Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated

Definitions

• the present invention relates to a curable resin composition.
• the present invention also relates to a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition.
• Patent Document 1 discloses an adhesive composition containing an epoxy resin and a siloxane-modified polyamideimide component, etc.
• Patent Document 2 discloses: A curable resin composition containing a polyimide silicone resin having two or more phenolic hydroxyl groups in one molecule and an epoxy resin or the like is disclosed. Further, as a curable resin composition using a non-silicone material, for example, Patent Document 3 discloses an epoxy resin composition containing an epoxy compound having a mesogenic structure, etc. Patent Document 4 discloses: A thermosetting resin composition containing a non-epoxy thermosetting resin or the like containing a mesogenic group in the molecule and not containing an epoxy group is disclosed. Furthermore, Patent Documents 5 and 6 disclose a resin composition containing an epoxy resin and a curing agent having a mesogenic skeleton in its molecule.
• the present disclosure 1 is a curable resin composition containing a curable resin and a curing agent, wherein the curing agent includes an imide oligomer having a crosslinkable functional group capable of reacting with the curable resin, and the imide The oligomer has mesogenic properties, or the curing agent is a curable resin composition containing other curing agents having mesogenic properties in addition to the imide oligomer.
• the present disclosure 2 is the curable resin composition of the present disclosure 1, wherein the crosslinkable functional group is at least one of an acid anhydride group and a phenolic hydroxyl group.
• the present disclosure 3 is the curable resin composition of the present disclosure 1 or 2, wherein the imide oligomer has a molecular weight of 5000 or less.
• the present disclosure 4 is the curable resin composition of the present disclosure 1, 2 or 3, wherein the curing agent has a structure represented by the following formula (1-1), (1-2), or (1-3) It is a thing.
• the present disclosure 5 is the curable resin composition of the present disclosure 1, 2, 3 or 4, wherein the curable resin contains an epoxy resin.
• the present disclosure 6 is the curable resin composition of the present disclosure 1, 2, 3, 4 or 5 further containing a thermally conductive filler.
• the present disclosure 7 is a cured product of the curable resin composition of the present disclosure 1, 2, 3, 4, 5 or 6.
• the present disclosure 8 is an adhesive using the curable resin composition of the present disclosure 1, 2, 3, 4, 5 or 6. Disclosure 9 is an adhesive film using the adhesive of Disclosure 8.
• a 1 and A 2 each independently represent an aromatic group or a condensed aromatic group
• a 3 is an aromatic group or a condensed aromatic group
• a 4 and A 5 each independently represent an aromatic group or a condensed aromatic group.
• the present invention will be described in detail below.
• the present inventors have found that an imide oligomer having a crosslinkable functional group capable of reacting with a curable resin is used as a curing agent for a curable resin composition, and an imide oligomer having mesogenic properties is used as the imide oligomer. or to use another curing agent having mesogenicity in addition to the imide oligomer as the curing agent.
• the present inventors have found that a curable resin composition having excellent heat resistance, thermal conductivity, low linear expansion, and adhesiveness can be obtained, and have completed the present invention.
• the curable resin composition of the present invention further contains a curing agent.
• the curing agent includes an imide oligomer having a crosslinkable functional group capable of reacting with the curable resin (hereinafter also referred to as "the imide oligomer according to the present invention").
• the imide oligomer according to the present invention By using the imide oligomer according to the present invention as the curing agent, the curable resin composition of the present invention is excellent in heat resistance, low linear expansion, and adhesiveness.
• the imide oligomer according to the present invention has mesogenic properties, or the curing agent includes other curing agents having mesogenic properties in addition to the imide oligomer according to the present invention. .
• the curable resin composition of the present invention is , which is excellent in thermal conductivity.
• the above-mentioned "having mesogenicity” refers to having a structural unit exhibiting liquid crystallinity.
• liquid crystallinity can be confirmed, for example, by observing under crossed Nicols while raising the temperature using a polarizing microscope equipped with a hot stage, and confirming whether or not an optical structure derived from the liquid crystal phase is observed. . It can also be confirmed by evaluating the phase transition temperature by differential scanning calorimetry (DSC measurement) or by evaluating the diffraction pattern by X-ray diffraction measurement (XRD measurement).
• DSC measurement differential scanning calorimetry
• XRD measurement X-ray diffraction measurement
• the curing agent preferably has a structure represented by formula (1-1), (1-2), or (1-3).
• the structure represented by the above formula (1-1), (1-2), or (1-3) can be a group exhibiting mesogenicity (mesogenic group), but the above formula (1-1) , (1-2), or (1-3) does not necessarily have mesogenicity.
• the crosslinkable functional group possessed by the imide oligomer according to the present invention may be at least one of an acid anhydride group and a phenolic hydroxyl group when an epoxy resin is used as the curable resin, depending on the type of curable resin used.
• the imide oligomer according to the present invention preferably has the crosslinkable functional groups at the ends of the main chain, more preferably at both ends of the main chain.
• the imide oligomer according to the present invention has a structure containing the crosslinkable functional group, the following formula (2-1) or the following formula (2-2), or the following formula (3-1) or the following formula (3-2 ) preferably has a structure represented by By having a structure represented by the following formula (2-1) or the following formula (2-2), or the following formula (3-1) or the following formula (3-2), the imide oligomer according to the present invention is , the reactivity and compatibility with the curable resin are excellent.
• A is an acid dianhydride residue
• B is an aliphatic diamine residue or an aromatic diamine residue
• Ar is an optionally substituted divalent aromatic group.
• A is an acid dianhydride residue
• B is an aliphatic triamine residue or an aromatic triamine residue
• Ar is an optionally substituted divalent aromatic group.
• the acid dianhydride residue is preferably a tetravalent group represented by the following formula (4-1) or the following formula (4-2).
• a 3 represents an aromatic group or a condensed aromatic group
• a 4 and A 5 each independently represent an aromatic group or a condensed aromatic group represents a group.
• Examples of acid dianhydrides from which the acid dianhydride residue is derived include acid dianhydrides represented by formula (10) described later.
• B in the formula (2-1) is the aliphatic diamine residue
• B in the formula (3-1) or the formula (3-2) is the aliphatic triamine residue
• a preferable lower limit of the carbon number of the aliphatic diamine residue and the aliphatic triamine residue is 4. Since the number of carbon atoms in the aliphatic diamine residue and the aliphatic triamine residue is 4 or more, the resulting curable resin composition has flexibility and workability before curing, and dielectric properties after curing. It will be better.
• a more preferable lower limit for the number of carbon atoms in the aliphatic diamine residue and the aliphatic triamine residue is 5, and a more preferable lower limit is 6. Although there is no particular upper limit for the number of carbon atoms in the aliphatic diamine residue and the aliphatic triamine residue, the practical upper limit is 60.
• Examples of the aliphatic diamine from which the aliphatic diamine residue is derived include aliphatic diamines derived from dimer acid, linear or branched aliphatic diamines, aliphatic ether diamines, and aliphatic alicyclic diamines. diamine and the like. Examples of the aliphatic diamines derived from the above dimer acids include dimer diamines and hydrogenated dimer diamines.
• linear or branched aliphatic diamines examples include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1, 11-undecanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 1,20-eicosanediamine, 2-methyl-1,8-octane diamine, 2-methyl-1,9-nonanediamine, 2,7-dimethyl-1,8-octanediamine and the like.
• aliphatic ether diamines examples include 2,2'-oxybis(ethylamine), 3,3'-oxybis(propylamine), 1,2-bis(2-aminoethoxy)ethane and the like.
• aliphatic alicyclic diamines examples include 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine.
• the aliphatic diamine residue is preferably an aliphatic diamine residue derived from the dimer acid.
• aliphatic triamines from which the above aliphatic triamine residues are derived include aliphatic triamines derived from trimer acid, linear or branched chain aliphatic triamines, aliphatic ether triamines, and aliphatic alicyclic triamines. triamine and the like.
• aliphatic triamines derived from trimer acids include trimer triamines and hydrogenated trimer triamines.
• linear or branched aliphatic triamines examples include 3,3′-diamino-N-methyldipropylamine, 3,3′-diaminodipropylamine, diethylenetriamine, bis(hexamethylene)triamine, 2,2 '-bis(methylamino)-N-methyldiethylamine and the like.
• the aliphatic triamine residue is preferably an aliphatic triamine residue derived from the trimer acid.
• a mixture of the dimer diamine and the trimer triamine can also be used as the aliphatic diamine and/or the aliphatic triamine.
• aliphatic diamines and/or aliphatic triamines derived from the dimer acid and/or the trimer acid include, for example, aliphatic diamines and/or triamines manufactured by BASF, and fatty acids manufactured by Croda. triamines and/or aliphatic triamines. Examples of the aliphatic diamines and/or aliphatic triamines manufactured by BASF include Versamin 551 and Versamin 552. Examples of the aliphatic diamines and/or aliphatic triamines manufactured by Croda include Priamine 1071, Priamine 1073, Priamine 1074, and Priamine 1075.
• the aromatic diamine residue is a divalent represented by the following formula (5-1) or the following formula (5-2) is preferably a group of
• Y is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a straight It is a chain or branched divalent hydrocarbon group or a divalent group having an aromatic ring.
• Y is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (5-1), Y is a divalent group having an aromatic ring.
• an oxygen atom may be present between the divalent group having the aromatic ring and each aromatic ring in formula (5-1).
• the hydrogen atoms of the aromatic rings in formulas (5-1) and (5-2) may be substituted.
• Y in the above formula (5-1) is a linear or branched divalent hydrocarbon group or a divalent group having an aromatic ring
• substituents in the case where the linear or branched divalent hydrocarbon group or the divalent group having an aromatic ring is substituted include, for example, a halogen atom, a linear or branched chain linear alkyl groups, linear or branched alkenyl groups, alicyclic groups, aryl groups, alkoxy groups, nitro groups, cyano groups and the like.
• Y in the above formula (5-1) may contain the same group as X in the above formula (4-2).
• aromatic diamine from which the aromatic diamine residue is derived examples include those in which the diamine represented by formula (11) described below is an aromatic diamine.
• the curing agent preferably does not contain a compound having a siloxane skeleton, as will be described later.
• the imide oligomer according to the present invention when it has a siloxane skeleton in its structure, it lowers the glass transition temperature of the cured product of the curable resin composition, contaminates the adherend, and may cause poor adhesion.
• an imide oligomer having no siloxane skeleton in its structure preferably an imide oligomer having no siloxane skeleton in its structure.
• the molecular weight of the imide oligomer according to the present invention is preferably 5000 or less.
• the obtained cured product of the curable resin composition is excellent in long-term heat resistance.
• a more preferable upper limit of the molecular weight of the imide oligomer according to the present invention is 4,000, and a further preferable upper limit is 3,000.
• the molecular weight of the imide oligomer according to the present invention is preferably 900 or more and 5000 or less when it has a structure represented by the above formula (2-1) or (3-1).
• the above-mentioned "molecular weight” is the molecular weight obtained from the structural formula for compounds whose molecular structure is specified. It may be expressed using the number average molecular weight.
• the above-mentioned "number average molecular weight” is a value obtained by performing measurement using tetrahydrofuran as a solvent by gel permeation chromatography (GPC) and converting it to polystyrene.
• GPC gel permeation chromatography
• Examples of the column used for measuring the polystyrene-equivalent number-average molecular weight by GPC include JAIGEL-2H-A (manufactured by Japan Analytical Industry Co., Ltd.).
• the imide oligomer according to the present invention is represented by the following formula (6-1), the following formula (6-2), the following formula (6-3), the following formula (6-4), or the following formula ( 6-5), or the following formula (7-1), the following formula (7-2), the following formula (7-3), the following formula (7-4), the following formula (7- 5), or an imide oligomer represented by the following formula (7-6).
• A is the acid dianhydride residue
• B is the aliphatic diamine residue or the aromatic diamine residue
• B is , may be the same or different.
• B is the above aliphatic triamine residue or the above aromatic triamine residue.
• X is a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group
• W is a hydrogen atom, a halogen atom , or an optionally substituted monovalent hydrocarbon group.
• n is the number of repetitions.
• A is the acid dianhydride residue, and in formulas (7-2) to (7-6), A is the same. may be different.
• R is a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group
• formula (7-1), formula (7 -2), Formula (7-4), and Formula (7-6) R may be the same or different.
• W is a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group.
• B is the aliphatic diamine residue or the aromatic diamine residue, and in formulas (7-4) and (7-5), B is , may be the same or different.
• B is, or the above aliphatic triamine residue or the above aromatic triamine residue.
• a in the above formulas (6-1) to (6-5) and the above formulas (7-1) to (7-6) is the following formula (8-1) or the following formula (8-2) It is preferably a tetravalent group represented.
• a 3 represents an aromatic group or a condensed aromatic group
• a 4 and A 5 each independently represent an aromatic group or a condensed aromatic group represents a group.
• * represents a bonding position.
• Y is a bond, an oxygen atom, a carbonyl group, a sulfur atom, a sulfonyl group, a straight It is a chain or branched divalent hydrocarbon group or a divalent group having an aromatic ring.
• Y is a hydrocarbon group, it may have an oxygen atom between the hydrocarbon group and each aromatic ring in formula (9-1), Y is a divalent group having an aromatic ring.
• an oxygen atom may be present between the divalent group having an aromatic ring and each aromatic ring in formula (9-1).
• the hydrogen atoms of the aromatic rings in formulas (9-1) and (9-2) may be substituted.
• an imide oligomer having a structure represented by the above formula (2-1) for example, an acid dianhydride represented by the following formula (10) and a diamine represented by the following formula (11) and the like. Also, by using an aliphatic triamine or an aromatic triamine instead of the diamine represented by the following formula (11), an imide oligomer having a structure represented by the above formula (3-1) can be produced.
• A is the same tetravalent group as A in formula (2-1) above.
• B is the same divalent group as B in formula (2-1) above, and R 1 to R 4 are each independently a hydrogen atom or a monovalent hydrocarbon group. .
• a specific example of the method for reacting the acid dianhydride represented by the above formula (10) with the diamine represented by the above formula (11) is shown below.
• the diamine represented by the above formula (11) is dissolved in advance in a solvent (for example, N-methylpyrrolidone) in which the amic acid oligomer obtained by the reaction is soluble, and the resulting solution is added with the above formula (10).
• An acid dianhydride represented by is added and reacted to obtain an amic acid oligomer solution.
• the solvent is removed by heating, pressure reduction, or the like, and the mixture is heated at about 200° C. or higher for 1 hour or longer to react the amic acid oligomer.
• the acid dianhydride represented by the above formula (10) and the acid anhydride represented by the following formula (12) may be added simultaneously or separately. Furthermore, by replacing a part of the diamine represented by the above formula (11) with a monoamine represented by the following formula (13), it has a desired number average molecular weight, and one end has the above formula (2-1) ) and having at the other end a structure derived from a monoamine represented by the following formula (13). In this case, the diamine represented by the above formula (11) and the monoamine represented by the following formula (13) may be added simultaneously or separately.
• Ar is an optionally substituted divalent aromatic group.
• Ar is an optionally substituted monovalent aromatic group
• R 5 and R 6 are each independently a hydrogen atom or a monovalent hydrocarbon group.
• an imide oligomer having a structure represented by the above formula (2-2) for example, an acid dianhydride represented by the above formula (10) and a phenolic compound represented by the following formula (14)
• an imide oligomer having a structure represented by the above formula (3-2) can be produced.
• Ar is an optionally substituted divalent aromatic group
• R 7 and R 8 are each independently a hydrogen atom or a monovalent hydrocarbon group.
• a specific example of the method of reacting the acid dianhydride represented by the above formula (10) with the phenolic hydroxyl group-containing monoamine represented by the above formula (14) is shown below.
• the phenolic hydroxyl group-containing monoamine represented by the above formula (14) is dissolved in advance in a solvent (for example, N-methylpyrrolidone etc.) in which the amic acid oligomer obtained by the reaction is soluble, and the above An acid dianhydride represented by formula (10) is added and reacted to obtain an amic acid oligomer solution.
• the solvent is removed by heating, pressure reduction, or the like, and the mixture is heated at about 200° C. or higher for 1 hour or longer to react the amic acid oligomer.
• the desired number average molecular weight can be obtained.
• An imide oligomer having a structure represented by the above formula (2-2) at both ends can be obtained.
• the phenolic hydroxyl group-containing monoamine represented by the above formula (14) with the monoamine represented by the above formula (13), it has a desired number average molecular weight, and one end has the above formula
• An imide oligomer having a structure represented by (2-2) and having a structure derived from a monoamine represented by the above formula (13) at the other end can be obtained.
• the phenolic hydroxyl group-containing monoamine represented by the above formula (14) and the monoamine represented by the above formula (13) may be added simultaneously or separately.
• the solvent is removed by heating, pressure reduction, or the like, and the mixture is heated at about 200° C. or higher for 1 hour or longer to react the amic acid oligomer.
• the molar ratio of the acid dianhydride represented by the above formula (10), the diamine represented by the above formula (11) and the phenolic hydroxyl group-containing monoamine represented by the above formula (14), and the imidization conditions By adjusting, it is possible to obtain an imide oligomer having a desired number average molecular weight and a structure represented by the above formula (2-2) at both ends.
• the phenolic hydroxyl group-containing monoamine represented by the above formula (14) by replacing part of the phenolic hydroxyl group-containing monoamine represented by the above formula (14) with the monoamine represented by the above formula (13), it has a desired number average molecular weight, and one end has the above formula An imide oligomer having a structure represented by (2-2) and having a structure derived from a monoamine represented by the above formula (13) at the other end can be obtained.
• the phenolic hydroxyl group-containing monoamine represented by the above formula (14) and the monoamine represented by the above formula (13) may be added simultaneously or separately.
• Examples of the acid dianhydride represented by the above formula (10) include pyromellitic dianhydride, 3,3′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, 4,4 '-Oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic dianhydride, 4,4'-bis(2,3-dicarboxylphenoxy)diphenyl ether acid dianhydride p-phenylenebis(trimellitate anhydride), 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 4 ,4′-biphthalic anhydride, 4,4′-carbonyldiphthalic anhydride, 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzo
• the acid dianhydride represented by the above formula (10) includes pyromellitic dianhydride, 4,4'-(4, 4'-Isopropylidenediphenoxy)diphthalic dianhydride, p-phenylenebis(trimellitate anhydride), 2,3,3',4'-biphenyltetracarboxylic dianhydride, 4,4'-biphthalic anhydride 4,4′-carbonyldiphthalic anhydride, 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate), 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′
• aromatic diamines include, for example, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis(4-(4-aminophenoxy ) phenyl
• Examples of the acid anhydride represented by the above formula (12) include phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1,2-naphthalic anhydride, and 2,3-naphthalic anhydride.
• Monoamines represented by the above formula (13) include, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,4-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 1-aminopyrene, 3- Chloroaniline, o-anisidine, m-anisidine, p-anisidine, 1-amino-2-methylnaphthalene, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 3,4-dimethyl Aniline, 4-ethylaniline, 4-ethynylaniline, 4-
• Examples of the phenolic hydroxyl group-containing monoamine represented by the above formula (14) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2 ,3-xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4 -amino-2,6-diphenylphenol and the like.
• 4-amino-o-cresol and 5-amino-o-cresol are preferred because they are excellent in availability and storage stability and provide a high glass transition temperature after curing.
• the imide oligomer according to the present invention is a plurality of types of imide oligomers having a structure represented by the above formula (2-1) or the above formula (2-2) ) and a mixture of each starting material (imide oligomer composition).
• the imide oligomer according to the present invention has a structure represented by the above formula (3-1). or multiple kinds of imide oligomers having a structure represented by the above formula (3-2) and each raw material (imide oligomer composition).
• the imide oligomer composition When the imide oligomer composition has an imidization rate of 70% or more, it can provide a cured product having excellent mechanical strength at high temperatures and long-term heat resistance when used as a curing agent.
• a preferable lower limit of the imidization rate of the imide oligomer composition according to the present invention is 75%, and a more preferable lower limit is 80%. Although there is no particular upper limit for the imidization rate of the imide oligomer composition according to the present invention, the practical upper limit is 98%.
• the above-mentioned "imidation rate” is measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (FT-IR), and is derived from the carbonyl group of amic acid at 1660 cm -1 It can be derived from the peak absorbance area in the vicinity by the following formula.
• Examples of the Fourier transform infrared spectrophotometer include UMA600 (manufactured by Agilent Technologies).
• the imide oligomer composition according to the present invention preferably dissolves in 3 g or more per 10 g of tetrahydrofuran at 25°C.
• the preferable lower limit of the content of the imide oligomer according to the present invention in the total 100 parts by weight of the curable resin and the curing agent (further curing accelerator if it contains a curing accelerator described later) is 20 parts by weight, preferably The upper limit is 80 parts by weight.
• the content of the imide oligomer according to the present invention is within this range, the resulting curable resin composition will be excellent in thermal conductivity, low linear expansion, and heat resistance after curing.
• a more preferable lower limit of the content of the imide oligomer according to the present invention is 25 parts by weight, and a more preferable upper limit thereof is 75 parts by weight.
• the content of the imide oligomer according to the present invention is total content of the imide oligomer composition and other imide oligomers).
• the other curing agents include, for example, phenolic hydroxyl groups, amino groups, carboxy groups, acid anhydride groups, A compound having a reactive functional group such as an active ester group can be used.
• the other curing agent preferably has a structure represented by the above formula (1-1), (1-2), or (1-3).
• the structure represented by the above formula (1-1), (1-2), or (1-3) can be a group exhibiting mesogenicity (mesogenic group), but the above formula (1-1) , (1-2), or (1-3) does not necessarily have mesogenicity.
• Examples of the above other curing agents include curing agents described in Patent Documents 5 and 6, and the like.
• the total of the curable resin and the curing agent is 100.
• a preferable lower limit of the total content of the imide oligomer according to the present invention and the other curing agent in the parts by weight is 20 parts by weight, and a preferable upper limit is 80 parts by weight.
• the total content of the imide oligomer according to the present invention and the other curing agent is within this range, the resulting curable resin composition is superior in adhesiveness and heat resistance after curing.
• the curable resin composition of the present invention contains a curable resin.
• the curable resin include epoxy resin, cyanate resin, phenol resin, polyimide resin, maleimide resin, benzoxazine resin, silicone resin, acrylic resin, and fluororesin.
• the said curable resin contains an epoxy resin.
• the curable resin may have no mesogenicity or may have mesogenicity.
• the curable resins may be used alone, or two or more of them may be used in combination.
• the epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallylbisphenol A type epoxy resin, and hydrogenated bisphenol type epoxy resin. , propylene oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, naphthylene ether type epoxy resin, phenol novolak type epoxy resin, ortho-cresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolak type epoxy resin, glycidylamine type epoxy resin, alkylpolyol type epoxy resin, Examples include rubber-modified epoxy resins and glycidyl ester compounds.
• the thermal conductivity is further improved.
• it preferably contains a non-mesogenic epoxy resin that is liquid at 25° C. because it has a low viscosity, facilitates adjustment of the processability of the resulting curable resin composition, and provides high adhesive strength.
• the above epoxy resins may be used alone, or two or more of them may be used in combination.
• the curable resin preferably does not contain a compound having a siloxane skeleton.
• the curable resin and the curing agent do not contain a compound having a siloxane skeleton. Since the curable resin and the curing agent do not contain a compound having a siloxane skeleton, it is possible to prevent the occurrence of poor contact due to low-molecular-weight siloxane compounds derived from the curable resin composition.
• the curable resin composition of the invention may contain a thermally conductive filler.
• the thermally conductive filler means a filler having a thermal conductivity of 10 W/m ⁇ K or more.
• the thermally conductive filler is a group consisting of alumina, aluminum nitride, silicon carbide, boron nitride, silicon nitride, magnesium oxide, zinc oxide, boron carbide, titanium carbide, zirconia, aluminum, and diamond. It is preferable to include at least one more selected one.
• thermally conductive filler examples include a plate shape, a spherical shape, an irregular shape, a crushed shape, and a polygonal shape. Further, the thermally conductive filler may be aggregated particles in which primary particles such as plate-like fillers are aggregated.
• the preferable lower limit of the average particle size of the thermally conductive filler is 0.1 ⁇ m, and the preferable upper limit thereof is 300 ⁇ m. When the average particle size of the thermally conductive filler is within this range, the resulting curable resin composition will be superior in coatability and thermal conductivity.
• a more preferable lower limit of the average particle size of the thermally conductive filler is 0.2 ⁇ m, and a more preferable upper limit thereof is 200 ⁇ m.
• the average particle diameter of the thermally conductive filler is determined by dispersing the thermally conductive filler in a solvent (water, organic solvent, etc.) using a particle size distribution analyzer such as NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS). can be measured.
• a preferred lower limit for the content of the thermally conductive filler in the curable resin composition of the present invention is 50% by volume.
• the content of the thermally conductive filler is 50% by volume or more, the obtained curable resin composition has excellent thermal conductivity.
• a more preferable lower limit for the content of the thermally conductive filler is 60% by volume.
• the upper limit of the content of the thermally conductive filler is preferably 95% by volume, and a more preferable upper limit is 90% by volume.
• the curable resin composition of the present invention may contain other fillers having a thermal conductivity of less than 10 W/m ⁇ K in addition to the above-mentioned thermally conductive fillers, as long as the objects of the present invention are not hindered. .
• Inorganic fillers and organic fillers can be used as the other fillers.
• the inorganic filler include silica, barium sulfate, glass powder, glass frit, glass fiber, and inorganic ion exchangers. Among them, silica and barium sulfate are preferred.
• the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferred.
• the other fillers may be used alone, or two or more of them may be used in combination.
• the curable resin composition of the present invention when the curable resin composition of the present invention contains the thermally conductive filler, the curable resin composition of the present invention preferably contains a dispersant. By containing the dispersant, the curable resin composition of the present invention can easily uniformize the dispersed state of the thermally conductive filler.
• dispersant examples include modified polyester compounds, modified polyether compounds, phosphate esters of modified polyether compounds, fatty acid derivatives, fatty acid polycarboxylic acid amine salts, cationic group-containing acrylic polymers, and polyurethane compounds.
• the dispersants may be used alone, or two or more of them may be used in combination.
• the preferred lower limit of the content of the dispersant in 100 parts by weight of the curable resin composition of the present invention is 0.05 parts by weight, and the preferred upper limit is 4 parts by weight.
• the content of the dispersant is within this range, it becomes easier to uniformize the dispersed state of the thermally conductive filler.
• a more preferred lower limit to the content of the dispersant is 0.1 parts by weight, and a more preferred upper limit is 3 parts by weight.
• the curable resin composition of the present invention preferably contains a curing accelerator.
• a curing accelerator By containing the curing accelerator, the curing time can be shortened and the productivity can be improved.
• the curing accelerator examples include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, phosphorus-based curing accelerators, photobase generators, sulfonium salt-based curing accelerators, and the like. . Of these, imidazole-based curing accelerators are preferred because of their excellent storage stability. The curing accelerators may be used alone, or two or more of them may be used in combination.
• the content of the curing accelerator has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight based on a total of 100 parts by weight of the curable resin, the curing agent and the curing accelerator.
• a more preferred lower limit to the content of the curing accelerator is 0.05 parts by weight, and a more preferred upper limit is 5 parts by weight.
• the curable resin composition of the present invention may contain a polymer component as long as the object of the present invention is not impaired.
• the polymer component serves as a film-forming component.
• a preferable lower limit of the number average molecular weight of the polymer component is 3,000, and a preferable upper limit thereof is 100,000. When the number average molecular weight of the polymer component is within this range, the resulting curable resin composition will be superior in flexibility and workability before curing and in heat resistance after curing.
• a more preferable lower limit of the number average molecular weight of the polymer component is 5,000, and a more preferable upper limit thereof is 80,000.
• polymer component examples include polyimide, phenoxy resin, polyamide, polyamideimide, polymaleimide, cyanate resin, benzoxazine resin, acrylic resin, urethane resin, and polyester.
• polyimide, polyamide, polyamideimide, and polymaleimide are preferable, and polyimide is more preferable.
• the above polymer components may be used alone, or two or more may be used in combination.
• the content of the polymer component has a preferred lower limit of 0 with respect to a total of 100 parts by weight of the curable resin, the curing agent (and the curing accelerator when the curing accelerator is contained), and the polymer component. .5 parts by weight, with a preferred upper limit of 40 parts by weight.
• the content of the polymer component is within this range, the resulting cured product of the curable resin composition is more excellent in heat resistance.
• a more preferable lower limit to the content of the polymer component is 1 part by weight, and a more preferable upper limit is 30 parts by weight.
• the curable resin composition may contain a solvent or a reactive diluent from the viewpoint of coatability, handleability, and the like.
• a solvent having a boiling point of less than 200° C. is preferable from the viewpoint of coatability, storage stability, and the like.
• the solvent having a boiling point of less than 200° C. include alcohol-based solvents, ketone-based solvents, ester-based solvents, hydrocarbon-based solvents, halogen-based solvents, ether-based solvents, and nitrogen-containing solvents.
• the alcohol solvent include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, tertiary butyl alcohol, and 2-ethylhexanol.
• Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and diacetone alcohol.
• Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, and butyl lactate.
• hydrocarbon solvent examples include benzene, toluene, xylene, normal hexane, isohexane, cyclohexane, methylcyclohexane, ethylcyclohexane, isooctane, normal decane, normal heptane and the like.
• halogen-based solvent examples include dichloromethane, chloroform, and trichlorethylene.
• ether solvent examples include diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate. , propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monotertiary butyl ether, propylene glycol monomethyl ether propionate, 3-methoxybutanol, diethylene glycol dimethyl ether, anisole, 4-methylanisole and the like. be done.
• nitrogen-containing solvent examples include acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like.
• ketone solvents with a boiling point of 60 ° C. or higher and lower than 200 ° C. from the viewpoint of handleability and solubility of imide oligomers, ketone solvents with a boiling point of 60 ° C. or higher and lower than 200 ° C., ester solvents with a boiling point of 60 ° C. or higher and lower than 200 ° C., and boiling points of 60 ° C. or higher and 200 ° C.
• At least one selected from the group consisting of ether-based solvents having a temperature of less than °C is preferred.
• solvents examples include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, cyclohexanone, methylcyclohexanone, diethylene glycol dimethyl ether, and anisole.
• the "boiling point” means a value measured under conditions of 101 kPa, or a value converted to 101 kPa using a boiling point conversion chart or the like.
• a reactive diluent having one or more crosslinkable functional groups in one molecule is preferable.
• the reactive diluent having one or more crosslinkable functional groups in one molecule include monofunctional epoxy resins.
• the monofunctional epoxy resin include monoglycidyl compounds and monoalicyclic epoxy compounds.
• Examples of the monoglycidyl compounds include tert-butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 1-(3-glycidoxypropyl) 1,1,3,3,3-pentamethyldisiloxane, N-glycidyl-N,N-bis[3-(trimethoxysilyl)propyl]amine and the like.
• Examples of the monoalicyclic epoxy compound include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. These reactive diluents may be used alone or in combination of two or more.
• the preferred lower limit of the content of the solvent or reactive diluent in 100 parts by weight of the curable resin composition of the present invention is 0.5 parts by weight, and the preferred upper limit is 30 parts by weight. When the content of the solvent or reactive diluent is within this range, the resulting curable resin composition will be superior in coatability and the like.
• a more preferred lower limit to the content of the solvent or reactive diluent is 1 part by weight, and a more preferred upper limit is 20 parts by weight.
• the curable resin composition of the present invention may further contain additives such as a coupling agent, a storage stabilizer, an anti-bleeding agent, a fluxing agent, and a leveling agent to the extent that the object of the present invention is not impaired. .
• Examples of the method for producing the curable resin composition of the present invention include a method of mixing a curable resin, a curing agent, a curing accelerator and the like using a mixer.
• Examples of the mixer include a homodisper, a universal mixer, a Banbury mixer, a kneader, and the like.
• the preferable lower limit of the thermal conductivity after curing of the curable resin composition of the present invention is 0.15 W/m ⁇ K.
• the thermal conductivity after curing is 0.15 W / m K or more, so that the curable resin composition of the present invention can dissipate heat. It can be suitably used as an adhesive.
• a more preferable lower limit of the thermal conductivity after curing is 0.2 W/m ⁇ K, and a more preferable lower limit is 0.3 W/m ⁇ K.
• the thermal conductivity after curing of the curable resin composition of the present invention there is no particular upper limit for the thermal conductivity after curing of the curable resin composition of the present invention when it does not contain the thermally conductive filler, but the practical upper limit is 0.5 W/m ⁇ K.
• the preferable lower limit of the thermal conductivity after curing of the curable resin composition of the present invention is 1 W/m ⁇ K.
• the thermal conductivity after curing of the curable resin composition of the present invention is 1 W / m K or more, so that the curable resin composition of the present invention is a heat-dissipating adhesive. It can be suitably used as.
• a more preferable lower limit of the thermal conductivity after curing of the curable resin composition of the present invention when containing the thermally conductive filler is 1.5 W/m ⁇ K, and a more preferable lower limit is 2 W/m ⁇ K.
• There is no particular upper limit for the thermal conductivity after curing of the curable resin composition of the present invention when it contains the thermally conductive filler but the practical upper limit is 20 W/m ⁇ K.
• the thermal conductivity can be measured according to ASTM D5470 at 23°C. Examples of a measuring device used for measuring the thermal conductivity include "T3Ster DynTIM Tester" manufactured by Mentor, a Siemens Business.
• As the cured product for measuring the thermal conductivity a cured product obtained by drying the curable resin composition and then heating it at 190° C. for 1 hour is used.
• the curable resin composition of the present invention has a preferable lower limit of viscosity at 25° C. of 10 mPa ⁇ s and a preferable upper limit of 600 mPa ⁇ s. When the viscosity at 25°C is within this range, the curable resin composition of the present invention is excellent in coatability.
• a more preferable lower limit of the viscosity at 25° C. is 20 mPa ⁇ s, and a more preferable upper limit is 500 mPa ⁇ s.
• the above-mentioned "viscosity" in this specification means the value measured on conditions of 10 rpm using an E-type viscometer. Examples of the E-type viscometer include TPE-100 (manufactured by Toki Sangyo Co., Ltd.).
• the preferable lower limit of the shear adhesive strength of the cured product to aluminum is 4 MPa.
• the curable resin composition of the present invention can be suitably used as a thermally conductive adhesive.
• a more preferable lower limit of the shear adhesive strength of the cured product to aluminum is 5 MPa.
• the practical upper limit is 20 MPa.
• the shear adhesive strength of the cured product to aluminum was measured using a Tensilon universal material tester (manufactured by A&D Co., Ltd., "RTC-1350A") at 25 ° C.
• the curable resin composition was applied so that the thickness after drying was 100 ⁇ m, dried to remove the solvent, and then an aluminum substrate having a thickness of 25 mm was placed on both sides of the curable resin composition.
• a material obtained by bonding and heating at 190° C. for 1 hour is used.
• the aluminum substrate for example, A-1050P or the like can be used.
• the curable resin composition of the present invention preferably has a lower limit of 350° C. for a 5% weight loss temperature after curing. Since the 5% weight loss temperature after curing is 350° C. or higher, the curable resin composition of the present invention can be suitably used as a thermally conductive adhesive (heat-dissipating adhesive) that particularly requires heat resistance. . Although there is no particular upper limit for the 5% weight loss temperature after curing, the practical upper limit is 450°C.
• the 5% weight loss temperature can be derived by performing thermogravimetric measurement using a thermogravimetry device under conditions of temperature elevation from 30°C to 500°C at a temperature elevation rate of 10°C/min.
• thermogravimetry apparatus examples include TG/DTA6200 (manufactured by Hitachi High-Tech Science). Further, as the cured product for measuring the 5% weight loss temperature, the curable resin composition was coated on the base PET film so that the thickness after drying was 100 ⁇ m, dried, and then dried at 190 ° C. It is used after being cured by heating for 1 hour.
• the curable resin composition of the present invention preferably has an average linear expansion coefficient of 80 ppm or less in a temperature range of 25 ° C. to 80 ° C. after curing, and is 70 ppm or less. is more preferable.
• the average coefficient of linear expansion is preferably as small as possible.
• the average coefficient of linear expansion can be measured using a thermomechanical analyzer for a cured product having a thickness of 400 ⁇ m. Specifically, under the conditions of a load of 5 g and a heating rate of 10° C./min, a cured product of a sample length of 1 cm was heated from 0° C. to 300° C., cooled once, and then again from 0° C. to 300° C.
• the average coefficient of linear expansion in the temperature range from 25° C. to 80° C. can be obtained based on the temperature and dimensional change data obtained in the second measurement.
• the curable resin composition is coated on the base PET film so that the thickness after drying is 100 ⁇ m, dried, and then laminated to obtain a thickness. is 400 ⁇ m and cured by heating at 190° C. for 1 hour.
• the thermomechanical analyzer include TMA/SS-6000 (manufactured by Hitachi High-Tech Science).
• a cured product of the curable resin composition of the present invention is also one aspect of the present invention.
• An adhesive using the curable resin composition of the present invention is also one aspect of the present invention.
• An adhesive film can be obtained by a method such as coating the adhesive of the present invention on a base film and then drying it.
• An adhesive film using the adhesive of the present invention is also one aspect of the present invention.
• the adhesive of the present invention can be suitably used as a heat conductive adhesive (heat dissipation adhesive), and the adhesive film of the present invention can be suitably used as a heat conductive adhesive film (heat dissipation adhesive film).
• the curable resin composition which is excellent in heat resistance, thermal conductivity, low linear expansion property, and adhesiveness can be provided. Moreover, according to the present invention, it is possible to provide a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition.
• an oligomer solution was obtained. After removing N-methylpyrrolidone from the obtained amic acid oligomer solution under reduced pressure, the solution was heated at 300° C. for 2 hours to obtain an imide oligomer composition A (imidization rate: 95%). The obtained imide oligomer composition A was subjected to 1 H-NMR, GPC and FT-IR analysis.
• the imide oligomer composition A was an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is 1,4-phenylenebis(1,3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylate) residue, B is a dimer diamine residue). Also, the number average molecular weight of the imide oligomer composition A was 1,500. Furthermore, using a polarizing microscope equipped with a hot stage, observation was performed under crossed Nicols while the temperature was raised from room temperature to 200° C., and an optical structure derived from a liquid crystal phase was observed. , was confirmed to have mesogenic properties.
• the imide oligomer composition B was an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is 1,4-phenylenebis(1,3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylate) residue, B contains a 1,2-bis(2-aminoethoxy)ethane residue).
• the number average molecular weight of the imide oligomer composition B was 1,100. Further, by observation with a polarizing microscope as in Synthesis Example 1, it was confirmed that the imide oligomer composition B had mesogenic properties.
• the imide oligomer composition C was an imide oligomer having a structure represented by the above formula (6-1) or (6-3) (A is a 4,4'-biphthalic anhydride residue, B is a dimer diamine residue). Also, the number average molecular weight of the imide oligomer composition C was 1,200. Furthermore, by observation with a polarizing microscope as in Synthesis Example 1, it was confirmed that the imide oligomer composition C had mesogenic properties.
• the imide oligomer composition D was an imide oligomer having a structure represented by the above formula (7-2) or (7-4) (A is 1,4-phenylenebis(1,3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylate) residue, B is a dimer diamine residue).
• the number average molecular weight of the imide oligomer composition D was 1,600. Furthermore, by observation with a polarizing microscope as in Synthesis Example 1, it was confirmed that the imide oligomer composition D had mesogenic properties.
• the imide oligomer composition E was an imide oligomer (A is 4,4′-(4,4′-isopropylidenediphenoxy ) containing a diphthalic anhydride residue and B being a dimer diamine residue).
• the imide oligomer composition E had a number average molecular weight of 1,600. Furthermore, it was confirmed by the same polarizing microscope observation as in Synthesis Example 1 that the imide oligomer composition E does not have mesogenicity.
• the imide oligomer composition F was an imide oligomer (A is 4,4′-(4,4′-isopropylidenediphenoxy ) a diphthalic anhydride residue, and B a 4,4′-bis(4-aminophenoxy)biphenyl residue).
• the number average molecular weight of the imide oligomer composition F was 1,400. Furthermore, by observation with a polarizing microscope as in Synthesis Example 1, it was confirmed that the imide oligomer composition F had mesogenic properties.
• the polyimide resin solution obtained had a solid concentration of 35% by weight and a number average molecular weight of 27,000.
• Examples 1 to 20 Comparative Examples 1 to 6
• each material was stirred and mixed to prepare curable resin compositions of Examples 1 to 20 and Comparative Examples 1 to 6.
• Each curable resin composition obtained in Examples and Comparative Examples is coated on a substrate PET film so that the thickness after drying is 100 ⁇ m, dried, and then heated at 190 ° C. for 1 hour. to produce a cured product.
• the thermal conductivity of the obtained cured product was measured at 23° C. using a measuring device (manufactured by Mentor, a Siemens Business, “T3Ster DynTIM Tester)”.
• the thermal conductivity is 0.3 W/m ⁇ K or more is marked with “ ⁇ ”, and the case where the thermal conductivity is 0.2 W/m ⁇ K or more and 0.3 W/m ⁇ K " ⁇ " when it was less than K, " ⁇ " when it was 0.15 W / m ⁇ K or more and less than 0.2 W / m ⁇ K, and when it was less than 0.15 W / m ⁇ K " ⁇ ”, the thermal conductivity was evaluated.
• the thermal conductivity is 2 W/m ⁇ K or more is marked with “ ⁇ ”, and the thermal conductivity is 1.5 W/m ⁇ K or more and less than 2 W/m ⁇ K. If it was 1 W / m ⁇ K or more and less than 1.5 W / m ⁇ K, it was " ⁇ ”, and if it was less than 1 W / m ⁇ K, it was " ⁇ ". evaluated.
• Each curable resin composition obtained in Examples and Comparative Examples was coated on a substrate PET film so that the thickness after drying was 100 ⁇ m, and dried to obtain an adhesive film.
• the PET film was peeled from the obtained adhesive film, laminated, and cured by heating at 190° C. for 1 hour to prepare a cured product having a thickness of 400 ⁇ m.
• a thermomechanical analyzer (“TMA/SS-6000" manufactured by Hitachi High-Tech Science Co., Ltd.)
• the resulting cured product was measured at a load of 5 g, a heating rate of 10° C./min, and a sample length of 1 cm from 0° C. to 300° C.
• the temperature was once cooled, and the temperature was again raised from 0°C to 300°C under the same conditions.
• the average coefficient of linear expansion in the temperature range from 25°C to 80°C was obtained.
• the low linear expansion property was evaluated as " ⁇ " when the average linear expansion coefficient was 80 ppm or less, " ⁇ ” when it was over 80 ppm and 100 ppm or less, and "x" when it exceeded 100 ppm.
• the curable resin composition which is excellent in heat resistance, thermal conductivity, low linear expansion property, and adhesiveness can be provided. Moreover, according to the present invention, it is possible to provide a cured product of the curable resin composition, and an adhesive and an adhesive film using the curable resin composition.

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• 2022
  • 2022-11-16 KR KR1020247010995A patent/KR20240099151A/ko active Pending
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  • 2022-11-16 CN CN202280074832.0A patent/CN118215700A/zh active Pending
  • 2022-11-16 WO PCT/JP2022/042510 patent/WO2023090347A1/ja not_active Ceased

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