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WO2020116467A1 - Thermosetting resin composition and sheet - Google Patents

Thermosetting resin composition and sheet Download PDF

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Publication number
WO2020116467A1
WO2020116467A1 PCT/JP2019/047289 JP2019047289W WO2020116467A1 WO 2020116467 A1 WO2020116467 A1 WO 2020116467A1 JP 2019047289 W JP2019047289 W JP 2019047289W WO 2020116467 A1 WO2020116467 A1 WO 2020116467A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
thermosetting resin
mass
component
present
Prior art date
Application number
PCT/JP2019/047289
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French (fr)
Japanese (ja)
Inventor
英治 神生
奈緒子 井上
橋本　卓幸
Original Assignee
ナガセケムテックス株式会社
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Priority to JP2020559934A priority Critical patent/JPWO2020116467A1/en
Publication of WO2020116467A1 publication Critical patent/WO2020116467A1/en

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Classifications

    • 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
    • C08G59/50—Amines
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a thermosetting resin composition and a sheet. More specifically, it relates to a thermosetting resin composition and sheet having excellent heat resistance and flexibility.
  • a material made of a polymaleimide compound is known as a material having excellent heat resistance, but it has excellent heat resistance, but its physical properties are so hard that it can only be used for a specific purpose.
  • materials having flexibility materials using various polymer materials are known, but polymer compounds are generally weak in heat and inferior in heat resistance.
  • a polyimide compound As a material having heat resistance and flexibility, a polyimide compound has been attracting attention in recent years, but it has a special structure and is selected as a material such that it is soluble only in a specific solvent and does not cure unless it is at a high temperature. There was a problem that the sex was narrow.
  • Patent Document 1 For example, in Patent Document 1, (A) a polymaleimide compound having two or more maleimide groups in a molecule, (B) an epoxy resin having two or more epoxy groups in a molecule, (C) an epoxy resin curing agent. And (D) a thermosetting resin composition comprising an adhesive resin containing a specific acrylic resin-based adhesive resin or a thermoplastic copolyester resin, and an electronic component molded and sealed with the resin composition. Furthermore, in Patent Document 2, a resin solution of polyimide or a polyimide precursor is applied onto a base substrate so that the thickness of the polyimide film is 50 ⁇ m or less, and heat treatment is completed to form a polyimide film on the base substrate.
  • the base substrate is removed in a state where the polyimide film and the stress relaxation layer are laminated, and a display device or a display device on the surface of the polyimide film opposite to the base substrate.
  • a method of manufacturing a display device for forming a member for use is disclosed.
  • an object of the present invention is to provide a resin composition having both heat resistance and flexibility after curing and curable at low temperature.
  • the present invention is the following thermosetting resin composition and sheet.
  • thermosetting resin composition of the present invention for solving the above-mentioned problems is characterized by containing the following components (A) to (D).
  • (D) Aromatic amine compound According to this feature, (A) to By containing the component (D), the flexibility of the cured product obtained by curing the thermosetting resin composition is improved, and the thermosetting resin composition having both heat resistance and flexibility can be obtained.
  • the component (A) is a compound having an aromatic ring. According to this feature, since the component (A) has an aromatic ring, a thermosetting resin composition having improved heat resistance after curing can be obtained.
  • thermosetting resin composition of the present invention is characterized in that the component (C) is a polyester having a structure of the following formula (1).
  • R 1 is each independently an alkyl group which may be substituted with a hydrogen atom or a halogen atom
  • X is a group containing an aromatic ring
  • Y is a single bond, an alkylene group or oxygen.
  • the atom, and the number of repetitions n represents an integer of 1 or more.
  • the content of the component (A) when the total content of the components (A) to (D) in the thermosetting resin composition is 100% by mass.
  • the content of the component (B) is 1 to 13 mass %
  • the content of the component (C) is 15 to 75 mass %
  • the content of the component (D) is 1 to 15 mass %. It is characterized by being. According to this feature, the effect of the present invention can be more exerted. Further, the heat resistance and flexibility after curing can be controlled according to the application of the thermosetting resin composition.
  • the sheet of the present invention for solving the above problems is characterized by containing a thermosetting resin composition containing components (A) to (D).
  • a sheet having a weight average molecular weight of 500 g/mol or more and containing a polymaleimide compound having two or more maleimide groups improves the flexibility of the sheet, and has both heat resistance and flexibility. can do.
  • thermosetting resin composition The thermosetting resin composition of the present invention is characterized by containing the following components (A) to (D).
  • the (A) polymaleimide compound in the thermosetting resin composition of the present invention is a compound having a weight average molecular weight of 500 g/mol or more and having two or more maleimide groups.
  • the lower limit of the weight average molecular weight is preferably 1000 g/mol or more, more preferably 1500 g/mol or more, and further preferably 2000 g/mol or more.
  • the upper limit is preferably 25,000 g/mol or less.
  • the (A) polymaleimide compound in the thermosetting resin composition of the present invention preferably has a number average molecular weight of 500 g/mol or more.
  • the lower limit of the number average molecular weight is preferably 1000 g/mol or more, more preferably 1500 g/mol or more, and further preferably 2000 g/mol or more.
  • the upper limit is preferably 25,000 g/mol or less.
  • the (A) polymaleimide compound in the thermosetting resin composition of the present invention has two or more maleimide groups.
  • the maleimide group is a structure represented by the following formula (2).
  • R 2 represents a substituent, and is preferably a hydrogen atom or alkyl having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms is preferably linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group and pentyl. Group, hexyl group and the like.
  • the (A) polymaleimide compound of the present invention preferably has a structure represented by the following formula (3).
  • m represents the number of repeating polyimide units containing 0, and is preferably 1 to 20, and more preferably 1 to 10.
  • the (A) polymaleimide compound may be a mixture of compounds of the formula (3) having different m.
  • Z is preferably each independently an aliphatic ring, an aromatic ring, or an aromatic ring having a hetero atom, and the ring structure thereof is bonded by an alkylene group or an ether structure. It may be.
  • R 3 is preferably each independently a structure containing an aliphatic ring, an aromatic ring, an aromatic ring having a hetero atom, an alkyl group, an alkylene group, a polyether group or a polysiloxane group.
  • R 2 is the same as that described in Formula (2) above.
  • the (A) polymaleimide compound of the present invention preferably has a structure represented by the following formulas (4) to (6).
  • R 3 and m are the same as those described in formula (3) above. More preferably, R 3 is a hydrocarbon group having a cyclic structure, and the number of carbon atoms is preferably 20 or more and 50 or less.
  • the (A) polymaleimide compound in the thermosetting resin composition of the present invention specifically, Designer Molecule Inc. (DMI) BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000GEL, BMI-3000 Commercial Grade, BMI-3000 powder, BMI-5000 powder, BMI-5000 Toluene, BMI-6000. And MIR-3000 manufactured by Nippon Kayaku Co., Ltd. and the like.
  • DMI Designer Molecule Inc.
  • thermosetting resin composition of the present invention specifically includes compounds represented by the following formulas (7) to (11).
  • R 4's each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and a phenyl group, and p is an average value and 1 ⁇ n Represents ⁇ 5.
  • the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group, and a pentyl group.
  • the content of the component (A) in the solid content of the thermosetting resin composition of the present invention is preferably 10 to 80% by mass.
  • the solid content refers to a component other than the solvent in the thermosetting resin composition of the present invention and a component that is dissolved or dispersed in the solvent.
  • the above components (A) to (D), the following curing agents (including latent curing agents), curing accelerators and the like are included.
  • thermosetting resin composition of the present invention when the total content of the components (A) to (D) is 100% by mass, the content of the component (A) is preferably 15 to 75% by mass, It is more preferably 20 to 60% by mass.
  • the (B) epoxy resin in the thermosetting resin composition of the present invention is not particularly limited, and is preferably various epoxy resins such as an aromatic epoxy resin, an aliphatic epoxy resin, and an alicyclic epoxy resin.
  • a polyfunctional epoxy resin having an average number of epoxy groups of 2 or more is preferable.
  • the average number of epoxy groups can be determined by dividing the weight average molecular weight determined by gel permeation chromatography (GPC) by the epoxy equivalent weight determined according to JIS K7236.
  • the aromatic epoxy resin preferably has an aromatic ring in one molecule and has an average number of epoxy groups of 2 or more.
  • bisphenol compounds such as bisphenol A and bisphenol F, or derivatives thereof; biphenyl compounds such as 4,4′-biphenol, 3,3′,5,5′-tetramethylbiphenyl-4,4′-diol, or their derivatives.
  • aromatic epoxy resins since the resulting cured product has good heat resistance and mechanical strength, bisphenol compounds such as bisphenol A and bisphenol F or derivatives thereof, phenol novolac resins, cresol novolac resins, and It is an epoxy resin obtained by epoxidizing a derivative of diaminodiphenylmethane skeleton.
  • a bisphenol-based epoxy resin is more preferable because the obtained cured product has an excellent balance of heat resistance and mechanical strength.
  • the aliphatic epoxy resin preferably has an aliphatic skeleton in one molecule and has an average number of epoxy groups of 2 or more.
  • an epoxy resin obtained by epoxidizing an aliphatic diol such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, nonanediol or decanediol, or a polyhydric alcohol such as pentaerythritol or sorbitol, or a derivative thereof.
  • Etc an epoxy resin obtained by epoxidizing an aliphatic diol such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, nonanediol or decanediol, or a polyhydric alcohol such as pentaerythritol or sorbitol, or a derivative thereof
  • the alicyclic epoxy resin preferably has an alicyclic skeleton in one molecule and has an average number of epoxy groups of 2 or more.
  • 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferably used because the resulting cured product is particularly excellent in heat resistance and mechanical strength.
  • the various epoxy resins such as the aromatic epoxy resin, the aliphatic epoxy resin and the alicyclic epoxy resin may be used alone or in combination of two or more kinds.
  • the content of the component (B) in the solid content of the thermosetting resin composition of the present invention is preferably 1 to 15% by mass.
  • the content of the component (B) is preferably 1 to 13 mass% when the total content of the components (A) to (D) is 100 mass %. is there.
  • the (C) polyester in the thermosetting resin composition of the present invention is a polymer obtained by reacting a diol compound with a dicarboxylic acid compound or a dicarboxylic acid halide.
  • the diol compound is not particularly limited, and examples thereof include an aliphatic diol, an alicyclic diol, and an aromatic diol, preferably an aromatic diol, and more preferably a dihydric phenol compound.
  • the dihydric phenol compound is preferably 4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-.
  • Biphenol 2,2',3,3',5,5'-hexamethyl-4,4'-biphenol, 3,3',5,5'-tetra-tert-butyl-2,2'-biphenol, 2 ,2'-bis(4-hydroxyphenyl)methane, 2,2'-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl) ) Pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1 ,1-bis(4-hydroxyphenyl)-2-ethylhexane
  • examples of the aliphatic diol include ethylene glycol and propylene glycol.
  • examples of the alicyclic diol include 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol.
  • the dicarboxylic acid or dicarboxylic acid halide is not particularly limited, and examples thereof include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and halides thereof, preferably aromatic dicarboxylic acid, more preferably wholly aromatic. It is a divalent carboxylic acid or a halide thereof.
  • Examples of the wholly aromatic divalent carboxylic acid or halide thereof include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'- Examples thereof include dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid and halides thereof.
  • Examples of the aliphatic dicarboxylic acid or halide thereof include adipic acid and sebacic acid.
  • Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and halides thereof.
  • the terminal structure of the (C) polyester in the thermosetting resin composition of the present invention is preferably a hydroxyl group.
  • the terminal structure of the (C) polyester By making the terminal structure of the (C) polyester a hydroxyl group, it can efficiently act on the curing of the (A) polymaleimide and (B) epoxy resin, and the heat resistance of the thermosetting resin composition after curing can be improved. It can be further improved.
  • the (C) polyester in the present invention is preferably a polyester having a structure of the following formula (1).
  • each R 1 is independently an alkyl group optionally substituted with a hydrogen atom or a halogen atom.
  • the alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group. , A pentyl group, a hexyl group and the like.
  • the halogen atom includes fluorine, chlorine, bromine and iodine atoms.
  • X is a group containing an aromatic ring.
  • the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring.
  • Specific examples of the structure of X include a phenylene group, a naphthalene group, a diphenylalkyl group, a diphenylether group, and a diphenylsulfone group. ..
  • Y is a single bond, an alkylene group or an oxygen atom.
  • the alkylene group include alkylene groups having 1 to 10 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group and a butylene group.
  • the weight average molecular weight of the (C) polyester in the present invention is preferably 5,000 to 150,000. By setting the weight average molecular weight within the above range, it is possible to improve the uniformity of each component in the thermosetting resin composition and the solvent solubility.
  • the glass transition temperature of the (C) polyester in the thermosetting resin composition of the present invention is preferably 180° C. or higher.
  • the lower limit value is more preferably 200°C or higher, and further preferably 220°C or higher.
  • the content of the component (C) in the solid content of the thermosetting resin composition of the present invention is preferably 10 to 80% by mass. By setting the content of the component (C) within the above range, a thermosetting resin composition having good heat resistance and flexibility can be obtained.
  • the content of the component (C) is preferably 15 to 75 mass% when the total content of the components (A) to (D) is 100 mass %. is there.
  • the (D) aromatic amine compound in the thermosetting resin composition of the present invention contributes to the curing of the (A) polymaleimide compound and (B) epoxy resin.
  • the aromatic amine compound (D) is preferably an amine compound having a benzene ring, and examples thereof include phenylenediamine, diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane and 4,4′-diamino.
  • the content of the (D) component is preferably 1 to 15% by mass. ..
  • thermosetting resin composition of the present invention may be dissolved in a solvent (E) to form a varnish.
  • the solvent is not particularly limited, but a ketone solvent, an ester solvent, an alcohol solvent or the like is preferable. Specific examples include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), and the like.
  • the amount of the solvent (E) is preferably 1 to 20,000 parts by mass based on 100 parts by mass of the solid content contained in the thermosetting resin composition.
  • the solid content is a component that is soluble in a solvent, and includes, for example, the above-mentioned components (A) to (D), the following curing agents (including latent curing agents), and curing accelerators.
  • the thermosetting resin composition of the present invention may further contain a curing agent.
  • the curing agent to be contained is not particularly limited, but preferably, a phenol-based curing agent (phenol resin or the like), a dicyandiamide-based curing agent (dicyandiamide or the like), a urea-based curing agent, an organic acid hydrazide-based curing agent, an amine adduct-based agent
  • the curing agent include acid curing agents, acid anhydride curing agents, and imidazole curing agents. These may be used alone or in combination of two or more.
  • the above-mentioned phenol-based curing agent is preferably a condensation polymerization of phenol or naphthol (for example, phenol, cresol, naphthol, alkylphenol, bisphenol, terpenephenol) and formaldehyde.
  • phenol or naphthol for example, phenol, cresol, naphthol, alkylphenol, bisphenol, terpenephenol
  • formaldehyde for example, phenol, cresol, naphthol, alkylphenol, bisphenol, terpenephenol
  • examples thereof include novolac, xylylene-modified novolac, decalin-modified novolac, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, and poly(di-p-hydroxyphenyl)methane. These may be used alone or in combination of two or more.
  • the acid anhydride-based curing agent examples include phthalic anhydride, hexahydrophthalic anhydride, and alkylhexahydrophthalic anhydride such as methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride.
  • alkyltetrahydrophthalic anhydride such as 3-methyltetrahydrophthalic anhydride, hymic acid anhydride, succinic anhydride, trimellitic anhydride, and pyromellitic anhydride. These may be used alone or in combination of two or more. Of these, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride are preferable.
  • the content of the curing agent can be appropriately set depending on the type of the curing agent.
  • the equivalent number of the functional group of the curing agent is preferably 0.001 to 2 equivalents, and more preferably 0.005 to 1.5 equivalents per equivalent of the epoxy group.
  • the dicyandiamide curing agent, urea curing agent, organic acid hydrazide curing agent, and amine adduct curing agent are latent curing agents.
  • the lower limit of the activation temperature of the latent curing agent is preferably 60°C or higher, more preferably 80°C or higher.
  • the upper limit of the activation temperature is preferably 250°C or lower, more preferably 180°C or lower.
  • the thermosetting resin composition of the present invention may contain a curing accelerator.
  • the curing accelerator is not particularly limited, but is preferably a modified imidazole-based curing accelerator, a modified aliphatic polyamine-based accelerator, a modified polyamine-based accelerator, or the like.
  • the curing accelerator is preferably used as a reaction product (adduct) with a resin such as an epoxy resin. These may be used alone or in combination of two or more.
  • the lower limit of the activation temperature of the curing accelerator is preferably 60°C or higher, more preferably 80°C or higher.
  • the upper limit of the activation temperature is preferably 250°C or lower, more preferably 180°C or lower.
  • the activation temperature is a temperature at which the thermosetting resin is rapidly accelerated by the action of the latent curing agent and/or the curing accelerator.
  • the amount of the curing accelerator can be appropriately set depending on the type of the curing accelerator, but it is usually 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the epoxy resin. Is.
  • the amount of the curing accelerator means the net amount of the curing accelerator excluding the components other than the curing accelerator (such as epoxy resin).
  • thermosetting resin composition of the present invention may contain a third component other than the above.
  • the third component include a thermoplastic resin, an inorganic filler, a polymerization initiator, a flame retardant, a pigment, a dispersant, a silane coupling agent, and a thixotropic agent.
  • the inorganic filler examples include silica, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride and the like.
  • the particle diameter (D50) at a cumulative volume of 50% in the volume particle size distribution is, for example, 0.01 to 100 ⁇ m.
  • the amount of the inorganic filler is preferably 1 to 5000 parts by mass, more preferably 10 to 3000 parts by mass, per 100 parts by mass of the total of the components (A) to (C).
  • the polymerization initiator develops curability when heated.
  • a radical generator an acid generator, a base generator or the like can be used.
  • benzophenone compounds, hydroxyketone compounds, azo compounds, organic peroxides, sulfonium salts such as aromatic sulfonium salts and aliphatic sulfonium salts can be used.
  • the amount of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the epoxy resin.
  • thermosetting resin composition of the present invention can be molded into a sheet, film or the like for use.
  • the form of the sheet is not particularly limited, and may be a single layer sheet or a multilayer sheet having two or more layers.
  • the thickness of the sheet of the present invention is not particularly limited, but is preferably 10 to 1500 ⁇ m, more preferably 20 to 500 ⁇ m. If the thickness is less than 10 ⁇ m, the surface hardness may be insufficient, and if it exceeds 1500 ⁇ m, the surface may be easily cracked, and the roll-to-roll winding may be difficult.
  • the sheet of the present invention is preferably in an uncured state, a semi-cured state, or a cured state.
  • the semi-cured state is a state in which the thermosetting resin composition contains a monomer and/or an oligomer, and is a state in which the three-dimensional crosslinked structure of the compound in the thermosetting resin composition is insufficiently developed. That is, if necessary, the coating film may be heated at 50 to 150° C. for 1 to 10 minutes to gel or B stage to form a sheet.
  • the term "B-stage” means that the resin composition is made into a semi-cured solid. When the B-stage resin composition is heated, it is melted and the curing reaction proceeds further.
  • the cured state means a state in which the thermosetting resin composition is completely cured.
  • thermosetting resin composition dissolved in the solvent shown above may be applied to a substrate, dried and then heated to cure the composition. Since the cured product of the thermosetting resin composition of the present invention contains the above-mentioned components (A) to (D), it exhibits heat resistance and flexibility after curing and curability at a relatively low temperature. It has the property of having both.
  • the method for producing the sheet of the present invention is not particularly limited, but a roll-to-roll process is preferably used from the viewpoint of productivity. Specifically, it can be obtained by coating various support films (PET, PMMA film and the like subjected to mold release treatment) with the resin composition of the present invention to a predetermined thickness and peeling the support film. Examples of the coating method include gravure coating, roll coating, bar coating, die coating, knife coating and the like.
  • a cured product can be obtained by proceeding with the curing of the thermosetting resin composition of the present invention.
  • the form of the cured product is preferably a sheet, a film or the like.
  • the thermosetting resin composition dissolved in the solvent shown above may be applied to a substrate, dried and then heated to cure the composition.
  • the curing temperature is not particularly limited, but it is preferably 220°C or lower.
  • the lower limit value is more preferably 90°C or higher, and further preferably 100°C or higher.
  • the upper limit value is more preferably 200°C or lower, and further preferably 190°C or lower.
  • the curing time is not particularly limited, but is preferably 30 minutes or more and 1500 minutes, and the lower limit value is more preferably 60 minutes or more. Since the thermosetting resin composition of the present invention contains the above-mentioned components (A) to (D), it can be cured at a low temperature of 220° C. or lower, and the heat of curing adversely affects the related materials. Can be suppressed.
  • the flexural modulus of the cured product obtained by curing the thermosetting resin composition of the present invention at ⁇ 40° C. is preferably 1.0 GPa or more, more preferably 1.4 GPa or more. Further, at 25° C., it is preferably 1.0 GPa or more, more preferably 1.4 GPa or more. Furthermore, at 250° C., it is preferably 0.01 GPa or more, more preferably 0.011 GPa or more.
  • the flexural modulus was measured in accordance with JIS K7171, using a Strograph VG20-E (manufactured by Toyo Seiki Seisaku-sho, Ltd.) under the conditions of a measured humidity of 50% RH, a load cell of 1.0 kN, and a head moving speed of 5 mm/min. Can be measured at.
  • the tensile strength of a cured product obtained by curing the thermosetting resin composition of the present invention is preferably 15 N or higher at 25°C.
  • the tensile strength can be measured using an autograph manufactured by Shimadzu Corporation under the conditions of a chuck thickness of 20 mm, a pulling speed of 5 mm/min, and a sheet thickness of 50 ⁇ m.
  • the elongation of the cured product obtained by curing the thermosetting resin composition of the present invention is preferably 10% or more at 25°C. Furthermore, at 25° C., it is more preferably 20% or more, further preferably 30% or more.
  • the elongation can be measured by using an autograph manufactured by Shimadzu Corporation under the conditions of a chuck thickness of 20 mm, a pulling speed of 5 mm/min, and a sheet thickness of 50 ⁇ m.
  • the cured product obtained by curing the thermosetting resin composition of the present invention has a heating weight loss temperature of 5.0% by mass of preferably 300°C or higher, more preferably 325°C, further preferably 350°C or higher.
  • the 5.0 mass% heating loss temperature is measured by a thermogravimetric analyzer (TGA) at a temperature rising rate of 10°C/min based on the mass at 25°C and the mass is reduced by 5.0% by mass. Can be measured as the temperature of.
  • the glass transition temperature Tg of the cured product obtained by curing the thermosetting resin composition of the present invention is preferably 50° C. or higher, more preferably 70° C. or higher.
  • the glass transition temperature Tg is preferably higher, and the upper limit value is not particularly limited, but is, for example, 250° C. or lower.
  • the glass transition temperature Tg of the cured product is measured using a differential scanning calorimetry (DSC) device (manufactured by Seiko Instruments Inc.) under the conditions of a temperature range of 30 to 250° C., a heating rate of 2° C./min, and a frequency of 1 MHz. be able to.
  • DSC differential scanning calorimetry
  • the cured product obtained by curing the thermosetting resin composition of the present invention since the cured product obtained by curing the thermosetting resin composition of the present invention has excellent heat resistance and flexibility, it is a sealant for electronic parts such as semiconductors, laminates, FRP (composite material). It can be preferably used as a component material that is required to have high mechanical/electrical connection reliability and is used in the fields of automobiles/aircrafts and electric/electronic materials such as interlayer insulating materials and adhesives. Further, due to its flexibility, it can be suitably used as a flexible base material used for wearable terminals.
  • thermosetting resin composition was obtained with the composition (parts by mass) shown in Table 1.
  • the viscosity of this thermosetting resin composition was measured under the conditions of 25° C. and a shear rate of 2.5 (1/s) using an HBT type viscometer (spindle type: No29) manufactured by Brookfield.
  • thermosetting resin composition prepared above was coated into a sheet by a coating method and cured at 180° C. for 120 minutes to prepare a cured sheet having a thickness of 50 ⁇ m.
  • Table 2 shows the evaluation results and the content of the components (A) to (D) expressed in mass% when the total content of the components (A) to (D) is 100 mass %.
  • [Evaluation methods] ⁇ 5.0% by mass heating loss temperature With a thermal mass measuring device (TGA), the temperature at which the mass is reduced by 5.0% by mass is measured at a temperature rising rate of 10°C/min with reference to the mass at 25°C. It was measured.
  • TGA thermal mass measuring device
  • Tensile strength and elongation The tensile strength and elongation at 25° C. of the test piece prepared from the cured sheet were measured with an autograph manufactured by Shimadzu Corporation under the conditions of a chuck distance of 20 mm and a tensile speed of 5 mm/min.
  • thermosetting resin composition containing the components (A) to (D) of the present invention can be cured at a low temperature of 180° C. and has both heat resistance and flexibility. It has been found that sheets can be formed. On the other hand, Comparative Examples 1 and 2 containing the polymaleimide having a weight average molecular weight of less than 500 g/mol resulted in inferior flexibility as compared with the sheets of Examples. Further, it was found that the sheet of Comparative Example 3 containing no (B) epoxy resin was inferior in elongation rate and heat resistance.
  • the silicon wafer sealed with the thermosetting resin composition was evaluated according to the following criteria and methods. After the above post-curing, the temperature was cooled to room temperature, and the amount of warpage was evaluated according to the following criteria. As a measurement method, a laser displacement meter was used to measure the average of the height differences between the center of the silicon wafer on the substrate side and two points on the wafer edge. As a result, the amount of warpage was less than 2 mm for both thicknesses of 200 ⁇ m and 50 ⁇ m.
  • thermosetting resin composition of the present invention Since the cured product obtained by curing the thermosetting resin composition of the present invention has excellent heat resistance and flexibility, it is used as a semiconductor encapsulant, laminate, FRP (composite material), interlayer insulating material, and adhesive. It can be suitably used as a component material that is required in high mechanical/electrical connection reliability and is used in the fields of automobiles/aircrafts and electric/electronic materials. Further, due to its flexibility, it can be suitably used as a flexible base material used for wearable terminals.

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Abstract

The present invention addresses the problem of providing a resin composition that can be cured at a low temperature and that has both heat resistance and flexibility after being cured. In order to solve the problem, the present invention provides a thermosetting resin composition characterized by containing components (A)-(D): (A) a poly-maleimide compound having two or more maleimide groups and having a weight average molecular weight not less than 500 g/mol; (B) an epoxy compound; (C) a polyester; and (D) an aromatic amine compound.

Description

熱硬化性樹脂組成物及びシートThermosetting resin composition and sheet
　本発明は、熱硬化性樹脂組成物及びシートに関する。さらに詳しくは、耐熱性と柔軟性に優れた熱硬化性樹脂組成物及びシートに関する。 The present invention relates to a thermosetting resin composition and a sheet. More specifically, it relates to a thermosetting resin composition and sheet having excellent heat resistance and flexibility.
　耐熱性に優れた材料として、ポリマレイミド化合物からなる材料が知られているが、耐熱性には優れているものの、その物性は硬く、用途として特定の用途にしか用いることができていなかった。
　一方、柔軟性を有する材料として、各種高分子材料を用いたものが知られているが、一般的に高分子化合物は熱に弱く、耐熱性に劣るという問題があった。 A material made of a polymaleimide compound is known as a material having excellent heat resistance, but it has excellent heat resistance, but its physical properties are so hard that it can only be used for a specific purpose.
On the other hand, as materials having flexibility, materials using various polymer materials are known, but polymer compounds are generally weak in heat and inferior in heat resistance.
　そして、耐熱性と柔軟性を備えた材料として、近年ポリイミド化合物が着目されているが、構造が特殊な材料であり、特定の溶媒にしか溶解しない、高温でないと硬化しない等、材料としての選択性が狭いという問題があった。 And, as a material having heat resistance and flexibility, a polyimide compound has been attracting attention in recent years, but it has a special structure and is selected as a material such that it is soluble only in a specific solvent and does not cure unless it is at a high temperature. There was a problem that the sex was narrow.
　例えば、特許文献１には、（Ａ）分子中に２個以上のマレイミド基を有するポリマレイミド化合物、（Ｂ）分子中に二個以上のエポキシ基を有するエポキシ樹脂、（Ｃ）エポキシ樹脂硬化剤、および（Ｄ）特定のアクリル樹脂系接着性樹脂または熱可塑性共重合ポリエステル樹脂を含有する接着性樹脂からなる熱硬化性樹脂組成物、ならびにそれで成形封止された電子部品が開示されている。
　さらに、特許文献２には、ベース基板上に、ポリイミド又はポリイミド前駆体の樹脂溶液をポリイミドフィルムの厚みが５０μｍ以下になるように塗布し、加熱処理を完了させ、ベース基板上にポリイミドフィルムを形成し、ポリイミドフィルム上に応力緩和層を形成した後、ポリイミドフィルムと応力緩和層が積層された状態でベース基板を除去し、かつ、ポリイミドフィルムのベース基板と反対側の面に表示装置または表示装置用部材を形成する表示装置の製造方法が開示されている。 For example, in Patent Document 1, (A) a polymaleimide compound having two or more maleimide groups in a molecule, (B) an epoxy resin having two or more epoxy groups in a molecule, (C) an epoxy resin curing agent. And (D) a thermosetting resin composition comprising an adhesive resin containing a specific acrylic resin-based adhesive resin or a thermoplastic copolyester resin, and an electronic component molded and sealed with the resin composition.
Furthermore, in Patent Document 2, a resin solution of polyimide or a polyimide precursor is applied onto a base substrate so that the thickness of the polyimide film is 50 μm or less, and heat treatment is completed to form a polyimide film on the base substrate. Then, after forming the stress relaxation layer on the polyimide film, the base substrate is removed in a state where the polyimide film and the stress relaxation layer are laminated, and a display device or a display device on the surface of the polyimide film opposite to the base substrate. A method of manufacturing a display device for forming a member for use is disclosed.
特開平６－３２９７２６号公報JP-A-6-329726 特開２０１７－１３９２２８号公報JP, 2017-139228, A
　これまで、様々な高耐熱材料及び柔軟性を備えた材料が開発されてきているが、それらは未だ満足できる物性を備えたものではない。
　そこで、本発明の課題は、硬化後に耐熱性及び柔軟性を併せ持ち、かつ低温で硬化可能な樹脂組成物を提供することである。 Up to now, various high heat resistant materials and materials having flexibility have been developed, but they are not yet provided with satisfactory physical properties.
Therefore, an object of the present invention is to provide a resin composition having both heat resistance and flexibility after curing and curable at low temperature.
　発明者は、上記課題に対して鋭意検討した結果、特定の重量平均分子量を有するポリマレイミド化合物を、エポキシ化合物、ポリエステル、芳香族アミン化合物と組み合わせることにより、上記課題を解決できることを見出し本発明を完成した。
　すなわち、本発明は、以下の熱硬化性樹脂組成物及びシートである。 The inventor, as a result of intensive studies on the above problems, found that the polymaleimide compound having a specific weight average molecular weight can be solved by combining the epoxy compound, the polyester, and the aromatic amine compound to solve the above problems. completed.
That is, the present invention is the following thermosetting resin composition and sheet.
　上記課題を解決するための本発明の熱硬化性樹脂組成物は、下記の（Ａ）～（Ｄ）成分を含有することを特徴とするものである。
　（Ａ）重量平均分子量が５００ｇ/ｍｏｌ以上であり、マレイミド基を２個以上有するポリマレイミド化合物
　（Ｂ）エポキシ化合物
　（Ｃ）ポリエステル
　（Ｄ）芳香族アミン化合物
　この特徴によれば、（Ａ）～（Ｄ）成分を含有することで、熱硬化性樹脂組成物を硬化した硬化物の柔軟性が向上し、耐熱性及び柔軟性を併せ持つ熱硬化性樹脂組成物とすることができる。 The thermosetting resin composition of the present invention for solving the above-mentioned problems is characterized by containing the following components (A) to (D).
(A) Polymaleimide compound having a weight average molecular weight of 500 g/mol or more and having two or more maleimide groups (B) Epoxy compound (C) Polyester (D) Aromatic amine compound According to this feature, (A) to By containing the component (D), the flexibility of the cured product obtained by curing the thermosetting resin composition is improved, and the thermosetting resin composition having both heat resistance and flexibility can be obtained.
　また、本発明の熱硬化性樹脂組成物の一実施態様としては、（Ａ）成分が、芳香環を有する化合物であることを特徴とするものである。
　この特徴によれば、（Ａ）成分が芳香環を有することで、硬化後により耐熱性が向上した熱硬化性樹脂組成物とすることができる。 Moreover, as one embodiment of the thermosetting resin composition of the present invention, the component (A) is a compound having an aromatic ring.
According to this feature, since the component (A) has an aromatic ring, a thermosetting resin composition having improved heat resistance after curing can be obtained.
　また、本発明の熱硬化性樹脂組成物の一実施態様としては、（Ｃ）成分が、下記式（１）の構造を有するポリエステルであることを特徴とするものである。
Figure JPOXMLDOC01-appb-C000002
 （式（１）中、Ｒ１はそれぞれ独立して、水素原子又はハロゲン原子で置換されていてもよいアルキル基を、Ｘは、芳香環を含む基を、Ｙは単結合、アルキレン基又は酸素原子を、繰り返し数ｎは１以上の整数を表す。）
　この特徴によれば、（Ｃ）成分が式（１）の構造を有するポリエステルであることで、より本発明の効果を発揮することができる。 Moreover, one embodiment of the thermosetting resin composition of the present invention is characterized in that the component (C) is a polyester having a structure of the following formula (1).
Figure JPOXMLDOC01-appb-C000002
 (In the formula (1), R 1 is each independently an alkyl group which may be substituted with a hydrogen atom or a halogen atom, X is a group containing an aromatic ring, and Y is a single bond, an alkylene group or oxygen. The atom, and the number of repetitions n represents an integer of 1 or more.)
According to this feature, since the component (C) is a polyester having the structure of the formula (1), the effects of the present invention can be more exerted.
　本発明の熱硬化性樹脂組成物の一実施態様としては、熱硬化性樹脂組成物において（Ａ）～（Ｄ）成分の合計含有量を１００質量％としたときの、（Ａ）成分の含有量が１５～７５質量％、（Ｂ）成分の含有量が１～１３質量％、（Ｃ）成分の含有量が１５～７５質量％、（Ｄ）成分の含有量が１～１５質量％であることを特徴とするものである。
　この特徴によれば、より本発明の効果を発揮することができる。また、熱硬化性樹脂組成物の用途に合わせて、硬化後の耐熱性及び柔軟性を制御することができる。 As one embodiment of the thermosetting resin composition of the present invention, the content of the component (A) when the total content of the components (A) to (D) in the thermosetting resin composition is 100% by mass. The content of the component (B) is 1 to 13 mass %, the content of the component (C) is 15 to 75 mass %, and the content of the component (D) is 1 to 15 mass %. It is characterized by being.
According to this feature, the effect of the present invention can be more exerted. Further, the heat resistance and flexibility after curing can be controlled according to the application of the thermosetting resin composition.
　また、上記課題を解決するための本発明のシートとしては、（Ａ）～（Ｄ）成分を含有する熱硬化性樹脂組成物を含有することを特徴とするものである。
　この特徴によれば、重量平均分子量が５００ｇ/ｍｏｌ以上であり、マレイミド基を２個以上有するポリマレイミド化合物を含有することで、シートの柔軟性が向上し、耐熱性及び柔軟性を併せ持つシートとすることができる。 The sheet of the present invention for solving the above problems is characterized by containing a thermosetting resin composition containing components (A) to (D).
According to this feature, a sheet having a weight average molecular weight of 500 g/mol or more and containing a polymaleimide compound having two or more maleimide groups improves the flexibility of the sheet, and has both heat resistance and flexibility. can do.
　本発明によれば、硬化後に耐熱性及び柔軟性を併せ持ち、かつ低温で硬化可能な樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a resin composition which has both heat resistance and flexibility after curing and can be cured at a low temperature.
　以下、本発明の好適な実施形態について詳細に説明する。ただし、本発明は、以下の実施形態に限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
［熱硬化性樹脂組成物］
　本発明の熱硬化性樹脂組成物は、下記の（Ａ）～（Ｄ）成分を含有することを特徴とするものである。
　（Ａ）重量平均分子量が５００ｇ/ｍｏｌ以上であり、マレイミド基を２個以上有するポリマレイミド化合物
　（Ｂ）エポキシ化合物
　（Ｃ）ポリエステル
　（Ｄ）芳香族アミン化合物 [Thermosetting resin composition]
The thermosetting resin composition of the present invention is characterized by containing the following components (A) to (D).
(A) Polymaleimide compound having a weight average molecular weight of 500 g/mol or more and having two or more maleimide groups (B) Epoxy compound (C) Polyester (D) Aromatic amine compound
＜（Ａ）ポリマレイミド化合物＞
　本発明の熱硬化性樹脂組成物における、（Ａ）ポリマレイミド化合物は、重量平均分子量が５００ｇ/ｍｏｌ以上であり、マレイミド基を２個以上有する化合物である。
　重量平均分子量の下限値としては、好ましくは１０００ｇ/ｍｏｌ以上であり、より好ましくは１５００ｇ/ｍｏｌ以上であり、さらに好ましくは２０００ｇ/ｍｏｌ以上である。上限値としては、好ましくは２５０００ｇ/ｍｏｌ以下である。
　（Ａ）ポリマレイミド化合物の重量平均分子量を５００ｇ/ｍｏｌ以上とすることで、硬化物の柔軟性が向上し、硬化後に耐熱性及び柔軟性を併せ持つ熱硬化性樹脂組成物とすることができる。また、（Ａ）ポリマレイミド化合物の重量平均分子量を２５０００ｇ/ｍｏｌ以下とすることで、硬化前において熱硬化性樹脂組成物の取扱い性を向上させることができる場合がある。 <(A) Polymaleimide compound>
The (A) polymaleimide compound in the thermosetting resin composition of the present invention is a compound having a weight average molecular weight of 500 g/mol or more and having two or more maleimide groups.
The lower limit of the weight average molecular weight is preferably 1000 g/mol or more, more preferably 1500 g/mol or more, and further preferably 2000 g/mol or more. The upper limit is preferably 25,000 g/mol or less.
By setting the weight average molecular weight of the (A) polymaleimide compound to 500 g/mol or more, the flexibility of the cured product is improved, and a thermosetting resin composition having both heat resistance and flexibility after curing can be obtained. Moreover, when the weight average molecular weight of the (A) polymaleimide compound is 25,000 g/mol or less, the handleability of the thermosetting resin composition before curing may be improved in some cases.
　さらに、本発明の熱硬化性樹脂組成物における、（Ａ）ポリマレイミド化合物は、数平均分子量が好ましくは５００ｇ/ｍｏｌ以上である。数平均分子量の下限値としては、好ましくは１０００ｇ/ｍｏｌ以上であり、より好ましくは１５００ｇ/ｍｏｌ以上であり、さらに好ましくは２０００ｇ/ｍｏｌ以上である。上限値としては、好ましくは２５０００ｇ/ｍｏｌ以下である。 Furthermore, the (A) polymaleimide compound in the thermosetting resin composition of the present invention preferably has a number average molecular weight of 500 g/mol or more. The lower limit of the number average molecular weight is preferably 1000 g/mol or more, more preferably 1500 g/mol or more, and further preferably 2000 g/mol or more. The upper limit is preferably 25,000 g/mol or less.
　さらに、本発明の熱硬化性樹脂組成物における、（Ａ）ポリマレイミド化合物は、マレイミド基を２個以上有するものである。マレイミド基とは、下記式（２）で表される構造である。 Furthermore, the (A) polymaleimide compound in the thermosetting resin composition of the present invention has two or more maleimide groups. The maleimide group is a structure represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　前記式（２）において、Ｒ２は置換基を示し、好ましくは、水素原子、炭素原子数１～２０個のアルキルである。炭素原子数１～２０個のアルキル基としては、好ましくは直鎖、分岐鎖であり、具体的には、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられる。 In the above formula (2), R 2 represents a substituent, and is preferably a hydrogen atom or alkyl having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is preferably linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group and pentyl. Group, hexyl group and the like.
　さらに、本発明の（Ａ）ポリマレイミド化合物は、好ましくは下記式（３）で表される構造である。
Figure JPOXMLDOC01-appb-C000004
 Furthermore, the (A) polymaleimide compound of the present invention preferably has a structure represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000004
　上記式（３）において、ｍは０を含むポリイミド単位の繰り返し数を表し、好ましくは１～２０であり、より好ましくは１～１０である。また、（Ａ）ポリマレイミド化合物は、ｍの異なる式（３）の化合物の混合物であってもよい。
　さらに、式（３）において、Ｚは、好ましくはそれぞれ独立して脂肪族環、芳香環、ヘテロ原子を有する芳香環を表し、それらの環構造がアルキレン基やエーテル構造によって結合されている構造であってもよい。
　式（３）においてＲ３は、好ましくはそれぞれ独立して、脂肪族環、芳香環、ヘテロ原子を有する芳香環、アルキル、アルキレン、ポリエーテル基、ポリシロキサン基を含む構造である。
　式（３）において、Ｒ２は上記式（２）において説明したものと同様である。 In the above formula (3), m represents the number of repeating polyimide units containing 0, and is preferably 1 to 20, and more preferably 1 to 10. Further, the (A) polymaleimide compound may be a mixture of compounds of the formula (3) having different m.
Further, in the formula (3), Z is preferably each independently an aliphatic ring, an aromatic ring, or an aromatic ring having a hetero atom, and the ring structure thereof is bonded by an alkylene group or an ether structure. It may be.
In the formula (3), R 3 is preferably each independently a structure containing an aliphatic ring, an aromatic ring, an aromatic ring having a hetero atom, an alkyl group, an alkylene group, a polyether group or a polysiloxane group.
In Formula (3), R 2 is the same as that described in Formula (2) above.
　さらに、本発明の（Ａ）ポリマレイミド化合物は、好ましくは下記式（４）～（６）で表される構造である。
Figure JPOXMLDOC01-appb-C000005
 　式（４）～（６）において、Ｒ３、ｍは上記式（３）において説明したものと同様である。より好ましくは、Ｒ３は、環式構造を有する炭化水素基であり、炭素原子数は、好ましくは２０以上５０以下である。 Furthermore, the (A) polymaleimide compound of the present invention preferably has a structure represented by the following formulas (4) to (6).
Figure JPOXMLDOC01-appb-C000005
 In formulas (4) to (6), R 3 and m are the same as those described in formula (3) above. More preferably, R 3 is a hydrocarbon group having a cyclic structure, and the number of carbon atoms is preferably 20 or more and 50 or less.
　さらに本発明の熱硬化性樹脂組成物における、（Ａ）ポリマレイミド化合物としては、具体的には、Ｄｅｓｉｇｎｅｒ　Ｍｏｌｅｃｕｌｅｓ　Ｉｎｃ．（ＤＭＩ）製の、ＢＭＩ－６８９、ＢＭＩ－１４００、ＢＭＩ－１５００、ＢＭＩ－１７００、ＢＭＩ－２５００、ＢＭＩ－３０００ＧＥＬ、ＢＭＩ－３０００Ｃｏｍｍｅｒｃｉａｌ　Ｇｒａｄｅ、ＢＭＩ－３０００ｐｏｗｄｅｒ、ＢＭＩ－５０００ｐｏｗｄｅｒ、ＢＭＩ－５０００Ｔｏｌｕｅｎｅ、ＢＭＩ－６０００や、日本化薬（株）製のＭＩＲ－３０００等が挙げられる。 Further, as the (A) polymaleimide compound in the thermosetting resin composition of the present invention, specifically, Designer Molecule Inc. (DMI) BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000GEL, BMI-3000 Commercial Grade, BMI-3000 powder, BMI-5000 powder, BMI-5000 Toluene, BMI-6000. And MIR-3000 manufactured by Nippon Kayaku Co., Ltd. and the like.
　さらに本発明の熱硬化性樹脂組成物における、（Ａ）ポリマレイミド化合物としては、具体的には下記式（７）～（１１）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000006
 Further, the (A) polymaleimide compound in the thermosetting resin composition of the present invention specifically includes compounds represented by the following formulas (7) to (11).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
 　式（７）～（１１）においてｍは上記式（３）において説明したものと同様である。
Figure JPOXMLDOC01-appb-C000007
 In formulas (7) to (11), m is the same as that described in formula (3) above.
Figure JPOXMLDOC01-appb-C000008
 （式（１２）において、Ｒ４は、それぞれ独立して、水素原子、炭素原子数１～５のアルキル基及びフェニル基からなる群より選ばれる基を表し、ｐは平均値であり１＜ｎ≦５を表す。炭素原子数１～５のアルキル基として、具体的には、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ブチル基、ペンチル基が挙げられる。）
Figure JPOXMLDOC01-appb-C000008
 (In the formula (12), R 4's each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and a phenyl group, and p is an average value and 1<n Represents ≦5. Specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group, and a pentyl group.)
　さらに、本発明の熱硬化性樹脂組成物の固形分中、（Ａ）成分の含有量は、好ましくは１０～８０質量％である。
　（Ａ）成分の含有量を上記範囲内とすることで、硬化後に良好な耐熱性及び柔軟性を有する熱硬化性樹脂組成物とすることができる。
　ここで、固形分とは、本発明の熱硬化性樹脂組成物において、溶剤以外の成分で、かつ溶剤に溶解又は分散する成分のことをいう。例えば、上記（Ａ）～（Ｄ）成分や下記の硬化剤（潜在性硬化剤を含む）、硬化促進剤等が含まれる。 Further, the content of the component (A) in the solid content of the thermosetting resin composition of the present invention is preferably 10 to 80% by mass.
By setting the content of the component (A) within the above range, a thermosetting resin composition having good heat resistance and flexibility after curing can be obtained.
Here, the solid content refers to a component other than the solvent in the thermosetting resin composition of the present invention and a component that is dissolved or dispersed in the solvent. For example, the above components (A) to (D), the following curing agents (including latent curing agents), curing accelerators and the like are included.
　さらに、本発明の熱硬化性樹脂組成物において（Ａ）～（Ｄ）成分の合計含有量を１００質量％としたときの、（Ａ）成分の含有量は、好ましくは１５～７５質量％、より好ましくは２０～６０質量％である。
　（Ａ）成分の含有量を上記範囲内とすることで、硬化後に良好な耐熱性及び柔軟性を有する熱硬化性樹脂組成物とすることができる。 Further, in the thermosetting resin composition of the present invention, when the total content of the components (A) to (D) is 100% by mass, the content of the component (A) is preferably 15 to 75% by mass, It is more preferably 20 to 60% by mass.
By setting the content of the component (A) within the above range, a thermosetting resin composition having good heat resistance and flexibility after curing can be obtained.
　＜（Ｂ）エポキシ樹脂＞
　本発明の熱硬化性樹脂組成物における（Ｂ）エポキシ樹脂は、特に限定されず、好ましくは芳香族系エポキシ樹脂、脂肪族エポキシ樹脂、及び脂環式エポキシ樹脂等の各種エポキシ樹脂であり、より好ましくは平均エポキシ基数が２個以上である多官能エポキシ樹脂である。本発明の熱硬化性樹脂組成物において（Ｂ）エポキシ樹脂を含有させることで、硬化後により耐熱性に優れた熱硬化性樹脂組成物とすることができ、電気・電子材料、構造用材料等に使用することができる。
　平均エポキシ基数は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により求めた重量平均分子量を、ＪＩＳ Ｋ７２３６に準じて求めたエポキシ当量で割ることにより求めることができる。 <(B) Epoxy resin>
The (B) epoxy resin in the thermosetting resin composition of the present invention is not particularly limited, and is preferably various epoxy resins such as an aromatic epoxy resin, an aliphatic epoxy resin, and an alicyclic epoxy resin. A polyfunctional epoxy resin having an average number of epoxy groups of 2 or more is preferable. By containing the epoxy resin (B) in the thermosetting resin composition of the present invention, it is possible to obtain a thermosetting resin composition having more excellent heat resistance after curing, such as electric/electronic materials and structural materials. Can be used for
The average number of epoxy groups can be determined by dividing the weight average molecular weight determined by gel permeation chromatography (GPC) by the epoxy equivalent weight determined according to JIS K7236.
　芳香族系エポキシ樹脂としては、好ましくは１分子中に芳香族環を有し、平均エポキシ基数が２個以上のものである。例えば、ビスフェノールＡ、ビスフェノールＦ等のビスフェノール化合物又はこれらの誘導体；４，４'－ビフェノール、３，３'，５，５'－テトラメチルビフェニル－４，４'－ジオール等のビフェニル化合物又はこれらの誘導体；トリヒドロキシフェニルメタン骨格、アミノフェノール骨格を有する３官能のフェノール樹脂；フェノールノボラック樹脂；クレゾールノボラック樹脂；フェニレン骨格を有するフェノールアラルキル樹脂；ビフェニレン骨格を有するフェノールアラルキル樹脂；ナフトールアラルキル樹脂；ジアミノジフェニルメタン骨格の誘導体等をエポキシ化したエポキシ樹脂等が挙げられる。 The aromatic epoxy resin preferably has an aromatic ring in one molecule and has an average number of epoxy groups of 2 or more. For example, bisphenol compounds such as bisphenol A and bisphenol F, or derivatives thereof; biphenyl compounds such as 4,4′-biphenol, 3,3′,5,5′-tetramethylbiphenyl-4,4′-diol, or their derivatives. Derivatives; trifunctional phenol resin having trihydroxyphenylmethane skeleton and aminophenol skeleton; phenol novolac resin; cresol novolac resin; phenol aralkyl resin having phenylene skeleton; phenol aralkyl resin having biphenylene skeleton; naphthol aralkyl resin; diaminodiphenylmethane skeleton Examples thereof include an epoxy resin obtained by epoxidizing a derivative or the like.
　これらの芳香族系エポキシ樹脂の中でも、得られる硬化物の耐熱性と機械強度が良好なため、好ましくはビスフェノールＡ、ビスフェノールＦ等のビスフェノール化合物又はこれらの誘導体、フェノールノボラック樹脂、クレゾールノボラック樹脂、及びジアミノジフェニルメタン骨格の誘導体をエポキシ化したエポキシ樹脂である。得られる硬化物が、耐熱性及び機械強度のバランスに優れることからビスフェノール系エポキシ樹脂がより好ましい。 Among these aromatic epoxy resins, since the resulting cured product has good heat resistance and mechanical strength, bisphenol compounds such as bisphenol A and bisphenol F or derivatives thereof, phenol novolac resins, cresol novolac resins, and It is an epoxy resin obtained by epoxidizing a derivative of diaminodiphenylmethane skeleton. A bisphenol-based epoxy resin is more preferable because the obtained cured product has an excellent balance of heat resistance and mechanical strength.
　脂肪族エポキシ樹脂としては、好ましくは１分子中に脂肪族骨格を有し、平均エポキシ基数が２個以上のものである。例えば、エチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオール、デカンジオール等の脂肪族ジオール、若しくはペンタエリスリトール、ソルビトール等の多価アルコール、又はこれらの誘導体等をエポキシ化したエポキシ樹脂等が挙げられる。 The aliphatic epoxy resin preferably has an aliphatic skeleton in one molecule and has an average number of epoxy groups of 2 or more. For example, an epoxy resin obtained by epoxidizing an aliphatic diol such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, nonanediol or decanediol, or a polyhydric alcohol such as pentaerythritol or sorbitol, or a derivative thereof. Etc.
　脂環式エポキシ樹脂としては、好ましくは１分子中に脂環式骨格を有し、平均エポキシ基数が２個以上のものである。例えば、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート；３，４－エポキシシクロヘキセニルメチル－３’，４’－エポキシシクロヘキセンカルボキシレート；２，３－ビス(ヒドロキシメチル)－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物；ジシクロペンタジエン型エポキシ樹脂；及び水素添加ビスフェノールＡ、水素添加ビスフェノールＦ、水素添加ビフェノール、シクロヘキサンジオール、シクロヘキサンジメタノール、シジロヘキサンジエタノール等の脂環構造を有するジオール又はこれらの誘導体等を挙げることができる。 The alicyclic epoxy resin preferably has an alicyclic skeleton in one molecule and has an average number of epoxy groups of 2 or more. For example, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate; 2,3-bis(hydroxymethyl) 1,2-Epoxy-4-(2-oxiranyl)cyclohexane adduct of 1-butanol; dicyclopentadiene type epoxy resin; and hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol And diols having an alicyclic structure such as silidrohexanediethanol or derivatives thereof.
　これらの脂環式エポキシ樹脂の中でも、得られる硬化物の耐熱性、機械強度が特に優れるため、３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレートを用いることが好ましい。
　上記芳香族系エポキシ樹脂、脂肪族エポキシ樹脂、脂環式エポキシ樹脂等の各種エポキシ樹脂は単独で用いてもよく、２種以上を併用してもよい。 Among these alicyclic epoxy resins, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferably used because the resulting cured product is particularly excellent in heat resistance and mechanical strength.
The various epoxy resins such as the aromatic epoxy resin, the aliphatic epoxy resin and the alicyclic epoxy resin may be used alone or in combination of two or more kinds.
　さらに、本発明の熱硬化性樹脂組成物の固形分中、（Ｂ）成分の含有量は、好ましくは１～１５質量％である。
　（Ｂ）成分の含有量を上記範囲内とすることで、硬化後に柔軟性を維持しつつ、比較的低温で硬化可能という効果を発揮することができる。 Further, the content of the component (B) in the solid content of the thermosetting resin composition of the present invention is preferably 1 to 15% by mass.
By setting the content of the component (B) within the above range, it is possible to exhibit the effect of being curable at a relatively low temperature while maintaining flexibility after curing.
　さらに、本発明の熱硬化性樹脂組成物において（Ａ）～（Ｄ）成分の合計含有量を１００質量％としたときの、（Ｂ）成分の含有量は、好ましくは１～１３質量％である。
　（Ｂ）成分の含有量を上記範囲内とすることで、硬化後に柔軟性を維持しつつ、比較的低温で硬化可能という効果を発揮することができる。 Further, in the thermosetting resin composition of the present invention, the content of the component (B) is preferably 1 to 13 mass% when the total content of the components (A) to (D) is 100 mass %. is there.
By setting the content of the component (B) within the above range, it is possible to exhibit the effect of being curable at a relatively low temperature while maintaining flexibility after curing.
＜（Ｃ）ポリエステル＞
　本発明の熱硬化性樹脂組成物における、（Ｃ）ポリエステルは、ジオール化合物とジカルボン酸化合物又はジカルボン酸ハライドを反応させて得られる重合体である。
　ジオール化合物としては、特に限定されないが、脂肪族ジオール、脂環族ジオール、芳香族ジオールなどが挙げられ、好ましくは芳香族ジオールであり、より好ましくは二価フェノール化合物である。 <(C) Polyester>
The (C) polyester in the thermosetting resin composition of the present invention is a polymer obtained by reacting a diol compound with a dicarboxylic acid compound or a dicarboxylic acid halide.
The diol compound is not particularly limited, and examples thereof include an aliphatic diol, an alicyclic diol, and an aromatic diol, preferably an aromatic diol, and more preferably a dihydric phenol compound.
　前記二価フェノール化合物としては、好ましくは、４，４’－ビフェノール、３，３’－ジメチル－４，４’－ビフェノール、３，３’，５，５’－テトラメチル－４，４’－ビフェノール、２，２’，３，３’，５，５’－ヘキサメチル－４，４’－ビフェノール、３，３’，５，５’－テトラ－ｔｅｒｔ－ブチル－２，２’－ビフェノール、２，２’－ビス（４－ヒドロキシフェニル）メタン、２，２’－ビス（４－ヒドロキシフェニル）プロパン、２，２－ビス（４－ヒドロキシフェニル）ブタン、２，２－ビス（４－ヒドロキシフェニル）ペンタン、２，２－ビス（４－ヒドロキシフェニル）ヘキサン、２，２－ビス（４－ヒドロキシフェニル）－３－メチルブタン、２，２－ビス（４－ヒドロキシフェニル）－４－メチルペンタン、１，１－ビス（４－ヒドロキシフェニル）－２－エチルヘキサン、２，２－ビス（４－ヒドロキシフェニル）ブタン、１，１－ビス（４－ヒドロキシフェニル）－２－メチルプロパン、２，２－ビス（４－ヒドロキシフェニル）オクタン、１，１－ビス（４－ヒドロキシフェニル）－３－メチルブタン、３，３－ビス（４－ヒドロキシフェニル）ペンタン）が挙げられる。 The dihydric phenol compound is preferably 4,4'-biphenol, 3,3'-dimethyl-4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-. Biphenol, 2,2',3,3',5,5'-hexamethyl-4,4'-biphenol, 3,3',5,5'-tetra-tert-butyl-2,2'-biphenol, 2 ,2'-bis(4-hydroxyphenyl)methane, 2,2'-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl) ) Pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1 ,1-bis(4-hydroxyphenyl)-2-ethylhexane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 2,2- And bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)-3-methylbutane, 3,3-bis(4-hydroxyphenyl)pentane).
　また、脂肪族ジオールとしては、例えば、エチレングリコール、プロピレングリコールが挙げられる。脂環族ジオールとしては、例えば、１，４－シクロヘキサンジオール、１，３－シクロヘキサンジオール、１，２－シクロヘキサンジオールが挙げられる。 Further, examples of the aliphatic diol include ethylene glycol and propylene glycol. Examples of the alicyclic diol include 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol.
　ジカルボン酸又ジカルボン酸ハライドとしては、特に限定されないが、脂肪族ジカルボン酸、脂環族ジカルボン酸、芳香族ジカルボン酸又はそれらのハライドが挙げられ、好ましくは芳香属ジカルボン酸、より好ましくは全芳香族二価カルボン酸又はそれらのハライドである。 The dicarboxylic acid or dicarboxylic acid halide is not particularly limited, and examples thereof include aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid and halides thereof, preferably aromatic dicarboxylic acid, more preferably wholly aromatic. It is a divalent carboxylic acid or a halide thereof.
　全芳香族二価カルボン酸又はそれらのハライドとしては、例えば、フタル酸、イソフタル酸、テレフタル酸、２，６－ナフタレンジカルボン酸、ジフェニルエーテル－２，２’－ジカルボン酸、ジフェニルエーテル－２，３’－ジカルボン酸、ジフェニルエーテル－２，４’－ジカルボン酸、ジフェニルエーテル－３，３’－ジカルボン酸、ジフェニルエーテル－３，４’－ジカルボン酸、ジフェニルエーテル－４，４’－ジカルボン酸又はそれらのハライドが挙げられる。 Examples of the wholly aromatic divalent carboxylic acid or halide thereof include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'- Examples thereof include dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid and halides thereof.
　脂肪族ジカルボン酸又はそれらのハライドとしては、例えば、アジピン酸、セバシン酸が挙げられる。脂環族ジカルボン酸としては、例えば、１，４－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、１，２－シクロヘキサンジカルボン酸又はそれらのハライドが挙げられる。 Examples of the aliphatic dicarboxylic acid or halide thereof include adipic acid and sebacic acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and halides thereof.
　さらに本発明の熱硬化性樹脂組成物における（Ｃ）ポリエステルの末端構造は、好ましくは水酸基である。
　（Ｃ）ポリエステルの末端構造を水酸基とすることで、（Ａ）ポリマレイミドや（Ｂ）エポキシ樹脂の硬化に関して効率的に作用することができ、熱硬化性樹脂組成物の硬化後の耐熱性をより向上させることができる。 Further, the terminal structure of the (C) polyester in the thermosetting resin composition of the present invention is preferably a hydroxyl group.
By making the terminal structure of the (C) polyester a hydroxyl group, it can efficiently act on the curing of the (A) polymaleimide and (B) epoxy resin, and the heat resistance of the thermosetting resin composition after curing can be improved. It can be further improved.
　さらに、本発明における（Ｃ）ポリエステルとしては、好ましくは下記式（１）の構造を有するポリエステルである。
Figure JPOXMLDOC01-appb-C000009
 Further, the (C) polyester in the present invention is preferably a polyester having a structure of the following formula (1).
Figure JPOXMLDOC01-appb-C000009
　式（１）中、Ｒ１はそれぞれ独立して、水素原子又はハロゲン原子で置換されていてもよいアルキル基である。アルキル基としては、好ましくは炭素原子数１～１０の直鎖、又は分岐鎖を有するアルキル基であり、具体的には、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられる。また、ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素原子が挙げられる。 In formula (1), each R 1 is independently an alkyl group optionally substituted with a hydrogen atom or a halogen atom. The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group. , A pentyl group, a hexyl group and the like. The halogen atom includes fluorine, chlorine, bromine and iodine atoms.
　式（１）中、Ｘは芳香環を含む基である。前記芳香環としては、ベンゼン環、ナフタレン環、アントラセン環、フルオレン環が挙げられ、Ｘの構造として具体的には、フェニレン、ナフタレン基、ジフェニルアルキル基、ジフェニルエーテル基、ジフェニルスルホン基等の基である。
　さらに、式（１）中、Ｙは単結合、アルキレン基又は酸素原子である。前記アルキレン基としては、炭素原子数１～１０個のアルキレン基が挙げられ、具体的にはメチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基等が挙げられる。 In formula (1), X is a group containing an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Specific examples of the structure of X include a phenylene group, a naphthalene group, a diphenylalkyl group, a diphenylether group, and a diphenylsulfone group. ..
Further, in the formula (1), Y is a single bond, an alkylene group or an oxygen atom. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group and a butylene group.
　本発明における（Ｃ）ポリエステルの重量平均分子量が５０００～１５００００であることが好ましい。重量平均分子量を上記範囲内とすることで、熱硬化性樹脂組成物における各成分の均一性や溶媒溶解性を向上させることができる。 The weight average molecular weight of the (C) polyester in the present invention is preferably 5,000 to 150,000. By setting the weight average molecular weight within the above range, it is possible to improve the uniformity of each component in the thermosetting resin composition and the solvent solubility.
　さらに本発明の熱硬化性樹脂組成物における、（Ｃ）ポリエステルのガラス転移温度は、好ましくは１８０℃以上である。下限値としては、より好ましくは２００℃以上であり、さらに好ましくは２２０℃以上である。（Ｃ）ポリエステルのガラス転移温度を１８０℃以上とすることにより、熱硬化性樹脂組成物の耐熱性をより向上させることができる。 Further, the glass transition temperature of the (C) polyester in the thermosetting resin composition of the present invention is preferably 180° C. or higher. The lower limit value is more preferably 200°C or higher, and further preferably 220°C or higher. By setting the glass transition temperature of the polyester (C) to 180° C. or higher, the heat resistance of the thermosetting resin composition can be further improved.
　さらに、本発明の熱硬化性樹脂組成物の固形分中、（Ｃ）成分の含有量は、好ましくは１０～８０質量％である。
　（Ｃ）成分の含有量を上記範囲内とすることで良好な耐熱性及び柔軟性を有する熱硬化性樹脂組成物とすることができる。 Further, the content of the component (C) in the solid content of the thermosetting resin composition of the present invention is preferably 10 to 80% by mass.
By setting the content of the component (C) within the above range, a thermosetting resin composition having good heat resistance and flexibility can be obtained.
　さらに、本発明の熱硬化性樹脂組成物において（Ａ）～（Ｄ）成分の合計含有量を１００質量％としたときの、（Ｃ）成分の含有量は、好ましくは１５～７５質量％である。
　（Ｃ）成分の含有量を上記範囲内とすることで、硬化後に良好な耐熱性及び柔軟性を有する熱硬化性樹脂組成物とすることができる。 Further, in the thermosetting resin composition of the present invention, the content of the component (C) is preferably 15 to 75 mass% when the total content of the components (A) to (D) is 100 mass %. is there.
By setting the content of the component (C) within the above range, a thermosetting resin composition having good heat resistance and flexibility after curing can be obtained.
＜（Ｄ）芳香族アミン化合物＞
　本発明の熱硬化性樹脂組成物における、（Ｄ）芳香族アミン化合物は、（Ａ）ポリマレイミド化合物や（Ｂ）エポキシ樹脂の硬化に寄与するものである。
　（Ｄ）芳香族アミン化合物としては、好ましくはベンゼン環を有するアミン化合物であり、例えば、フェニレンジアミン、ジアミノジフェニルメタン、４，４’－ジアミノ－３，３’－ジメチルジフェニルメタン、４，４’－ジアミノ－３，３’－ジエチルジフェニルメタン、ジアミノジフェニルスルホン、ジメチルベンジルアミン、ｍ－キシリレンジアミン、テトラメチルジアミノジフェニルメタン、テトラエチルジアミノジフェニルメタン、ジエチルジメチルジアミノジフェニルメタン、ジメチルジアミノトルエン、ジアミノジエチルトルエン、ジアミノジプロピルトルエン、ジアミノジブチルトルエン、ジアミノジフェニルスルホン、ジアミノジトリルスルホン、ビス（４－アミノー３－エチルフェニル）メタン、ポリテトラメチレンオキシド－ジ－ｐ－アミノベンゾエート等の芳香族ポリアミン類が挙げられ、より好ましくは４，４’－ジアミノ－３，３’－ジメチルジフェニルメタンである。
　また、上記各種の（Ｄ）芳香族アミン化合物は、単独で用いてもよく、２種以上を併用してもよい。 <(D) Aromatic amine compound>
The (D) aromatic amine compound in the thermosetting resin composition of the present invention contributes to the curing of the (A) polymaleimide compound and (B) epoxy resin.
The aromatic amine compound (D) is preferably an amine compound having a benzene ring, and examples thereof include phenylenediamine, diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane and 4,4′-diamino. -3,3'-diethyldiphenylmethane, diaminodiphenylsulfone, dimethylbenzylamine, m-xylylenediamine, tetramethyldiaminodiphenylmethane, tetraethyldiaminodiphenylmethane, diethyldimethyldiaminodiphenylmethane, dimethyldiaminotoluene, diaminodiethyltoluene, diaminodipropyltoluene, Aromatic polyamines such as diaminodibutyltoluene, diaminodiphenyl sulfone, diaminoditolyl sulfone, bis(4-amino-3-ethylphenyl)methane, polytetramethylene oxide-di-p-aminobenzoate and the like are mentioned, more preferably 4 , 4'-diamino-3,3'-dimethyldiphenylmethane.
Further, the various (D) aromatic amine compounds may be used alone or in combination of two or more kinds.
　さらに、本発明の熱硬化性樹脂組成物（Ａ）～（Ｄ）成分の合計含有量を１００質量％としたときの、（Ｄ）成分の含有量は、好ましくは１～１５質量％である。
　（Ｄ）成分の含有量を上記範囲内とすることで、良好な硬化性という効果を発揮することができる。 Furthermore, when the total content of the thermosetting resin compositions (A) to (D) of the present invention is 100% by mass, the content of the (D) component is preferably 1 to 15% by mass. ..
By setting the content of the component (D) within the above range, the effect of good curability can be exhibited.
＜（Ｅ）溶剤＞
　本発明の熱硬化性樹脂組成物は、（Ｅ）溶剤に溶解させてワニスの形態としてもよい。溶剤としては特に限定されないが、好ましくは、ケトン系溶剤、エステル系溶剤、アルコール系溶剤等である。具体的には、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）、シクロヘキサノン、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）等を挙げることができる。 <(E) Solvent>
The thermosetting resin composition of the present invention may be dissolved in a solvent (E) to form a varnish. The solvent is not particularly limited, but a ketone solvent, an ester solvent, an alcohol solvent or the like is preferable. Specific examples include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), and the like.
　前記（Ｅ）溶剤の量は、熱硬化性樹脂組成物に含まれる固形分１００質量部あたり、好ましくは１～２００００質量部である。ここで、固形分とは、溶剤に溶解する成分であり、例えば、上記（Ａ）～（Ｄ）成分や下記の硬化剤（潜在性硬化剤を含む）、硬化促進剤等が含まれる。 The amount of the solvent (E) is preferably 1 to 20,000 parts by mass based on 100 parts by mass of the solid content contained in the thermosetting resin composition. Here, the solid content is a component that is soluble in a solvent, and includes, for example, the above-mentioned components (A) to (D), the following curing agents (including latent curing agents), and curing accelerators.
＜（Ｆ）硬化剤＞
　本発明の熱硬化性樹脂組成物は、更に硬化剤を含有することができる。含有される硬化剤としては、特に限定されないが、好ましくは、フェノール系硬化剤（フェノール樹脂等）、ジシアンジアミド系硬化剤（ジシアンジアミド等）、尿素系硬化剤、有機酸ヒドラジド系硬化剤、アミンアダクト系硬化剤、酸無水物系硬化剤、イミダゾール系硬化剤などである。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 <(F) Curing agent>
The thermosetting resin composition of the present invention may further contain a curing agent. The curing agent to be contained is not particularly limited, but preferably, a phenol-based curing agent (phenol resin or the like), a dicyandiamide-based curing agent (dicyandiamide or the like), a urea-based curing agent, an organic acid hydrazide-based curing agent, an amine adduct-based agent Examples of the curing agent include acid curing agents, acid anhydride curing agents, and imidazole curing agents. These may be used alone or in combination of two or more.
　上記フェノール系硬化剤としては、好ましくはフェノール類またはナフトール類（例えば、フェノール、クレゾール、ナフトール、アルキルフェノール、ビスフェノール、テルペンフェノールなど）と、ホルムアルデヒドとを、縮合重合させたものである。具体的には、例えば、フェノールノボラック、ｏ－クレゾールノボラック、ｐ－クレゾールノボラック、α－ナフトールノボラック樹脂、β－ナフトールノボラック樹脂、ｔ－ブチルフェノールノボラック、ジシクロペンタジエンクレゾール、ポリパラビニルフェノール、ビスフェノールＡ型ノボラック、キシリレン変性ノボラック、デカリン変性ノボラック、ポリ（ジ－ｏ－ヒドロキシフェニル）メタン、ポリ（ジ－ｍ－ヒドロキシフェニル）メタン、及びポリ（ジ－ｐ－ヒドロキシフェニル）メタン等が挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The above-mentioned phenol-based curing agent is preferably a condensation polymerization of phenol or naphthol (for example, phenol, cresol, naphthol, alkylphenol, bisphenol, terpenephenol) and formaldehyde. Specifically, for example, phenol novolac, o-cresol novolac, p-cresol novolac, α-naphthol novolac resin, β-naphthol novolac resin, t-butylphenol novolac, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type Examples thereof include novolac, xylylene-modified novolac, decalin-modified novolac, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, and poly(di-p-hydroxyphenyl)methane. These may be used alone or in combination of two or more.
　上記酸無水物系硬化剤としては、具体的には、無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸などのアルキルヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、３－メチルテトラヒドロ無水フタル酸などのアルキルテトラヒドロ無水フタル酸、無水ハイミック酸、無水コハク酸、無水トリメリット酸、無水ピロメリット酸等を挙げることができる。これらは単独で用いてもよく２種以上を組み合わせて用いてもよい。これらのうち、好ましくは、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。 Specific examples of the acid anhydride-based curing agent include phthalic anhydride, hexahydrophthalic anhydride, and alkylhexahydrophthalic anhydride such as methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride. Examples thereof include alkyltetrahydrophthalic anhydride such as 3-methyltetrahydrophthalic anhydride, hymic acid anhydride, succinic anhydride, trimellitic anhydride, and pyromellitic anhydride. These may be used alone or in combination of two or more. Of these, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride are preferable.
　硬化剤の含有量は、硬化剤の種類によって適宜設定することができる。ただし、好ましくはエポキシ基１当量あたり、硬化剤の官能基の当量数が０．００１～２当量であり、より好ましくは０．００５～１．５当量となる量である。 The content of the curing agent can be appropriately set depending on the type of the curing agent. However, the equivalent number of the functional group of the curing agent is preferably 0.001 to 2 equivalents, and more preferably 0.005 to 1.5 equivalents per equivalent of the epoxy group.
　なお、ジシアンジアミド系硬化剤、尿素系硬化剤、有機酸ヒドラジド系硬化剤、アミンアダクト系硬化剤は、潜在性硬化剤である。潜在性硬化剤の活性温度の下限値は、好ましくは６０℃以上であり、より好ましくは８０℃以上である。また、活性温度の上限値は、好ましくは２５０℃以下であり、より好ましくは１８０℃以下である。活性化温度を上記範囲内とすることで、活性温度以上で迅速に硬化する熱硬化性樹脂組成物を得ることができる。 Note that the dicyandiamide curing agent, urea curing agent, organic acid hydrazide curing agent, and amine adduct curing agent are latent curing agents. The lower limit of the activation temperature of the latent curing agent is preferably 60°C or higher, more preferably 80°C or higher. The upper limit of the activation temperature is preferably 250°C or lower, more preferably 180°C or lower. By setting the activation temperature within the above range, it is possible to obtain a thermosetting resin composition that is rapidly cured at the activation temperature or higher.
＜（Ｇ）硬化促進剤＞
　さらに本発明の熱硬化性樹脂組成物は、硬化促進剤を含んでもよい。硬化促進剤は、特に限定されないが、好ましくは変性イミダゾール系硬化促進剤、変性脂肪族ポリアミン系促進剤、変性ポリアミン系促進剤などである。硬化促進剤は、エポキシ樹脂などの樹脂との反応生成物（アダクト）として使用することが好ましい。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。硬化促進剤の活性温度は、保存安定性の点から、下限値としては、好ましくは６０℃以上であり、より好ましくは８０℃以上である。また、活性温度の上限値としては、好ましくは２５０℃以下であり、より好ましくは１８０℃以下である。 <(G) Curing accelerator>
Further, the thermosetting resin composition of the present invention may contain a curing accelerator. The curing accelerator is not particularly limited, but is preferably a modified imidazole-based curing accelerator, a modified aliphatic polyamine-based accelerator, a modified polyamine-based accelerator, or the like. The curing accelerator is preferably used as a reaction product (adduct) with a resin such as an epoxy resin. These may be used alone or in combination of two or more. From the viewpoint of storage stability, the lower limit of the activation temperature of the curing accelerator is preferably 60°C or higher, more preferably 80°C or higher. The upper limit of the activation temperature is preferably 250°C or lower, more preferably 180°C or lower.
　ここで、活性温度とは、潜在性硬化剤および／または硬化促進剤の作用により、熱硬化性樹脂の硬化が急速に早められる温度である。 Here, the activation temperature is a temperature at which the thermosetting resin is rapidly accelerated by the action of the latent curing agent and/or the curing accelerator.
　硬化促進剤の量は、硬化促進剤の種類によって適宜設定することができるが、通常、エポキシ樹脂１００質量部あたり、好ましくは０．１～２０質量部であり、より好ましくは１～１０質量部である。なお、硬化促進剤をアダクトとして使用する場合、硬化促進剤の量は、硬化促進剤以外の成分（エポキシ樹脂など）を除いた硬化促進剤の正味の量を意味する。 The amount of the curing accelerator can be appropriately set depending on the type of the curing accelerator, but it is usually 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the epoxy resin. Is. When the curing accelerator is used as an adduct, the amount of the curing accelerator means the net amount of the curing accelerator excluding the components other than the curing accelerator (such as epoxy resin).
＜（Ｈ）その他の添加剤＞
　さらに本発明の熱硬化性樹脂組成物は、上記以外の第三成分を含んでもよい。第三成分としては、熱可塑性樹脂、無機フィラー、重合開始剤、難燃剤、顔料、分散剤、シランカップリング剤、チキソ性付与剤などを挙げることができる。 <(H) Other additives>
Further, the thermosetting resin composition of the present invention may contain a third component other than the above. Examples of the third component include a thermoplastic resin, an inorganic filler, a polymerization initiator, a flame retardant, a pigment, a dispersant, a silane coupling agent, and a thixotropic agent.
　無機フィラーとしては、例えば、シリカ、タルク、炭酸カルシウム、チタンホワイト、ベンガラ、炭化珪素、窒化ホウ素などを挙げることができる。無機フィラーの平均粒径は、体積粒度分布の累積体積５０％における粒径（Ｄ５０）は、例えば０．０１～１００μｍである。無機フィラーの量は、配合する場合、（Ａ）～（Ｃ）成分の合計１００質量部あたり、好ましくは１～５０００質量部であり、より好ましくは１０～３０００質量部である。 Examples of the inorganic filler include silica, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride and the like. Regarding the average particle diameter of the inorganic filler, the particle diameter (D50) at a cumulative volume of 50% in the volume particle size distribution is, for example, 0.01 to 100 μm. When compounded, the amount of the inorganic filler is preferably 1 to 5000 parts by mass, more preferably 10 to 3000 parts by mass, per 100 parts by mass of the total of the components (A) to (C).
　重合開始剤は、加熱により、硬化性を発現する。重合開始剤としては、ラジカル発生剤、酸発生剤、塩基発生剤などを用いることができる。具体的には、ベンゾフェノン系化合物、ヒドロキシケトン系化合物、アゾ化合物、有機過酸化物、芳香族スルホニウム塩、脂肪族スルホニウム塩などのスルホニウム塩などを用いることができる。重合開始剤の量は、配合する場合、エポキシ樹脂１００質量部あたり、好ましくは０．１～２０質量部であり、より好ましくは１～１０質量部である。 ㆍThe polymerization initiator develops curability when heated. As the polymerization initiator, a radical generator, an acid generator, a base generator or the like can be used. Specifically, benzophenone compounds, hydroxyketone compounds, azo compounds, organic peroxides, sulfonium salts such as aromatic sulfonium salts and aliphatic sulfonium salts can be used. When compounded, the amount of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the epoxy resin.
＜シート＞
　本発明の熱硬化性樹脂組成物は、シートやフィルム等の形態に成形して使用することができる。シートの形態は、特に限定されず、単層シートであってもよく、２層以上の多層シートであってもよい。
　本発明のシートの厚みは、特に限定されないが、好ましくは１０～１５００μｍであり、より好ましくは２０～５００μｍである。厚みが１０μｍ未満であると、表面硬度が不十分となることがあり、１５００μｍを超えると、割れ易くなり、ロール・ツー・ロールでの巻き取りが困難となることがある。 <Sheet>
The thermosetting resin composition of the present invention can be molded into a sheet, film or the like for use. The form of the sheet is not particularly limited, and may be a single layer sheet or a multilayer sheet having two or more layers.
The thickness of the sheet of the present invention is not particularly limited, but is preferably 10 to 1500 μm, more preferably 20 to 500 μm. If the thickness is less than 10 μm, the surface hardness may be insufficient, and if it exceeds 1500 μm, the surface may be easily cracked, and the roll-to-roll winding may be difficult.
　本発明のシートは、好ましくは未硬化状態、半硬化状態、又は硬化状態のものである。半硬化状態とは、熱硬化性樹脂組成物がモノマーおよび／またはオリゴマーを含む状態であり、熱硬化性樹脂組成物中における化合物の三次元架橋構造の発達が不十分な状態をいう。すなわち、必要に応じて、塗膜を５０～１５０℃で１分～１０分間加熱してゲル化したり、Ｂステージ化したりして、シート化してもよい。なお、Ｂステージ化とは、樹脂組成物を半硬化状態の固体にすることをいう。Ｂステージの樹脂組成物を加熱すると溶融し、硬化反応が更に進行する。硬化状態とは、前記熱硬化性樹脂組成物を完全に硬化させたものをいう。 The sheet of the present invention is preferably in an uncured state, a semi-cured state, or a cured state. The semi-cured state is a state in which the thermosetting resin composition contains a monomer and/or an oligomer, and is a state in which the three-dimensional crosslinked structure of the compound in the thermosetting resin composition is insufficiently developed. That is, if necessary, the coating film may be heated at 50 to 150° C. for 1 to 10 minutes to gel or B stage to form a sheet. The term "B-stage" means that the resin composition is made into a semi-cured solid. When the B-stage resin composition is heated, it is melted and the curing reaction proceeds further. The cured state means a state in which the thermosetting resin composition is completely cured.
　シート、フィルム等に成形する方法としては、上記に示した溶媒に溶解した前記熱硬化性樹脂組成物を基材に塗工し、乾燥後、加熱等を行うことで硬化を行うことができる。
　本発明の熱硬化性樹脂組成物からなる硬化物は、前記（Ａ）～（Ｄ）成分を含有していることから、硬化後の耐熱性及び柔軟性、また比較的低温での硬化性を併せ持つという特性を有している。 As a method for forming a sheet, a film or the like, the thermosetting resin composition dissolved in the solvent shown above may be applied to a substrate, dried and then heated to cure the composition.
Since the cured product of the thermosetting resin composition of the present invention contains the above-mentioned components (A) to (D), it exhibits heat resistance and flexibility after curing and curability at a relatively low temperature. It has the property of having both.
　本発明のシートの製造方法としては、特に限定されないが、生産性の観点から、ロール・ツー・ロールプロセスが好適に用いられる。具体的には、各種支持フィルム（離型処理をしたＰＥＴ、ＰＭＭＡフィルム等）に本発明の樹脂組成物を所定の膜厚でコーティングし、支持フィルムを剥離することで得ることが出来る。コーティング方法としては、グラビアコート、ロールコーティング、バーコーティング、ダイコーティング、ナイフコーティング等が挙げられる。 The method for producing the sheet of the present invention is not particularly limited, but a roll-to-roll process is preferably used from the viewpoint of productivity. Specifically, it can be obtained by coating various support films (PET, PMMA film and the like subjected to mold release treatment) with the resin composition of the present invention to a predetermined thickness and peeling the support film. Examples of the coating method include gravure coating, roll coating, bar coating, die coating, knife coating and the like.
＜硬化物＞
　本発明の熱硬化性樹脂組成物の硬化を進めることにより、硬化物とすることができる。前記硬化物の形態としては、好ましくはシート、フィルム等の形態である。シート、フィルム等に成形する方法としては、上記に示した溶媒に溶解した前記熱硬化性樹脂組成物を基材に塗工し、乾燥後、加熱等を行うことで硬化を行うことができる。 <Cured product>
A cured product can be obtained by proceeding with the curing of the thermosetting resin composition of the present invention. The form of the cured product is preferably a sheet, a film or the like. As a method for forming a sheet, a film or the like, the thermosetting resin composition dissolved in the solvent shown above may be applied to a substrate, dried and then heated to cure the composition.
　本発明の熱硬化性樹脂組成物において、硬化温度は特に限定されないが、好ましくは２２０℃以下である。下限値としては、より好ましくは９０℃以上であり、さらに好ましくは１００℃以上である。上限値としては、より好ましくは２００℃以下であり、さらに好ましくは１９０℃以下である。また硬化時間は特に限定されないが、好ましくは３０分以上１５００分であり、下限値としては、より好ましくは６０分以上である。
　本発明の熱硬化性樹脂組成物は、前記（Ａ）～（Ｄ）成分を含有していることから２２０℃以下という低温で硬化することができ、硬化における熱によって関係材料が悪影響を受けることを抑制することができる。 In the thermosetting resin composition of the present invention, the curing temperature is not particularly limited, but it is preferably 220°C or lower. The lower limit value is more preferably 90°C or higher, and further preferably 100°C or higher. The upper limit value is more preferably 200°C or lower, and further preferably 190°C or lower. The curing time is not particularly limited, but is preferably 30 minutes or more and 1500 minutes, and the lower limit value is more preferably 60 minutes or more.
Since the thermosetting resin composition of the present invention contains the above-mentioned components (A) to (D), it can be cured at a low temperature of 220° C. or lower, and the heat of curing adversely affects the related materials. Can be suppressed.
＜硬化物の物性＞
　本発明の熱硬化性樹脂組成物を硬化してなる硬化物の曲げ弾性率は、－４０℃において、好ましくは１．０ＧＰａ以上であり、より好ましくは１．４ＧＰａ以上である。
　さらに、２５℃において、好ましくは１．０ＧＰａ以上であり、より好ましくは１．４ＧＰａ以上である。
　さらに、２５０℃において、好ましくは０．０１ＧＰａ以上であり、より好ましくは０．０１１ＧＰａ以上である。
　曲げ弾性率の測定は、いずれもＪＩＳ　Ｋ７１７１に準じて、ストログラフＶＧ２０－Ｅ（東洋精機製作所社製）を用いて、測定湿度５０％ＲＨ、ロードセル１．０ｋＮ、ヘッド移動速度５ｍｍ／ｍｉｎの条件で測定することができる。 <Physical properties of cured product>
The flexural modulus of the cured product obtained by curing the thermosetting resin composition of the present invention at −40° C. is preferably 1.0 GPa or more, more preferably 1.4 GPa or more.
Further, at 25° C., it is preferably 1.0 GPa or more, more preferably 1.4 GPa or more.
Furthermore, at 250° C., it is preferably 0.01 GPa or more, more preferably 0.011 GPa or more.
The flexural modulus was measured in accordance with JIS K7171, using a Strograph VG20-E (manufactured by Toyo Seiki Seisaku-sho, Ltd.) under the conditions of a measured humidity of 50% RH, a load cell of 1.0 kN, and a head moving speed of 5 mm/min. Can be measured at.
　本発明の熱硬化性樹脂組成物を硬化してなる硬化物の引張強度は、２５℃において、好ましくは１５Ｎ以上である。
　引張強度の測定は、島津製作所製オートグラフを用い、チャック間２０ｍｍ、引張速度５ｍｍ／分の条件にて、シート厚さ５０μｍの条件で測定することができる。 The tensile strength of a cured product obtained by curing the thermosetting resin composition of the present invention is preferably 15 N or higher at 25°C.
The tensile strength can be measured using an autograph manufactured by Shimadzu Corporation under the conditions of a chuck thickness of 20 mm, a pulling speed of 5 mm/min, and a sheet thickness of 50 μm.
　本発明の熱硬化性樹脂組成物を硬化してなる硬化物の伸び率は、２５℃において、好ましくは１０％以上である。さらに、２５℃において、より好ましくは２０％以上であり、さらに好ましくは３０％以上である。
　伸び率の測定は、島津製作所製オートグラフを用い、チャック間２０ｍｍ、引張速度５ｍｍ／分の条件にて、シート厚さ５０μｍの条件で測定することができる。 The elongation of the cured product obtained by curing the thermosetting resin composition of the present invention is preferably 10% or more at 25°C. Furthermore, at 25° C., it is more preferably 20% or more, further preferably 30% or more.
The elongation can be measured by using an autograph manufactured by Shimadzu Corporation under the conditions of a chuck thickness of 20 mm, a pulling speed of 5 mm/min, and a sheet thickness of 50 μm.
　本発明の熱硬化性樹脂組成物を硬化してなる硬化物の５．０質量％加熱減量温度は、好ましくは３００℃以上であり、より好ましくは３２５℃、さらに好ましくは３５０℃以上である。
　５．０質量％加熱減量温度の測定は、熱質量測定装置（ＴＧＡ）にて、２５℃での質量を基準に、昇温速度１０℃／分で測定して５．０質量％減量したときの温度として測定することができる。 The cured product obtained by curing the thermosetting resin composition of the present invention has a heating weight loss temperature of 5.0% by mass of preferably 300°C or higher, more preferably 325°C, further preferably 350°C or higher.
The 5.0 mass% heating loss temperature is measured by a thermogravimetric analyzer (TGA) at a temperature rising rate of 10°C/min based on the mass at 25°C and the mass is reduced by 5.0% by mass. Can be measured as the temperature of.
　本発明の熱硬化性樹脂組成物を硬化してなる硬化物のガラス転移温度Ｔｇは、好ましくは５０℃以上であり、より好ましくは７０℃以上である。ガラス転移温度Ｔｇはより高い方が好ましく、上限値は特に限定されないが、例えば、２５０℃以下である。
　硬化物のガラス転移温度Ｔｇは、示差走査熱量測定（ＤＳＣ）装置（セイコーインスツル社製）を用いて、温度範囲３０～２５０℃、昇温速度２℃／分、周波数１ＭＨｚの条件で測定することができる。 The glass transition temperature Tg of the cured product obtained by curing the thermosetting resin composition of the present invention is preferably 50° C. or higher, more preferably 70° C. or higher. The glass transition temperature Tg is preferably higher, and the upper limit value is not particularly limited, but is, for example, 250° C. or lower.
The glass transition temperature Tg of the cured product is measured using a differential scanning calorimetry (DSC) device (manufactured by Seiko Instruments Inc.) under the conditions of a temperature range of 30 to 250° C., a heating rate of 2° C./min, and a frequency of 1 MHz. be able to.
＜用途＞
　上記のとおり、本発明の熱硬化性樹脂組成物を硬化してなる硬化物は耐熱性と柔軟性に優れているため、半導体等の電子部品用封止剤、積層板、ＦＲＰ（複合材料）、層間絶縁材、接着剤等の自動車・航空機及び電気・電子材料用分野等で用いられる、高い機械的・電気的接続信頼性が求められる部品材料として好適に用いることができる。さらに、その柔軟性により、ウエアラブル端末に用いるフレキシブル基材としても好適に用いることができる。 <Use>
As described above, since the cured product obtained by curing the thermosetting resin composition of the present invention has excellent heat resistance and flexibility, it is a sealant for electronic parts such as semiconductors, laminates, FRP (composite material). It can be preferably used as a component material that is required to have high mechanical/electrical connection reliability and is used in the fields of automobiles/aircrafts and electric/electronic materials such as interlayer insulating materials and adhesives. Further, due to its flexibility, it can be suitably used as a flexible base material used for wearable terminals.
　以下に実施例を挙げて本発明をさらに具体的に説明するが、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 The present invention will be described in more detail with reference to the following examples, but can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following specific examples.
＜熱硬化性樹脂組成物の作製＞
　表１に示す配合（質量部）にて、熱硬化性樹脂組成物を得た。この熱硬化性樹脂組成物の粘度を、２５℃、せん断速度２．５（１／ｓ）の条件下、ブルックフィールド社製、ＨＢＴ型粘度計（スピンドルタイプ：Ｎｏ２９）を用いて測定した。 <Preparation of thermosetting resin composition>
A thermosetting resin composition was obtained with the composition (parts by mass) shown in Table 1. The viscosity of this thermosetting resin composition was measured under the conditions of 25° C. and a shear rate of 2.5 (1/s) using an HBT type viscometer (spindle type: No29) manufactured by Brookfield.
上記材料の詳細を以下に示す。
（Ａ）ポリマレイミド化合物：
実施例１：商品名ＢＭＩ６８９（Ｄｅｓｉｇｎｅｒ　Ｍｏｌｅｃｕｌｅｓ　Ｉｎｃ製）
実施例２：商品名ＢＭＩ１７００（Ｄｅｓｉｇｎｅｒ　Ｍｏｌｅｃｕｌｅｓ　Ｉｎｃ製）
実施例３、６、７：商品名ＢＭＩ１４００（Ｄｅｓｉｇｎｅｒ　Ｍｏｌｅｃｕｌｅｓ　Ｉｎｃ製）
実施例４：商品名ＢＭＩ３０００（Ｄｅｓｉｇｎｅｒ　Ｍｏｌｅｃｕｌｅｓ　Ｉｎｃ製）実施例５：商品名ＢＭＩ６０００（Ｄｅｓｉｇｎｅｒ　Ｍｏｌｅｃｕｌｅｓ　Ｉｎｃ製）
比較例１：商品名ＢＭＩ（ケイ・アイ化成（株）製）
比較例２：商品名ＢＭＩ７０（ケイ・アイ化成（株）製）
（Ｂ）エポキシ樹脂：商品名ＥＰＣ８３０ＬＶＰ（ＤＩＣ（株）製）
（Ｃ）ポリエステル：商品名ユニファイナーＭ２０００Ｈ（ユニチカ（株）製）
（Ｄ）芳香族アミン化合物：４，４’－ジアミノ－３，３’－ジエチルジフェニルメタン、商品名ＫＡＹＡＨＡＲＤ　ＡＡ（日本化薬（株）製） Details of the above materials are shown below.
(A) Polymaleimide compound:
Example 1: Trade name BMI689 (manufactured by Designer Moleculars Inc)
Example 2: Brand name BMI1700 (manufactured by Designer Moleculars Inc)
Examples 3, 6, and 7: Trade name BMI1400 (designer molecules Inc.)
Example 4: Product name BMI3000 (manufactured by Designer Moleculars Inc) Example 5: Product name BMI6000 (manufactured by Designer Moleculars Inc)
Comparative Example 1: Trade name BMI (Kai Kasei Co., Ltd.)
Comparative Example 2: Product name BMI70 (Kai Kasei Co., Ltd.)
(B) Epoxy resin: trade name EPC830LVP (manufactured by DIC Corporation)
(C) Polyester: Product name Unifiner M2000H (manufactured by Unitika Ltd.)
(D) Aromatic amine compound: 4,4′-diamino-3,3′-diethyldiphenylmethane, trade name KAYAHARD AA (manufactured by Nippon Kayaku Co., Ltd.)
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
＜シートの作製＞
　上記で作製した熱硬化性樹脂組成物を、コーティング法によりシート状にコートし、１８０℃で１２０分で硬化を行い、厚みが５０μｍの硬化シートを作製した。 <Production of sheet>
The thermosetting resin composition prepared above was coated into a sheet by a coating method and cured at 180° C. for 120 minutes to prepare a cured sheet having a thickness of 50 μm.
＜シートの評価＞
　上記で作製した硬化シートについて、下記の評価を行った。評価結果と（Ａ）～（Ｄ）成分の合計含有量を１００質量％としたときの（Ａ）～（Ｄ）成分の含有量を質量％で表記したものを表２に示す。
［評価方法］
・５．０質量％加熱減量温度
　熱質量測定装置（ＴＧＡ）にて、２５℃での質量を基準に、昇温速度１０℃／分で測定して５．０質量％減量したときの温度を測定した。
・引張強度、伸び率
　島津製作所製オートグラフで、硬化シートから作製した試験片を、チャック間２０ｍｍ、引張速度５ｍｍ／分の条件にて、２５℃の引張強度、伸び率を測定した。 <Sheet evaluation>
The following evaluation was performed on the cured sheet produced above. Table 2 shows the evaluation results and the content of the components (A) to (D) expressed in mass% when the total content of the components (A) to (D) is 100 mass %.
[Evaluation methods]
・5.0% by mass heating loss temperature With a thermal mass measuring device (TGA), the temperature at which the mass is reduced by 5.0% by mass is measured at a temperature rising rate of 10°C/min with reference to the mass at 25°C. It was measured.
Tensile strength and elongation The tensile strength and elongation at 25° C. of the test piece prepared from the cured sheet were measured with an autograph manufactured by Shimadzu Corporation under the conditions of a chuck distance of 20 mm and a tensile speed of 5 mm/min.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表２をみると、本発明の（Ａ）～（Ｄ）成分を含有した熱硬化性樹脂組成物は、１８０℃という低温で硬化することが可能であり、かつ耐熱性及び柔軟性を併せ持ったシートを形成できることがわかった。一方、重量平均分子量が５００ｇ/ｍｏｌ未満のポリマレイミドを含有する比較例１及び２は、実施例のシートに比べて柔軟性が劣る結果となった。さらに、（Ｂ）エポキシ樹脂を含有しない比較例３のシートは、伸び率及び耐熱性に劣ることがわかった。 As shown in Table 2, the thermosetting resin composition containing the components (A) to (D) of the present invention can be cured at a low temperature of 180° C. and has both heat resistance and flexibility. It has been found that sheets can be formed. On the other hand, Comparative Examples 1 and 2 containing the polymaleimide having a weight average molecular weight of less than 500 g/mol resulted in inferior flexibility as compared with the sheets of Examples. Further, it was found that the sheet of Comparative Example 3 containing no (B) epoxy resin was inferior in elongation rate and heat resistance.
＜シリコンウエハの封止試験＞
　次に、上記で実施例３の熱硬化性樹脂組成物から作製されたシートで、１８０℃、１２０分で硬化させ、シリコンウエハ上の封止を行った。
　直径５インチ（約１２５ｍｍ）×厚み２００μｍのシリコンウエハ上に硬化後の樹脂組成物の厚みが２００μｍ又は５０μｍとなるように封止を行った。 <Silicone wafer sealing test>
Next, the sheet prepared from the thermosetting resin composition of Example 3 was cured at 180° C. for 120 minutes to seal on a silicon wafer.
A silicon wafer having a diameter of 5 inches (about 125 mm) and a thickness of 200 μm was sealed so that the cured resin composition had a thickness of 200 μm or 50 μm.
［評価方法］
　上記熱硬化性樹脂組成物で封止されたシリコンウエハについて、以下の基準及び方法で評価した。
　上記、後硬化後、室温まで冷却し、反り量を以下の基準で評価した。測定方法はレーザー変位計を用いて、シリコンウエハの基板側中心部と、ウエハ端部２点との高低差の平均を測定した結果、厚み２００μｍ、５０μｍとも反り量が２ｍｍ未満であった。 [Evaluation methods]
The silicon wafer sealed with the thermosetting resin composition was evaluated according to the following criteria and methods.
After the above post-curing, the temperature was cooled to room temperature, and the amount of warpage was evaluated according to the following criteria. As a measurement method, a laser displacement meter was used to measure the average of the height differences between the center of the silicon wafer on the substrate side and two points on the wafer edge. As a result, the amount of warpage was less than 2 mm for both thicknesses of 200 μm and 50 μm.
　本発明の熱硬化性樹脂組成物を硬化してなる硬化物は耐熱性と柔軟性に優れたているため、半導体用封止剤、積層板、ＦＲＰ（複合材料）、層間絶縁材、接着剤等の自動車・航空機及び電気・電子材料用分野等で用いられる、高い機械的・電気的接続信頼性が求められる部品材料として好適に用いることができる。さらに、その柔軟性により、ウエアラブル端末に用いるフレキシブル基材として好適に用いることができる。

  Since the cured product obtained by curing the thermosetting resin composition of the present invention has excellent heat resistance and flexibility, it is used as a semiconductor encapsulant, laminate, FRP (composite material), interlayer insulating material, and adhesive. It can be suitably used as a component material that is required in high mechanical/electrical connection reliability and is used in the fields of automobiles/aircrafts and electric/electronic materials. Further, due to its flexibility, it can be suitably used as a flexible base material used for wearable terminals.

Claims (6)

  1. 　下記の（Ａ）～（Ｄ）成分を含有することを特徴とする、熱硬化性樹脂組成物。
    　（Ａ）重量平均分子量が５００ｇ/ｍｏｌ以上であり、マレイミド基を２個以上含有するポリマレイミド化合物
    　（Ｂ）エポキシ化合物
    　（Ｃ）ポリエステル
    　（Ｄ）芳香族アミン化合物     A thermosetting resin composition comprising the following components (A) to (D).
    (A) Polymaleimide compound having a weight average molecular weight of 500 g/mol or more and containing two or more maleimide groups (B) Epoxy compound (C) Polyester (D) Aromatic amine compound
  2. 　前記（Ａ）成分が、芳香環を有するマレイミド化合物であることを特徴とする、請求項１に記載の熱硬化性樹脂組成物。 The thermosetting resin composition according to claim 1, wherein the component (A) is a maleimide compound having an aromatic ring.
  3. 　前記（Ｃ）成分が、水酸基末端のポリエステルであることを特徴とする、請求項１又は２に記載の熱硬化性樹脂組成物。 The thermosetting resin composition according to claim 1 or 2, wherein the component (C) is a hydroxyl-terminated polyester.
  4. 　前記（Ｃ）成分が、下記式（１）の構造を有するポリエステルであることを特徴とする、請求項１～３の何れか１項に記載の熱硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、Ｒ１はそれぞれ独立して、水素原子又はハロゲン原子で置換されていてもよいアルキル基を、Ｘは、芳香環を含む基を、Ｙは、単結合、アルキレン基又は酸素原子を、繰り返し数ｎは１以上の整数を表す。）     The thermosetting resin composition according to any one of claims 1 to 3, wherein the component (C) is a polyester having a structure of the following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (1), R 1 is each independently an alkyl group which may be substituted with a hydrogen atom or a halogen atom, X is a group containing an aromatic ring, Y is a single bond, an alkylene group or The oxygen atom and the number of repetitions n represent an integer of 1 or more.)
  5. 　前記熱硬化性樹脂組成物において（Ａ）～（Ｄ）成分の合計含有量を１００質量％としたときの、（Ａ）成分の含有量が１５～７５質量％、（Ｂ）成分の含有量が１～１３質量％、（Ｃ）成分の含有量が１５～７５質量％、（Ｄ）成分の含有量が１～１５質量％であることを特徴とする、請求項１～４の何れか１項に記載の熱硬化性樹脂組成物。 In the thermosetting resin composition, when the total content of the components (A) to (D) is 100% by mass, the content of the component (A) is 15 to 75% by mass, and the content of the component (B) is Is 1 to 13% by mass, the content of the component (C) is 15 to 75% by mass, and the content of the component (D) is 1 to 15% by mass. The thermosetting resin composition according to item 1.
  6. 　シートであって、請求項１～５の何れか１項に記載の熱硬化性樹脂組成物を含有することを特徴とする、シート。

          A sheet, comprising the thermosetting resin composition according to any one of claims 1 to 5.

PCT/JP2019/047289 2018-12-04 2019-12-03 Thermosetting resin composition and sheet WO2020116467A1 (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60192779A (en) * 1984-03-14 1985-10-01 Mitsubishi Gas Chem Co Inc Adhesive composition
JPH02283757A (en) * 1989-04-25 1990-11-21 Du Pont Mitsui Polychem Co Ltd Thermoplastic polyester resin composition
JPH02311550A (en) * 1989-05-25 1990-12-27 Mitsubishi Electric Corp Resin composition for laminate
JPH06329762A (en) * 1993-05-21 1994-11-29 Sumitomo Chem Co Ltd Thermosetting resin composition and electronic component
JP2001011295A (en) * 1999-07-02 2001-01-16 Sumitomo Chem Co Ltd Thermosetting resin composition for build-up method, insulating material for build-up method, and build-up printed wiring board
JP2017179184A (en) * 2016-03-31 2017-10-05 太陽インキ製造株式会社 Curable resin composition, dry film and cured product thereof
WO2017195304A1 (en) * 2016-05-11 2017-11-16 日立化成株式会社 Liquid resin composition for encapsulation and electronic component/device
JP2018012248A (en) * 2016-07-20 2018-01-25 日立化成株式会社 Laminate, metal-clad laminate and printed wiring board
JP2018065904A (en) * 2016-10-18 2018-04-26 日立化成株式会社 Thermosetting resin composition
JP2018131513A (en) * 2017-02-14 2018-08-23 三菱瓦斯化学株式会社 Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60192779A (en) * 1984-03-14 1985-10-01 Mitsubishi Gas Chem Co Inc Adhesive composition
JPH02283757A (en) * 1989-04-25 1990-11-21 Du Pont Mitsui Polychem Co Ltd Thermoplastic polyester resin composition
JPH02311550A (en) * 1989-05-25 1990-12-27 Mitsubishi Electric Corp Resin composition for laminate
JPH06329762A (en) * 1993-05-21 1994-11-29 Sumitomo Chem Co Ltd Thermosetting resin composition and electronic component
JP2001011295A (en) * 1999-07-02 2001-01-16 Sumitomo Chem Co Ltd Thermosetting resin composition for build-up method, insulating material for build-up method, and build-up printed wiring board
JP2017179184A (en) * 2016-03-31 2017-10-05 太陽インキ製造株式会社 Curable resin composition, dry film and cured product thereof
WO2017195304A1 (en) * 2016-05-11 2017-11-16 日立化成株式会社 Liquid resin composition for encapsulation and electronic component/device
JP2018012248A (en) * 2016-07-20 2018-01-25 日立化成株式会社 Laminate, metal-clad laminate and printed wiring board
JP2018065904A (en) * 2016-10-18 2018-04-26 日立化成株式会社 Thermosetting resin composition
JP2018131513A (en) * 2017-02-14 2018-08-23 三菱瓦斯化学株式会社 Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board

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