.0 mm, for example.
- an aluminum base circuit board composed of a conductor layer made of copper, an insulating adhesive layer, and an aluminum layer using the epoxy resin composition of the present embodiment
- a releasability is imparted.
- the release PET is peeled off, sandwiched between an aluminum substrate and a copper foil, and cured by heating and pressing, an adhesive layer is formed on the aluminum substrate surface, and this adhesive layer
- a method of placing a copper foil on the substrate and curing it while heating and pressing, or a method of forming an insulating adhesive layer on the aluminum substrate surface and curing it, and then forming a copper conductor layer by copper plating, etc. May be adopted.
- any of a method of volatilizing the solvent by heating after applying the varnish, a method of applying a solventless paste, or a method of bonding the resin sheet may be used.
- the weight average molecular weight of the phenoxy resin was analyzed using gel permeation chromatography. Specifically, an HLC-8320 main body manufactured by Tosoh Corporation and a column manufactured by Tosoh Corporation, TSK-gel GMHXL, TSK-gel GMHXL, and TSK-gel G2000H were used in series. Tetrahydrofuran was used as the eluent, and the flow rate was 1 ml / min. The temperature of the column chamber was 40 degrees. Detection was performed using an RI detector. The weight average molecular weight was determined using a standard polystyrene calibration curve.
- Non-volatile content of phenoxy resin solution The nonvolatile content of the phenoxy resin solution was obtained by weighing about 1 g of a sample in an aluminum cup, drying in a hot air circulation oven at 200 ° C. for 1 hour, and calculating the nonvolatile content based on the remaining weight without volatilization. .
- Synthesis Example 1-1 A separable flask equipped with a stirrer, a nitrogen blowing port, a pressure reducing device, a condenser, a reflux port equipped with an oil / water separation tank, and an alkali metal hydroxide aqueous solution dropping port, 300 parts by weight of 1,6-dihydroxynaphthalene, and 1387 of epichlorohydrin. .5 parts by weight, 208.1 parts by weight of high-solve MDM were charged, heated to 60 ° C. after nitrogen purge, dissolved, and 31.1 parts by weight of 48.8% by weight sodium hydroxide aqueous solution, paying attention to heat generation Charged and reacted for 1 hour.
- Synthesis Example 1-2 To a separable flask equipped with a reflux port equipped with a stirrer, nitrogen inlet, thermocouple, and cooler, 61.2% of the diglycidyl ether type epoxy resin of 1,6-dihydroxynaphthalene obtained in Synthesis Example 1-1 was obtained. Part by weight, 38.8 parts by weight of 4,4′-biphenol and 25 parts by weight of cyclohexanone were charged, heated to 145 ° C., dissolved, and stirred for 1 hour. Thereafter, 0.1 part by weight of tris- (2,6-dimethoxyphenyl) phosphine was charged as a reaction catalyst, and the temperature was raised to 165 ° C.
- the reaction was followed by gel permeation chromatography, and when the weight average molecular weight was reached, cyclohexanone was added and cooled to stop the reaction.
- the resulting solution was uniform and had a solid content of 30.5% by weight.
- the obtained phenoxy resin was a light brown liquid and had an epoxy equivalent of 5750 g / eq, a number average molecular weight of 7,800 and a weight average molecular weight of 47,600.
- Synthesis Example 2-1 The synthesis was performed in the same manner as in Synthesis Example 1-1 except that 2,7-dihydroxynaphthalene was used, and a diglycidyl ether type epoxy resin of 2,7-dihydroxynaphthalene was obtained.
- the obtained resin was a brown liquid, but had crystallinity and became a white solid.
- the epoxy equivalent was 145.0 g / eq.
- Synthesis Example 2-2 A synthetic example except that 56.7 parts by weight of diglycidyl ether type epoxy resin of 2,7-dihydroxynaphthalene obtained in Synthesis Example 2-1 as an epoxy resin having a naphthalene skeleton and 43.3 parts by weight of bisphenol A were charged. The reaction was terminated when the weight average molecular weight reached around 40,000 in the same procedure as in 1-2, and a solution having a solid content of 30.5% by weight was obtained. The obtained phenoxy resin was a light brown liquid, and the weight average molecular weight was 44,600.
- Synthesis Example 2-3 The synthesis was performed in the same manner as in Synthesis Example 1-1 except that 1,5-dihydroxynaphthalene was used to obtain a 1,5-dihydroxynaphthalene diglycidyl ether type epoxy resin. During the synthesis, the temperature was kept so as not to precipitate crystals. The obtained resin had crystallinity and became a white solid. Moreover, the epoxy equivalent was 149.3 g / eq.
- Synthesis Example 3-1 In a 2000 ml four-necked flask, 186.0 g (1.0 mol) of 4,4′-dihydroxybiphenyl and 600 g of diethylene glycol dimethyl ether were charged and heated to 150 ° C. with stirring under a nitrogen stream. A solution in which 52.5 g (0.3 mol) of 4-bischloromethylbenzene was dissolved was dropped, and the mixture was heated to 170 ° C. and reacted for 2 hours. After the reaction, it was dropped into a large amount of pure water and recovered by reprecipitation to obtain 202 g of a pale yellow crystalline resin.
- Synthesis Example 3-2 115 g of the resin obtained in Synthesis Example 3-1 was dissolved in 549 g of epichlorohydrin and 82.4 g of diethylene glycol dimethyl ether, and 82.4 g of 48% aqueous sodium hydroxide solution was added dropwise at 62 ° C. under reduced pressure (about 130 Torr) over 4 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for another hour.
- Example 1 A diglycidyl ether type epoxy resin of 3,3 ′, 5,5′-tetramethylbiphenol (manufactured by Mitsubishi Chemical Corporation) was placed in a separable flask equipped with a reflux port equipped with a stirrer, nitrogen inlet, thermocouple, and cooler. YX-4000, epoxy equivalent 186, solid) 61.2 parts by weight, 4,4′-biphenol 33.9 parts by weight, cyclohexanone 25 parts by weight, heated to 145 ° C. and dissolved. Stir for 1 hour. Thereafter, 0.1 part by weight of tris- (2,6-dimethoxyphenyl) phosphine was charged as a reaction catalyst, and the temperature was raised to 165 ° C.
- the reaction was followed by gel permeation chromatography, and when the weight average molecular weight was reached, cyclohexanone was added and cooled to stop the reaction.
- the resulting solution was uniform and had a solid content of 29.7% by weight.
- the obtained phenoxy resin was a pale yellow liquid and had an epoxy equivalent of 11,400 g / eq, a number average molecular weight of 15,300, and a weight average molecular weight of 40,600.
- Epoxy resin composition (a) Epoxy resin Epoxy resin (1): Bisphenol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name; YD-825GS, epoxy equivalent 180, liquid) Epoxy resin (2): Biphenylene aralkylphenol type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000, epoxy equivalent 275, softening point 56 ° C.) Epoxy resin (3): Triphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EPPN-501H, epoxy equivalent 170, semi-solid, softening point 60 ° C.) Epoxy resin (4): 1,5-dihydroxynaphthalene type epoxy resin obtained in Synthesis Example 2-3 (softening point 172 ° C.) Epoxy resin (5): biphenol aralkyl type epoxy resin obtained in Synthesis Example 3-2 (softening point 135 ° C.) (B
- Results are shown in Tables 1-3.
- the blending amounts of epoxy resin, curing agent, phenoxy resin, alumina powder, silane coupling agent, and solvent (cyclohexanone) are shown in parts by weight.
Abstract
Description
(イ)エポキシ樹脂、
(ロ)硬化剤、及び
(ハ)下記一般式(1)で表される重量平均分子量が10,000~200,000の範囲内である非結晶性フェノキシ樹脂、
を含有するエポキシ樹脂組成物である。このエポキシ樹脂組成物において、前記(イ)成分は、メソゲン基を有する結晶性エポキシ樹脂を(イ)成分の全量に対して5~100重量%の範囲内で含有するものであり、前記(ハ)成分を、前記(イ)及び(ハ)成分中の固形分の合計100重量部に対して5~90重量部の範囲内で含有する。 That is, the epoxy resin composition of the present invention comprises the following components (a) to (c):
(A) epoxy resin,
(B) a curing agent, and (c) an amorphous phenoxy resin having a weight average molecular weight represented by the following general formula (1) in the range of 10,000 to 200,000,
Is an epoxy resin composition containing In this epoxy resin composition, the component (a) contains a crystalline epoxy resin having a mesogenic group within a range of 5 to 100% by weight based on the total amount of the component (a). Component) is contained within a range of 5 to 90 parts by weight with respect to 100 parts by weight of the total solid content in the components (a) and (c).
(ニ)無機充填剤、
を含有するものであってもよい。 The epoxy resin composition of the present invention further comprises the following components (d),
(D) inorganic filler,
May be contained.
(ホ)溶剤、
を含有するものであってもよい。 The epoxy resin composition of the present invention further comprises the following components (e),
(E) solvent,
May be contained.
(イ)成分のエポキシ樹脂としては、例えば、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、o-クレゾールノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、脂環式エポキシ樹脂、臭素化エポキシ樹脂等の分子中にエポキシ基を2個以上有するエポキシ樹脂を例示することができる。これらのエポキシ樹脂は1種又は2種以上を用いることができる。 <(I) Component: Epoxy resin>
As the component (a) epoxy resin, for example, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, o-cresol novolak Exemplified epoxy resins with two or more epoxy groups in the molecule such as epoxy resin, biphenyl novolac epoxy resin, triphenylmethane epoxy resin, dicyclopentadiene epoxy resin, alicyclic epoxy resin, brominated epoxy resin can do. These epoxy resins can be used alone or in combination of two or more.
(ロ)成分の硬化剤は、エポキシ樹脂を硬化させる目的で配合されるものであり、エポキシ樹脂組成物から絶縁層、接着剤層や樹脂フィルムを作製した場合に、十分な絶縁性、密着性、耐熱性、機械的強度等を付与する。本実施の形態で用いる(ロ)成分の硬化剤としては、イミダゾール系硬化剤又は非イミダゾール系硬化剤を用いることができる。 <(B) component: curing agent>
The component (b) curing agent is blended for the purpose of curing the epoxy resin. When an insulating layer, an adhesive layer or a resin film is produced from the epoxy resin composition, sufficient insulation and adhesion are obtained. , Impart heat resistance, mechanical strength, etc. As the (b) component curing agent used in the present embodiment, an imidazole curing agent or a non-imidazole curing agent can be used.
(ハ)成分の非結晶性フェノキシ樹脂は、ビフェニレン骨格又はナフタレン骨格を有する。非結晶性フェノキシ樹脂は、エポキシ樹脂組成物をワニスの状態としたときに結晶の析出を防ぎ、有機溶剤への溶解状態を保持するとともに、エポキシ樹脂組成物から絶縁層、接着剤層や樹脂フィルムを作製した際の可とう性を向上させる成分である。 <(C) Amorphous phenoxy resin>
The amorphous phenoxy resin as the component (c) has a biphenylene skeleton or a naphthalene skeleton. Amorphous phenoxy resin prevents precipitation of crystals when the epoxy resin composition is in a varnish state and maintains a dissolved state in an organic solvent, and from the epoxy resin composition to an insulating layer, an adhesive layer, and a resin film. It is a component which improves the flexibility at the time of producing.
本実施の形態のエポキシ樹脂組成物は、上記必須成分に加え、必要に応じて、例えば溶剤、ゴム成分、フッ素系、シリコーン系等の消泡剤、レベリング剤等を添加することができる。また、金属基板、銅配線等の部材との密着性向上の観点から、例えば、シランカップリング剤、熱可塑性オリゴマー等の密着性付与剤を添加することができる。さらに、本実施の形態のエポキシ樹脂組成物には、無機充填剤、有機充填剤を添加してもよい。無機充填剤としては、例えば、アルミナ、シリカ、窒化ホウ素、窒化アルミニウム、窒化ケイ素、炭酸カルシウム、炭酸マグネシウム等を挙げることができる。また、有機充填剤としては、例えば、シリコンパウダー、ナイロンパウダー、アクリロニトリル-ブタジエン系架橋ゴム等を挙げることができる。これらの充填剤については、1種又は2種以上を用いることができる。また、本実施の形態のエポキシ樹脂組成物には、必要に応じて、例えばフタロシアニン・グリーン、フタロシアニン・ブルー、カーボンブラック等の着色剤を配合することができる。 <Optional component>
In addition to the above essential components, for example, a solvent, a rubber component, a fluorine-based or silicone-based antifoaming agent, a leveling agent, and the like can be added to the epoxy resin composition of the present embodiment as necessary. Moreover, from the viewpoint of improving the adhesion to members such as a metal substrate and copper wiring, for example, an adhesion imparting agent such as a silane coupling agent or a thermoplastic oligomer can be added. Furthermore, you may add an inorganic filler and an organic filler to the epoxy resin composition of this Embodiment. Examples of the inorganic filler include alumina, silica, boron nitride, aluminum nitride, silicon nitride, calcium carbonate, magnesium carbonate and the like. Examples of the organic filler include silicon powder, nylon powder, acrylonitrile-butadiene-based crosslinked rubber, and the like. About these fillers, 1 type (s) or 2 or more types can be used. In addition, the epoxy resin composition of the present embodiment can be blended with a colorant such as phthalocyanine / green, phthalocyanine / blue, or carbon black, if necessary.
本実施の形態のエポキシ樹脂組成物は、上記の必須成分および任意成分を混合することにより調製できる。この場合、溶剤を含むワニスの形態とすることが好ましい。すなわち、本実施の形態のエポキシ樹脂組成物は、所定の溶剤に溶解又は分散させてワニスを形成するようにしてもよい。 [varnish]
The epoxy resin composition of the present embodiment can be prepared by mixing the above essential components and optional components. In this case, it is preferable to use a varnish containing a solvent. That is, the epoxy resin composition of the present embodiment may be dissolved or dispersed in a predetermined solvent to form a varnish.
本実施の形態においては、上記ワニスを支持材としてのベースフィルム上に塗布し、乾燥させることでBステージ状態の樹脂シートを形成することができる。また、上記ワニスを銅箔上に塗布し、乾燥させることによって樹脂シート付き銅箔を形成することもできる。Bステージ状態の樹脂シート(樹脂シート付き銅箔)は、折り曲げた場合に表面に割れ(クラック)が発生すると製品としての価値が損なわれる。このようなBステージ状態での表面割れは、常温で固体のメソゲン基を有する結晶性エポキシ樹脂を多く配合することによって発生しやすくなる。上記のとおり、本実施の形態のエポキシ樹脂組成物は、メソゲン基を有する結晶性エポキシ樹脂と非結晶性フェノキシ樹脂とを組み合わせて配合したことにより、樹脂シートの可撓性が向上し、さらにワニス中での結晶の析出が抑制される結果としてクラックの発生も抑制できる。また、本実施の形態において、硬化剤としてイミダゾール化合物のみを使用した場合、エポキシ樹脂組成物に占める固体の樹脂成分の割合を低く抑えることができる。また、イミダゾール化合物は、例えばフェノールノボラック系の硬化剤成分を配合した場合と比較すると、硬化剤としての配合量も低く抑えることができる。そのため、常温で液状又は半固形の成分をより多く配合することが可能となり、Bステージ状態での柔軟性、可とう性が向上し、表面割れを防止することができる。 [Resin sheet / copper foil with resin sheet]
In this Embodiment, the resin sheet of a B-stage state can be formed by apply | coating the said varnish on the base film as a support material, and making it dry. Moreover, the copper foil with a resin sheet can also be formed by apply | coating the said varnish on copper foil, and making it dry. When the B-stage resin sheet (copper foil with a resin sheet) is bent, its value as a product is lost when cracks occur on the surface. Such surface cracks in the B-stage state are likely to occur when a large amount of a crystalline epoxy resin having a mesogenic group that is solid at room temperature is blended. As described above, the epoxy resin composition of the present embodiment is obtained by combining the crystalline epoxy resin having a mesogenic group and the amorphous phenoxy resin, thereby improving the flexibility of the resin sheet, and further varnishing. As a result of suppressing the precipitation of crystals therein, the generation of cracks can also be suppressed. Moreover, in this Embodiment, when only an imidazole compound is used as a hardening | curing agent, the ratio of the solid resin component which occupies for an epoxy resin composition can be restrained low. In addition, the amount of the imidazole compound as a curing agent can be reduced as compared with, for example, a case where a phenol novolac-based curing agent component is blended. Therefore, it becomes possible to mix | blend more liquid or semi-solid components at normal temperature, the softness | flexibility in a B stage state, a flexibility, and a surface crack can be prevented.
本実施の形態の硬化物は、例えば、エポキシ樹脂組成物から上記Bステージ状態の樹脂シート(又は樹脂シート付き銅箔)を調製した後、例えば150℃~250℃の範囲内の温度に加熱して硬化させることによって製造できる。このようにして得られる硬化物は、結晶性を有していないが、優れた熱伝導性を有している。高熱伝導が要求される用途においては、硬化物の熱伝導率は、例えば10W/mK以上であることが好ましく、13W/mK以上であることがより好ましい。硬化物の熱伝導率が10W/mK以上であることにより、放熱特性が優れたものとなり、高温環境で使用される回路基板等への適用が可能になる。 [Cured product]
The cured product of this embodiment is prepared by, for example, preparing the B-stage resin sheet (or copper foil with a resin sheet) from the epoxy resin composition and then heating it to a temperature in the range of 150 ° C. to 250 ° C., for example. Can be produced by curing. The cured product thus obtained does not have crystallinity but has excellent thermal conductivity. In applications where high thermal conductivity is required, the thermal conductivity of the cured product is preferably, for example, 10 W / mK or more, and more preferably 13 W / mK or more. When the cured product has a thermal conductivity of 10 W / mK or more, it has excellent heat dissipation characteristics and can be applied to a circuit board or the like used in a high temperature environment.
次に、本実施の形態のエポキシ樹脂組成物を用いて金属ベース回路基板を製造する方法の一例について説明する。ここでは、アルミニウム基板を用いたアルミニウムベース回路基板を例示する。まず、エポキシ樹脂組成物から上記の樹脂シート付き銅箔を得た後、この樹脂シート付き銅箔を、アルミニウム基板の上にバッチ式真空プレスを用いて、例えば、温度150~250℃、圧力1.0~30MPaの条件で接着する。この際、アルミニウム基板面に樹脂シート面を接触させ、支持材としての銅箔を上面とした状態で加熱、加圧して、エポキシ樹脂を硬化させることにより、アルミニウム基板に貼り付ける。このようにして、樹脂シートを絶縁性の接着剤層として、銅箔層とアルミニウム基板との間に介在させた積層体を得ることができる。次に、エッチングによって所定箇所の銅箔を除去することにより回路配線を形成し、最終的にアルミニウムベース回路基板を得ることができる。なお、アルミニウム基板の厚さについては、特に制限はないが、一般的には例えば0.5~3.0mmとすることができる。 [Metal-based circuit board manufacturing method]
Next, an example of a method for producing a metal base circuit board using the epoxy resin composition of the present embodiment will be described. Here, an aluminum base circuit board using an aluminum substrate is illustrated. First, after obtaining the above-mentioned copper foil with a resin sheet from the epoxy resin composition, the copper foil with a resin sheet is placed on an aluminum substrate by using a batch type vacuum press, for example, at a temperature of 150 to 250 ° C. and a pressure of 1 Adhere under conditions of 0 to 30 MPa. At this time, the resin sheet surface is brought into contact with the aluminum substrate surface, and the epoxy resin is cured by applying heat and pressure in a state where the copper foil as a support material is the upper surface, thereby being attached to the aluminum substrate. In this way, a laminate in which the resin sheet is used as an insulating adhesive layer and interposed between the copper foil layer and the aluminum substrate can be obtained. Next, by removing the copper foil at a predetermined location by etching, circuit wiring can be formed, and finally an aluminum base circuit board can be obtained. The thickness of the aluminum substrate is not particularly limited, but can generally be set to 0.5 to 3.0 mm, for example.
フェノキシ樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィを用いて分析した。具体的には東ソー株式会社製HLC-8320本体に、東ソー株式会社製のカラム、TSK-gel GMHXL,TSK-gel GMHXL、TSK-gel G2000Hを直列に備えたものを使用した。また、溶離液にはテトラヒドロフランを用い、流速は1ml/minとした。カラム室の温度は40度とした。検出はRI検出器を使用し、測定をおこなった。重量平均分子量は、標準ポリスチレン検量線を用いて求めた。 [Weight average molecular weight of phenoxy resin]
The weight average molecular weight of the phenoxy resin was analyzed using gel permeation chromatography. Specifically, an HLC-8320 main body manufactured by Tosoh Corporation and a column manufactured by Tosoh Corporation, TSK-gel GMHXL, TSK-gel GMHXL, and TSK-gel G2000H were used in series. Tetrahydrofuran was used as the eluent, and the flow rate was 1 ml / min. The temperature of the column chamber was 40 degrees. Detection was performed using an RI detector. The weight average molecular weight was determined using a standard polystyrene calibration curve.
フェノキシ樹脂溶液の不揮発分は、アルミカップに試料約1gをはかりとり、200℃の熱風循環式オーブン中で1時間乾燥させ、揮発せずに残った重量をもとに不揮発分を計算により求めた。 [Non-volatile content of phenoxy resin solution]
The nonvolatile content of the phenoxy resin solution was obtained by weighing about 1 g of a sample in an aluminum cup, drying in a hot air circulation oven at 200 ° C. for 1 hour, and calculating the nonvolatile content based on the remaining weight without volatilization. .
メソゲン基を有する結晶性エポキシ樹脂の結晶性の評価は、メソゲン基を有する結晶性エポキシ樹脂100重量部に対してアセトンを100重量部加えて溶解した後、不溶解物及び析出物をろ別し、乾燥して固形物を得た。得られた固形物の示差走査熱量分析をおこない、融点に基づく吸熱ピーク温度が確認できるか否かで結晶性を評価した。 [Evaluation of crystallinity of crystalline epoxy resin having mesogenic group]
The crystallinity of the crystalline epoxy resin having a mesogenic group is evaluated by adding 100 parts by weight of acetone to 100 parts by weight of the crystalline epoxy resin having a mesogenic group and then dissolving the insoluble matter and the precipitate. And dried to obtain a solid. The obtained solid was subjected to differential scanning calorimetry, and the crystallinity was evaluated based on whether or not the endothermic peak temperature based on the melting point could be confirmed.
所定量のBステージの樹脂シートを用いて、圧縮プレス成形機にて180℃で10分加熱し、プレスから取り出した後、さらに乾燥機中にて180℃で50分加熱することにより、直径50mm、厚さ5mmの円盤状試験片を得た。この試験片を、英弘精機製熱伝導率測定装置HC-110を用いて、定常法により25℃での熱伝導率[W/m・K]を測定した。 [Thermal conductivity]
Using a predetermined amount of B-stage resin sheet, heated at 180 ° C. for 10 minutes in a compression press molding machine, taken out from the press, and further heated at 180 ° C. for 50 minutes in a dryer to give a diameter of 50 mm. A disk-shaped test piece having a thickness of 5 mm was obtained. This test piece was measured for thermal conductivity [W / m · K] at 25 ° C. by a steady method using a thermal conductivity measuring device HC-110 manufactured by Eihiro Seiki.
攪拌機、窒素吹きこみ口、減圧装置と冷却器と油水分離槽を備えた還流口、アルカリ金属水酸化物水溶液滴下口を備えたセパラブルフラスコに1,6-ジヒドロキシナフタレン300重量部、エピクロルヒドリンを1387.5重量部、ハイソルブMDMを208.1重量部仕込み、窒素パージの後60℃まで昇温、溶解したのちに水酸化ナトリウム48.8重量%水溶液を31.1重量部、発熱に注意しながら仕込み、1時間反応した。その後窒素の導入を停止し、160Torr、63℃の条件で、水酸化ナトリウム48.8重量%水溶液の290.0重量部を8時間かけて滴下した。滴下が終了したら150℃まで昇温し、さらに10Torrまで減圧してエピクロルヒドリンとハイソルブMDMを留去した。得られた樹脂にトルエンを加えたのち珪藻土を用いて濾過し、水酸化ナトリウム0.1重量%水溶液にて洗浄後油水分離して水相を取り除いた。さらに水を加えて洗浄後、油水分離して水相を取り除いた。得られた樹脂溶液から水とトルエンを取り除き、1,6-ジヒドロキシナフタレンのジグリシジルエーテル型エポキシ樹脂を得た。得られたエポキシ樹脂は褐色液状であり、そのエポキシ当量は143.8g/eqであった。 Synthesis Example 1-1
A separable flask equipped with a stirrer, a nitrogen blowing port, a pressure reducing device, a condenser, a reflux port equipped with an oil / water separation tank, and an alkali metal hydroxide aqueous solution dropping port, 300 parts by weight of 1,6-dihydroxynaphthalene, and 1387 of epichlorohydrin. .5 parts by weight, 208.1 parts by weight of high-solve MDM were charged, heated to 60 ° C. after nitrogen purge, dissolved, and 31.1 parts by weight of 48.8% by weight sodium hydroxide aqueous solution, paying attention to heat generation Charged and reacted for 1 hour. Thereafter, the introduction of nitrogen was stopped, and 290.0 parts by weight of an aqueous solution of 48.8% by weight of sodium hydroxide was added dropwise over 8 hours under the conditions of 160 Torr and 63 ° C. When the dropping was completed, the temperature was raised to 150 ° C., and the pressure was reduced to 10 Torr to distill off epichlorohydrin and high-solve MDM. Toluene was added to the obtained resin, followed by filtration using diatomaceous earth. After washing with a 0.1 wt% sodium hydroxide aqueous solution, oil-water separation was performed to remove the aqueous phase. Further, water was added for washing, followed by oil / water separation to remove the aqueous phase. Water and toluene were removed from the obtained resin solution to obtain a 1,6-dihydroxynaphthalene diglycidyl ether type epoxy resin. The obtained epoxy resin was a brown liquid, and its epoxy equivalent was 143.8 g / eq.
攪拌機、窒素吹き込み口、熱電対、冷却機を備えた還流口を供えたセパラブルフラスコに、合成例1-1で得られた1,6-ジヒドロキシナフタレンのジグリシジルエーテル型エポキシ樹脂を61.2重量部、4,4’-ビフェノールを38.8重量部、シクロヘキサノンを25重量部仕込み、145℃まで昇温、溶解して1時間撹拌した。その後、反応触媒としてトリス-(2,6-ジメトキシフェニル)ホスフィンを0.1重量部仕込み、165℃まで昇温した。反応の経過とともに粘度が上昇するが、適宜シクロヘキサノンを加えて一定のトルクとなるよう撹拌を継続した。反応はゲルパーミエーションクロマトグラフィにて追跡し、所定の重量平均分子量となったところでシクロヘキサノンを加えて冷却し、反応を停止した。得られた溶液は均一であり、固形分が30.5重量%であった。得られたフェノキシ樹脂は淡褐色液状であり、そのエポキシ当量は5750g/eq、数平均分子量は7,800、重量平均分子量は47,600であった。 Synthesis Example 1-2
To a separable flask equipped with a reflux port equipped with a stirrer, nitrogen inlet, thermocouple, and cooler, 61.2% of the diglycidyl ether type epoxy resin of 1,6-dihydroxynaphthalene obtained in Synthesis Example 1-1 was obtained. Part by weight, 38.8 parts by weight of 4,4′-biphenol and 25 parts by weight of cyclohexanone were charged, heated to 145 ° C., dissolved, and stirred for 1 hour. Thereafter, 0.1 part by weight of tris- (2,6-dimethoxyphenyl) phosphine was charged as a reaction catalyst, and the temperature was raised to 165 ° C. The viscosity increased with the progress of the reaction, but cyclohexanone was appropriately added and stirring was continued to obtain a constant torque. The reaction was followed by gel permeation chromatography, and when the weight average molecular weight was reached, cyclohexanone was added and cooled to stop the reaction. The resulting solution was uniform and had a solid content of 30.5% by weight. The obtained phenoxy resin was a light brown liquid and had an epoxy equivalent of 5750 g / eq, a number average molecular weight of 7,800 and a weight average molecular weight of 47,600.
2,7-ジヒドロキシナフタレンを用いた他は合成例1-1と同様の手順で合成をおこない、2,7-ジヒドロキシナフタレンのジグリシジルエーテル型エポキシ樹脂を得た。得られた樹脂は褐色液状であるが、結晶性を有しており、白色の固体となった。また、そのエポキシ当量は145.0g/eqであった。 Synthesis Example 2-1
The synthesis was performed in the same manner as in Synthesis Example 1-1 except that 2,7-dihydroxynaphthalene was used, and a diglycidyl ether type epoxy resin of 2,7-dihydroxynaphthalene was obtained. The obtained resin was a brown liquid, but had crystallinity and became a white solid. Moreover, the epoxy equivalent was 145.0 g / eq.
ナフタレン骨格を有するエポキシ樹脂として合成例2-1で得られた2,7-ジヒドロキシナフタレンのジグリシジルエーテル型エポキシ樹脂を56.7重量部、ビスフェノールAを43.3重量部仕込んだ他は合成例1-2と同様な手順で重量平均分子量が40000前後となったところで反応を終了し、固形分が30.5重量%の溶液を得た。得られたフェノキシ樹脂は淡褐色液状であり、重量平均分子量は44,600であった。 Synthesis Example 2-2
A synthetic example except that 56.7 parts by weight of diglycidyl ether type epoxy resin of 2,7-dihydroxynaphthalene obtained in Synthesis Example 2-1 as an epoxy resin having a naphthalene skeleton and 43.3 parts by weight of bisphenol A were charged. The reaction was terminated when the weight average molecular weight reached around 40,000 in the same procedure as in 1-2, and a solution having a solid content of 30.5% by weight was obtained. The obtained phenoxy resin was a light brown liquid, and the weight average molecular weight was 44,600.
1,5-ジヒドロキシナフタレンを用いた他は合成例1-1と同様の手順で合成をおこない、1,5-ジヒドロキシナフタレンのジグリシジルエーテル型エポキシ樹脂を得た。合成の際は結晶が析出しないように保温した。得られた樹脂は結晶性を有しており、白色の固体となった。また、そのエポキシ当量は149.3g/eqであった。 Synthesis Example 2-3
The synthesis was performed in the same manner as in Synthesis Example 1-1 except that 1,5-dihydroxynaphthalene was used to obtain a 1,5-dihydroxynaphthalene diglycidyl ether type epoxy resin. During the synthesis, the temperature was kept so as not to precipitate crystals. The obtained resin had crystallinity and became a white solid. Moreover, the epoxy equivalent was 149.3 g / eq.
2000mlの4口フラスコに、4,4’-ジヒドロキシビフェニル186.0g(1.0モル)、ジエチレングリコールジメチルエーテル600gを仕込み、窒素気流下、攪拌しながら150℃まで昇温させ、ジエチレングリコールジメチルエーテル260gに1,4-ビスクロロメチルベンゼン52.5g(0.3モル)を溶解させた溶液を滴下した後、170℃まで昇温して2時間反応させた。反応後、大量の純水に滴下して再沈殿により回収し、淡黄色で結晶性の樹脂202gを得た。 Synthesis Example 3-1
In a 2000 ml four-necked flask, 186.0 g (1.0 mol) of 4,4′-dihydroxybiphenyl and 600 g of diethylene glycol dimethyl ether were charged and heated to 150 ° C. with stirring under a nitrogen stream. A solution in which 52.5 g (0.3 mol) of 4-bischloromethylbenzene was dissolved was dropped, and the mixture was heated to 170 ° C. and reacted for 2 hours. After the reaction, it was dropped into a large amount of pure water and recovered by reprecipitation to obtain 202 g of a pale yellow crystalline resin.
合成例3-1で得た樹脂115gをエピクロルヒドリン549g、ジエチレングリコールジメチルエーテル82.4gに溶解し、減圧下(約130Torr)62℃にて48%水酸化ナトリウム水溶液82.4gを4時間かけて滴下した。この間、生成する水はエピクロルヒドリンとの共沸により系外に除き、留出したエピクロルヒドリンは系内に戻した。滴下終了後、さらに1時間反応を継続した。その後、エピクロルヒドリンを留去し、メチルイソブチルケトン966gを加えた後、水洗により塩を除いた。その後、24%水酸化ナトリウム水溶液19.2g加え、85℃で2時間反応させた。反応後、濾過、水洗を行なった後、溶媒であるメチルイソブチルケトンを減圧留去し、エポキシ樹脂145gを得た。エポキシ当量は173.0g/eq、加水分解性塩素は490ppmであった。得られた樹脂は下記式(6)で表されるビフェノールアラルキル型エポキシ樹脂であった。なお、式(6)中、nは繰り返し単位を表す数を意味する。 Synthesis Example 3-2
115 g of the resin obtained in Synthesis Example 3-1 was dissolved in 549 g of epichlorohydrin and 82.4 g of diethylene glycol dimethyl ether, and 82.4 g of 48% aqueous sodium hydroxide solution was added dropwise at 62 ° C. under reduced pressure (about 130 Torr) over 4 hours. During this time, the generated water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for another hour. Thereafter, epichlorohydrin was distilled off, 966 g of methyl isobutyl ketone was added, and then the salt was removed by washing with water. Thereafter, 19.2 g of a 24% aqueous sodium hydroxide solution was added and reacted at 85 ° C. for 2 hours. After the reaction, filtration and washing with water were performed, and then methyl isobutyl ketone as a solvent was distilled off under reduced pressure to obtain 145 g of an epoxy resin. Epoxy equivalent was 173.0 g / eq, and hydrolyzable chlorine was 490 ppm. The obtained resin was a biphenol aralkyl type epoxy resin represented by the following formula (6). In formula (6), n means a number representing a repeating unit.
攪拌機、窒素吹き込み口、熱電対、冷却機を備えた還流口を供えたセパラブルフラスコに、3,3’,5,5’-テトラメチルビフェノールのジグリシジルエーテル型エポキシ樹脂(三菱化学株式会社製、商品名;YX-4000、エポキシ当量186、固形)を61.2重量部、4,4’-ビフェノールを33.9重量部、シクロヘキサノンを25重量部仕込み、145℃まで昇温、溶解して1時間撹拌した。その後、反応触媒としてトリス-(2,6-ジメトキシフェニル)ホスフィンを0.1重量部仕込み、165℃まで昇温した。反応の経過とともに粘度が上昇するが、適宜シクロヘキサノンを加えて一定のトルクとなるよう撹拌を継続した。反応はゲルパーミエーションクロマトグラフィにて追跡し、所定の重量平均分子量となったところでシクロヘキサノンを加えて冷却し、反応を停止した。得られた溶液は均一であり、固形分が29.7重量%であった。得られたフェノキシ樹脂は淡黄色液状であり、そのエポキシ当量は11,400g/eq、数平均分子量は15,300、重量平均分子量は40,600であった。 [Example 1]
A diglycidyl ether type epoxy resin of 3,3 ′, 5,5′-tetramethylbiphenol (manufactured by Mitsubishi Chemical Corporation) was placed in a separable flask equipped with a reflux port equipped with a stirrer, nitrogen inlet, thermocouple, and cooler. YX-4000, epoxy equivalent 186, solid) 61.2 parts by weight, 4,4′-biphenol 33.9 parts by weight, cyclohexanone 25 parts by weight, heated to 145 ° C. and dissolved. Stir for 1 hour. Thereafter, 0.1 part by weight of tris- (2,6-dimethoxyphenyl) phosphine was charged as a reaction catalyst, and the temperature was raised to 165 ° C. The viscosity increased with the progress of the reaction, but cyclohexanone was appropriately added and stirring was continued to obtain a constant torque. The reaction was followed by gel permeation chromatography, and when the weight average molecular weight was reached, cyclohexanone was added and cooled to stop the reaction. The resulting solution was uniform and had a solid content of 29.7% by weight. The obtained phenoxy resin was a pale yellow liquid and had an epoxy equivalent of 11,400 g / eq, a number average molecular weight of 15,300, and a weight average molecular weight of 40,600.
実施例1における3,3’,5,5’-テトラメチルビフェノールのジグリシジルエーテル型エポキシ樹脂を61.2重量部、及び4,4’-ビフェノールを33.9重量部の代わりに、ビスフェノールA型エポキシ樹脂(新日鉄住金化学株式会社製、商品名;YD-8125、エポキシ当量175、液状)を65.8重量部、及び4,4’-ビフェノールを34.2重量部使用した以外、実施例1と同様にして反応を行ったところ、溶液中に固体が析出し、フェノキシ樹脂溶液を得ることができなかった。 (Comparative Example 1)
Instead of 61.2 parts by weight of diglycidyl ether type epoxy resin of 3,3 ′, 5,5′-tetramethylbiphenol and 33.9 parts by weight of 4,4′-biphenol in Example 1, bisphenol A Except for using 65.8 parts by weight of epoxy resin (trade name; YD-8125, epoxy equivalent 175, liquid) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and 34.2 parts by weight of 4,4′-biphenol. When the reaction was carried out in the same manner as in No. 1, a solid precipitated in the solution, and a phenoxy resin solution could not be obtained.
実施例1における3,3’,5,5’-テトラメチルビフェノールのジグリシジルエーテル型エポキシ樹脂を61.2重量部、及び4,4’-ビフェノールを33.9重量部の代わりに、合成例2-2で得られた2,7-ジヒドロキシナフタレンのジグリシジルエーテル型エポキシ樹脂を62.0重量部、及び4,4’-ビフェノールを38.1重量部使用した以外、実施例1と同様にして反応を行ったところ、溶液中に固体が析出し、フェノキシ樹脂溶液を得ることができなかった。 (Comparative Example 2)
Synthesis Example 3 instead of 61.2 parts by weight of diglycidyl ether type epoxy resin of 3,3 ′, 5,5′-tetramethylbiphenol and 33.9 parts by weight of 4,4′-biphenol in Example 1 Except that 62.0 parts by weight of the diglycidyl ether type epoxy resin of 2,7-dihydroxynaphthalene obtained in 2-2 and 38.1 parts by weight of 4,4′-biphenol were used, the same procedure as in Example 1 was performed. As a result, a solid was precipitated in the solution, and a phenoxy resin solution could not be obtained.
エポキシ樹脂組成物、及び樹脂フィルムを作製するために使用した原料とその略号は以下のとおりである。 [Examples 2 to 12 and Comparative Examples 3 to 6]
The raw materials and their abbreviations used for producing the epoxy resin composition and the resin film are as follows.
(イ)エポキシ樹脂
エポキシ樹脂(1):ビスフェノール型エポキシ樹脂(新日鉄住金化学株式会社製、商品名;YD-825GS、エポキシ当量180、液状)
エポキシ樹脂(2):ビフェニレンアラルキルフェノール型エポキシ樹脂(日本化薬株式会社製、商品名;NC-3000、エポキシ当量275、軟化点56℃)
エポキシ樹脂(3):トリフェニルメタン型エポキシ樹脂(日本化薬株式会社製、商品名;EPPN-501H、エポキシ当量170、半固形、軟化点60℃)
エポキシ樹脂(4):合成例2-3で得られた1,5-ジヒドロキシナフタレン型エポキシ樹脂(軟化点172℃)
エポキシ樹脂(5):合成例3-2で得られたビフェノールアラルキル型エポキシ樹脂(軟化点135℃)
(ロ)硬化剤
硬化剤(1):2-フェニル-4,5-ジヒドロキシメチルイミダゾール(四国化成工業株式会社製、商品名;キュアゾール2PHz-PW)
(ハ)フェノキシ樹脂
フェノキシ樹脂(1):実施例1で得られたビフェノールアラルキル型フェノキシ樹脂
フェノキシ樹脂(2):合成例1-2で得られた1,6-ジヒドロキシナフタレン型フェノキシ樹脂
フェノキシ樹脂(3):ビスフェノールA型フェノキシ樹脂(新日鉄住金化学株式会社製、商品名;YP-50)
フェノキシ樹脂(4):ビスフェノールAF型フェノキシ樹脂(新日鉄住金化学株式会社製、商品名;ZX-1356-2)
(ニ)シランカップリング剤
シランカップリング剤(1):チッソ株式会社製、商品名;サイラーエースS-510 (A) Epoxy resin composition (a) Epoxy resin Epoxy resin (1): Bisphenol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name; YD-825GS, epoxy equivalent 180, liquid)
Epoxy resin (2): Biphenylene aralkylphenol type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000, epoxy equivalent 275, softening point 56 ° C.)
Epoxy resin (3): Triphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EPPN-501H, epoxy equivalent 170, semi-solid, softening point 60 ° C.)
Epoxy resin (4): 1,5-dihydroxynaphthalene type epoxy resin obtained in Synthesis Example 2-3 (softening point 172 ° C.)
Epoxy resin (5): biphenol aralkyl type epoxy resin obtained in Synthesis Example 3-2 (softening point 135 ° C.)
(B) Curing agent Curing agent (1): 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: Curesol 2PHz-PW)
(C) Phenoxy resin Phenoxy resin (1): Biphenol aralkyl type phenoxy resin phenoxy resin obtained in Example 1 (2): 1,6-dihydroxynaphthalene type phenoxy resin phenoxy resin obtained in Synthesis Example 1-2 ( 3): Bisphenol A type phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: YP-50)
Phenoxy resin (4): Bisphenol AF type phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1356-2)
(D) Silane coupling agent Silane coupling agent (1): manufactured by Chisso Corporation, trade name: Siler Ace S-510
アルミナ粉末(1): アドマテックス社製、商品名;AO-802、球状、結晶性、最大粒子径;10μm、平均粒子径D50;0.7μm、Na+;1.3ppm
アルミナ粉末(2): マイクロン社製、商品名;AL10-75R、球状、結晶性、最大粒子径;75μm、平均粒子径D50;10μm、Na+;3.9ppm
アルミナ粉末(3): マイクロン社製、商品名;AL35-75R、球状、結晶性、最大粒子径;75μm、平均粒子径D50;35μm、Na+;1.8ppm (B) Spherical filler alumina powder (1): manufactured by Admatechs Co., Ltd., trade name: AO-802, spherical, crystalline, maximum particle size: 10 μm, average particle size D 50 ; 0.7 μm, Na + ; 1.3 ppm
Alumina powder (2): Micron Corporation, trade name: AL10-75R, spherical, crystallinity, maximum particle diameter: 75 μm, average particle diameter D 50 ; 10 μm, Na + ; 3.9 ppm
Alumina powder (3): Micron Corporation, trade name: AL35-75R, spherical, crystalline, maximum particle size: 75 μm, average particle size D 50 ; 35 μm, Na + ; 1.8 ppm
上記の原料を表1~3に示す割合で配合した。まず、フェノキシ樹脂のみを、攪拌機付容器にて、シクロヘキサノンに攪拌、溶解した。次に、シクロヘキサノン溶液に、エポキシ樹脂、シランカップリング剤を配合し、80℃に加温した。これを室温まで冷却後、24時間静置して結晶析出の有無を確認した。結晶析出が無かったものに関しては引き続き硬化剤及びアルミナ粉末を配合し、攪拌、分散させ、エポキシ樹脂組成物のワニスを作製した。 (Preparation of varnish of epoxy resin composition)
The above raw materials were blended in the proportions shown in Tables 1 to 3. First, only the phenoxy resin was stirred and dissolved in cyclohexanone in a container with a stirrer. Next, an epoxy resin and a silane coupling agent were blended in the cyclohexanone solution and heated to 80 ° C. This was cooled to room temperature and allowed to stand for 24 hours to confirm the presence or absence of crystal precipitation. In the case of no crystal precipitation, the curing agent and alumina powder were continuously blended, stirred and dispersed to prepare an epoxy resin composition varnish.
上記で得られたワニスを、厚さ50μmの離型処理PETフィルム(三菱化学製MRX-50)に、乾燥後の樹脂層の厚さが200μmとなるように塗工し、130℃で15分乾燥させることで、Bステージの樹脂シートを作製した。このBステージの樹脂シートを180℃で硬化させて、硬化物を得た。 (Production of resin sheet and cured product)
The varnish obtained above was applied to a 50 μm-thick release-treated PET film (MRX-50 manufactured by Mitsubishi Chemical Co., Ltd.) so that the resin layer after drying had a thickness of 200 μm, and the coating was performed at 130 ° C. for 15 minutes By drying, a B-stage resin sheet was produced. The B-stage resin sheet was cured at 180 ° C. to obtain a cured product.
Claims (15)
- 下記(イ)~(ハ)成分、
(イ)エポキシ樹脂、
(ロ)硬化剤、及び
(ハ)下記一般式(1)で表される重量平均分子量が10,000~200,000の範囲内である非結晶性フェノキシ樹脂、
を含有するエポキシ樹脂組成物であって、
前記(イ)成分は、メソゲン基を有する結晶性エポキシ樹脂を(イ)成分の全量に対して5~100重量%の範囲内で含有するものであり、
前記(ハ)成分を、前記(イ)及び(ハ)成分中の固形分の合計100重量部に対して5~90重量部の範囲内で含有するエポキシ樹脂組成物。
(A) epoxy resin,
(B) a curing agent, and (c) an amorphous phenoxy resin having a weight average molecular weight represented by the following general formula (1) in the range of 10,000 to 200,000,
An epoxy resin composition containing
The component (a) contains a crystalline epoxy resin having a mesogenic group within a range of 5 to 100% by weight based on the total amount of the component (a).
An epoxy resin composition containing the component (c) within a range of 5 to 90 parts by weight with respect to a total of 100 parts by weight of the solid content in the components (a) and (c).
- 前記メソゲン基が、ビフェニレン基である請求項1に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, wherein the mesogenic group is a biphenylene group.
- 前記メソゲン基が、ナフタレン基である請求項1に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, wherein the mesogenic group is a naphthalene group.
- 前記(ハ)成分は、前記式(1)において、X及びYが前記式(2)で表されるビフェニレン骨格を有する非結晶性フェノキシ樹脂である請求項2に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 2, wherein the component (c) is an amorphous phenoxy resin having a biphenylene skeleton in which X and Y are represented by the formula (2) in the formula (1).
- 前記式(1)において、Xが、前記式(2)におけるR1~R8のうち、少なくとも4つが炭素数4以下のアルキル基であり、残りが水素原子であるビフェニレン骨格である請求項4に記載のエポキシ樹脂組成物。 5. In the formula (1), X is a biphenylene skeleton in which at least four of R 1 to R 8 in the formula (2) are alkyl groups having 4 or less carbon atoms, and the rest are hydrogen atoms. The epoxy resin composition described in 1.
- 前記式(1)において、Yが、前記式(2)におけるR1~R8のすべてが水素原子である非置換のビフェニレン骨格である請求項5に記載のエポキシ樹脂組成物。 6. The epoxy resin composition according to claim 5, wherein Y in the formula (1) is an unsubstituted biphenylene skeleton in which all of R 1 to R 8 in the formula (2) are hydrogen atoms.
- 前記式(1)において、Xが、3,3’位及び5,5’位に炭素数4以下のアルキル基が置換したテトラアルキルビフェニレン基であり、Yが、非置換のビフェニレン基である請求項2に記載のエポキシ樹脂組成物。 In the formula (1), X is a tetraalkylbiphenylene group in which an alkyl group having 4 or less carbon atoms is substituted at the 3,3′-position and the 5,5′-position, and Y is an unsubstituted biphenylene group. Item 3. The epoxy resin composition according to Item 2.
- 前記(ハ)成分は、前記式(1)において、Xが前記式(3)で表されるナフタレン骨格を有する非結晶性フェノキシ樹脂である請求項3に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 3, wherein the component (c) is an amorphous phenoxy resin having a naphthalene skeleton represented by the formula (3) in the formula (1).
- 前記式(1)において、Xが、1位及び6位にそれぞれ単結合を有するナフタレン骨格であり、Yが、前記式(2)におけるR1~R8のすべてが水素原子である非置換のビフェニレン骨格である請求項8に記載のエポキシ樹脂組成物。 In the above formula (1), X is a naphthalene skeleton having a single bond at each of the 1-position and 6-position, and Y is an unsubstituted group in which all of R 1 to R 8 in the formula (2) are hydrogen atoms The epoxy resin composition according to claim 8, which is a biphenylene skeleton.
- さらに、次の成分(ニ)、
(ニ)無機充填剤、
を含有する請求項1から請求項9のいずれか1項に記載のエポキシ樹脂組成物。 In addition, the following ingredients (d),
(D) inorganic filler,
The epoxy resin composition according to any one of claims 1 to 9, comprising: - さらに、次の成分(ホ)、
(ホ)溶剤、
を含有する請求項1から請求項10のいずれか1項に記載のエポキシ樹脂組成物。 In addition, the following ingredients (e),
(E) solvent,
The epoxy resin composition according to any one of claims 1 to 10, comprising: - 請求項1から請求項11のいずれか1項に記載のエポキシ樹脂組成物をフィルム状に形成してなる樹脂シート。 A resin sheet formed by forming the epoxy resin composition according to any one of claims 1 to 11 into a film shape.
- 請求項1から請求項11のいずれか1項に記載のエポキシ樹脂組成物を硬化させてなる硬化物。 A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 11.
- 3,3’位及び5,5’位にメチル基が置換したテトラメチルビフェニレン基、並びに非置換のビフェニレン基を有し、重量平均分子量が10,000~200,000の範囲内であるフェノキシ樹脂。 Phenoxy resin having a tetramethylbiphenylene group substituted with a methyl group at the 3,3 ′ and 5,5 ′ positions and an unsubstituted biphenylene group and having a weight average molecular weight in the range of 10,000 to 200,000 .
- 3,3’位及び5,5’位にメチル基が置換したテトラメチルビフェニレン基と、非置換のビフェニレン基のモル比率が、略1:1である請求項14に記載のフェノキシ樹脂。 The phenoxy resin according to claim 14, wherein the molar ratio of the tetramethylbiphenylene group substituted with a methyl group at the 3,3 'and 5,5' positions to the unsubstituted biphenylene group is about 1: 1.
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JP2015157907A (en) * | 2014-02-24 | 2015-09-03 | 三菱化学株式会社 | Epoxy compound and method of producing the same, epoxy compound-containing composition and cured product |
KR20180102692A (en) * | 2016-09-12 | 2018-09-17 | 미츠비시 가스 가가쿠 가부시키가이샤 | Resin composition, prepreg, metal foil clad laminate, resin sheet and printed wiring board |
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JPWO2018139112A1 (en) * | 2017-01-24 | 2019-04-18 | Dic株式会社 | Epoxy resin, epoxy resin composition containing the same, and cured product using the epoxy resin composition |
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CN104254555A (en) | 2014-12-31 |
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