Classifications

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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
  • C07D491/18—Bridged systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
• • 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
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/26—Di-epoxy compounds heterocyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3236—Heterocylic compounds
  • C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/34—Epoxy compounds containing three or more epoxy groups obtained by epoxidation of an unsaturated polymer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the present invention relates to a glycidyl group-containing compound having a specific structure, a curable resin composition containing the same, a cured product, and a laminate containing a layer consisting of the cured product.
• Cured products obtained from epoxy resins have excellent heat resistance, mechanical strength, electrical properties, adhesive properties, etc., and are indispensable materials in various fields such as electricity and electronics, paints, and adhesives.
• thermosetting resins such as epoxy resins have low long-term reliability.
• cured products of epoxy resins deteriorate due to oxidation, cracks may occur.
• thermosetting resins such as epoxy resins cannot be dissolved in solvents (insoluble) or even at high temperatures (infusible), making them easy to recycle and reuse. Since the cured product becomes waste after use, it is a challenge to reduce waste and reduce the burden on the environment.
• microcapsule particles containing the first thermosetting resin and the second thermosetting resin precursor can be used.
• discloses a method of creating a self-repairable sealing material for example, see Patent Document 2.
• Non-Patent Document 1 As a method of imparting self-healing properties to a cured epoxy resin product, it has been proposed to incorporate a bonding site by Diels-Alder reaction (see, for example, Non-Patent Document 1).
• Patent Document 1 the adhesive after disassembly is discarded, and although the base material that is the adhesive is recyclable, there is a problem that the recyclability as a whole is insufficient. Furthermore, although the technology disclosed in Patent Document 2 has self-repair properties to a certain extent, it is not a solution from the viewpoint of reuse, and the problem of waste when it is no longer needed remains. In the technology provided in the above-mentioned Non-Patent Document 1, there is a possibility that the low-molecular compound generated by the Retro-Diels-Alder reaction will volatilize from the cured product, resulting in a decrease in mass or contaminating the mold during remolding. be.
• an object of the present invention is to provide a compound that is a curable resin but can easily achieve repairability, remoldability, and easy disassembly in the cured product, and a curable resin composition using the compound.
• Our goal is to provide products and their cured products.
• the present invention includes the following aspects.
• a glycidyl group characterized in that a conjugated diene structure (A) having one or more glycidyl groups and a parent diene structure (B) having one or more glycidyl groups are connected by a Diels-Alder reaction. Containing compounds.
• R 1 is a glycidyl group or a substituent having one or more glycidyl groups
• R 2 to R 11 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, or a carboxy group.
• a cyano group an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, an amido group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a glycidyl group
• the carbon atom or nitrogen of the alkoxy group, aralkyloxy group, aryloxy group, amino group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group, aralkyl group, aryl group, glycidyl group It may have a substituent on the atom.
• At least one of R 2 to R 5 in formulas (1) and (1') and at least one of R 2 to R 11 in formulas (2) and (2') is a glycidyl group, or A group having one or more glycidyl groups.
• each Ar is independently a structure having an aromatic ring that is unsubstituted or has a substituent
• X is a structural unit represented by the following formula (3-1)
• Y is a structural unit represented by the following formula (3-2)
• R 21 and R 22 are each independently a hydrogen atom, a methyl group or an ethyl group
• R' is a divalent hydrocarbon group having 2 to 12 carbon atoms
• R 23 , R 24 , R 27 and R 28 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group
• R 25 , R 26 , R 29 and R 30 are each independently a hydrogen atom or a methyl group
• n 1 is an integer from 4 to 16
• n 2 is an average value of repeating units, and is 2 to 30.
• R 31 and R 32 are each independently a glycidyl ether group or a 2-methylglycidyl ether group
• R 33 and R 34 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group
• R 35 and R 36 are hydrogen atoms or methyl groups
• m1, m2, p1, p2, q are repeated average values
• m1 and m2 are each independently from 0 to 25
• m1+m2 ⁇ 1 p1 and p2 are each independently 0 to 5
• q is 0.5 to 5.
• the bond between the structural unit X represented by the above formula (3-1) and the structural unit Y represented by the above formula (3-2) may be random or block, and one molecule
• the total number of structural units X and Y present in the structure is m1 and m2, respectively.
• a laminate comprising a base material and a layer containing the cured product according to [13].
• the present invention it is possible to impart repairability, remoldability, and easy disassembly properties to a cured product made of a curable resin composition, and there is no mass loss during remolding, and the cured product itself can be improved. It can contribute to extending the lifespan and reducing waste.
• a conjugated diene structure (A) having one or more glycidyl groups and a parent diene structure (B) having one or more glycidyl groups are connected by a Diels-Alder reaction. It is characterized by being In addition, the glycidyl group in the present invention does not mean only a glycidyl group without a substituent, but also includes a glycidyl group having a substituent on a carbon atom.
• the Diels-Alder reaction is not limited to the Diels-Alder reaction in the narrow sense, which is a reaction of a conjugated diene structure or a parent diene structure that does not contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom; It also includes the Hetero-Diels-Alder reaction, which is a reaction of a conjugated diene structure or a parent diene structure containing a heteroatom such as a sulfur atom.
• the reversible bond by the Diels-Alder reaction is a reaction in which a conjugated diene and a parent diene undergo an addition reaction to form a six-membered ring. Since the Diels-Alder reaction is an equilibrium reaction, the Retro-Diels-Alder reaction occurs at a predetermined temperature and dissociation (dissociation and crosslinking) occurs.
• a glycidyl group-containing compound as an embodiment of the present invention is incorporated into a crosslinked structure by a curing reaction based on the glycidyl group, but if the cured product is subjected to impact and cracks or is crushed, , exhibits easy disassembly by being cut at the reversible bonding portion.
• the reversible bond can be reversibly reshaped even in a low temperature range including room temperature, and can exhibit functions such as repairability and remoldability. Even if the cured product used is crushed, it is easy to repair the cured product by placing it at a low temperature including room temperature or in a heated/heated state based on reversible bonding.
• a glycidyl group-containing compound as one embodiment of the present invention is formed by linking a conjugated diene structure (A) having one or more glycidyl groups and a parent diene structure (B) having one or more glycidyl groups.
• the glycidyl group for example, as a glycidyl ether group or diglycidylamino group, is linked to a compound having a conjugated diene structure or a parent diene structure, which will be described later, directly or via another group such as an aromatic ring. This is preferable from the viewpoint of easy availability.
• one molecule may have a plurality of different types of glycidyl groups, such as a glycidyl ether group and a diglycidylamino group.
• the conjugated diene structure (A) is not particularly limited, and includes an aliphatic hydrocarbon skeleton such as a 1,3-butadiene skeleton; an aromatic hydrocarbon skeleton such as anthracene; and a ring such as cyclopentadiene and dicyclopentadiene.
• Formula diene; examples include heterocyclic skeletons such as imidazole ring, furan ring, triazine ring, thiophene ring, and pyrrole ring.
• it is essential to have a glycidyl group in the compound having these skeletons and rings, but it may have various other substituents as long as it does not inhibit the Diels-Alder reaction. .
• the number of glycidyl groups in one molecule is not limited to one, and may have multiple glycidyl groups, but it is easy to obtain and synthesize the compound, and when used as a curable resin composition. From the viewpoint of balance between reactivity and ease of disassembly and remolding of the cured product, the number is preferably 1 to 3, and more preferably 1 to 2.
• the parent diene structure (B) is not particularly limited, and examples include compounds having a maleimide group, an acryloyl group, a vinyl ketone group, an acetylene group, an allyl group, a diazo group, a nitro group, a benzoquinone skeleton, etc. .
• it is essential to have a glycidyl group in the compound having these functional groups, but various other substituents may be present as long as the Diels-Alder reaction is not inhibited.
• the number of glycidyl groups in one molecule is not limited to one, and may have multiple glycidyl groups, but it is easy to obtain and synthesize the compound, and when used as a curable resin composition. From the viewpoint of balance between reactivity and ease of dismantling and remolding of the cured product, the number is preferably 1 to 3, and more preferably 1 to 2. Compounds containing these functional groups may also contain various substituents and structures as long as they do not inhibit the Diels-Alder reaction.
• the glycidyl group-containing compound as one form of the present invention is not particularly limited as long as it is a combination of the above-mentioned conjugated diene structure (A) and parent diene structure (B), but it can be used in a curable resin composition.
• the epoxy equivalent of the compound is preferably in the range of 100 to 500 g/eq.
• the conjugated diene structure (A) is preferably a furan-derived structure or an anthracene-derived structure
• the parent diene structure (B) is preferably a structure derived from maleimide
• the combination has a dissociation temperature of 100°C or higher, particularly preferably 120°C or higher. When used at a higher temperature, the dissociation temperature can be set to 130°C or higher.
• the conjugated diene structure (A) is an anthracene-derived structure, and the parent diene structure (B) is a maleimide-derived structure. is preferred.
• the conjugated diene structure (A) is a furan-derived structure or an anthracene-derived structure and the parent diene structure (B) is a maleimide-derived structure
• a furan compound having a substituent having a glycidyl group on the ring is used.
• a method using an anthracene compound and a maleimide compound having a substituent having a glycidyl group is preferable because the production method is simple.
• a glycidyl group-containing compound that is one embodiment of the present invention can be represented by the following structural formula.
• R 1 is a glycidyl group or a substituent having one or more glycidyl groups
• R 2 to R 11 each independently represent a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, a carboxy group, a cyano group, alkoxy group, aralkyloxy group, aryloxy group, amino group, amido group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group, aralkyl group, aryl group or glycidyl group,
• the carbon atom or nitrogen of the alkoxy group, aralkyloxy group, aryloxy group, amino group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group, aralkyl group, aryl group, glycidyl group It may have a substituent on the atom.
• the method for producing the glycidyl group-containing compound that is one embodiment of the present invention is not particularly limited. Depending on the desired structure, it can be produced stepwise using known reactions, and it can also be obtained by appropriately combining commercially available raw materials. Typical synthesis methods will be described below.
• the Diels-Alder reaction in which a conjugated diene and a parent diene undergo an addition reaction to form a six-membered ring is an equilibrium reaction, and at a higher temperature than the temperature at which the addition reaction proceeds, the addition reaction moiety dissociates and the original It is widely known that the retro-Diels-Alder reaction proceeds, which is a reverse reaction in which the conjugated diene and the parent diene are returned. A known method may be used for the Diels-Alder reaction.
• a conjugated diene compound and a parent diene compound are mixed in equimolar amounts, or in some cases in excess of one component, heated and melted or dissolved in a solvent, stirred at a temperature of room temperature to 110°C for 1 to 24 hours, and then purified as is. It can be obtained by filtration or solvent distillation without purification, or it can be obtained by commonly used isolation and purification methods such as recrystallization, reprecipitation, and chromatography.
• a furan compound having a hydroxyl group or an amino group which is a precursor of a glycidyl group, and specifically, the furan compounds listed in the following formula are used. Any of the compounds can be used.
• the hydroxyl group in the compound can be converted into a glycidyl ether group, for example, by a known method as described in the Examples, and the amino group can similarly be converted into a diglycidyl amino group.
• a hydroxyl group or an amino group may be bonded to any position on the ring.
• the compounds shown below are particularly preferred from the viewpoint of the balance between reactivity, physical properties of cured products, and easy disassembly, repairability, and remoldability.
• an anthracene compound having a hydroxyl group or an amino group which is a precursor of a glycidyl group, and specifically, an anthracene compound listed in the following formula. Any of the compounds can be used.
• 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene and hydroxyanthracene are preferable because of their good curability, and 9-(4-hydroxybenzyl)-10-(4- Hydroxyphenyl)anthracene and monohydroxyanthracene are particularly preferred in view of the balance between reactivity, physical properties of cured products, and repairability and remolding properties.
• the hydroxyl group in the compound can be converted into a glycidyl ether group, for example, by a known method as described in the Examples, and the amino group can similarly be converted into a diglycidyl amino group.
• a maleimide compound having a hydroxyl group or an amino group which is a precursor of a glycidyl group
• the maleimide compound having a hydroxyl group or an amino group include any of the compounds listed in the following formulas.
• hydroxyphenylmaleimide is preferable in terms of curability when it is converted into a glycidyl ether
• monohydroxyphenylmaleimide is a particularly preferable raw material in view of the balance between reactivity, physical properties of cured products, and repairability and remoldability. be.
• parahydroxyphenylmaleimide is particularly preferred from the viewpoint of heat resistance of the cured product.
• the hydroxyl group in the compound can be converted into a glycidyl ether group, for example, by a known method as described in the Examples, and the amino group can similarly be converted into a diglycidyl amino group.
• the structures of the above furan compounds, anthracene compounds, and maleimide compounds each independently include a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, and an aryl group. It includes those having an oxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group as a substituent.
• an alkoxy group, an aralkyloxy group, an aryloxy group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkyl group, a cycloalkyl group, an aralkyl group, and an aryl group. also include those in which various substituents are further bonded to the carbon atom/nitrogen atom they have.
• the glycidyl group-containing compound of the present invention can be made into a curable resin composition by using a compound (I) that is reactive with the glycidyl group-containing compound.
• the curable resin composition can be suitably used for various electrical and electronic components such as adhesives, paints, photoresists, printed wiring boards, and semiconductor sealing materials.
• Examples of the compound (I) that is reactive with the glycidyl group-containing compound include various known compounds such as amine compounds, acid anhydrides, amide compounds, phenolic hydroxyl group-containing compounds, carboxylic acid compounds, and thiol compounds.
• Examples include curing agents for epoxy resins.
• the curing agent can be appropriately selected depending on the physical properties of the desired cured product, but it is particularly preferable to use a hydroxyl group-containing compound from the viewpoint of mechanical strength, adhesion to the substrate, etc.
• amine compounds examples include trimethylenediamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, and N,N,N',N'-tetramethyldiamine.
• Aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, picoline;
• Epoxy compound addition polyamine Michael addition polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone-blocked polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine complex, boron trifluoride-mono Examples include modified amine compounds such as ethylamine complexes.
• the acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, polypropylene glycol maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hexahydrophthalic anhydride. acids, methylhexahydrophthalic anhydride, and the like.
• the phenolic hydroxyl group-containing compound includes bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, Bisphenols such as 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, phenol novolac resin, cresol Novolak resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyrock resin), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol- Phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, bipheny
• the amide compounds include dicyandiamide and polyamide amine.
• the polyamide amine includes, for example, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid, carboxylic acid compounds such as fatty acids and dimer acids, and aliphatic polyamines and polyoxyalkylenes. Examples include those obtained by reacting polyamines having chains.
• carboxylic acid compound examples include carboxylic acid polymers such as carboxylic acid-terminated polyester, polyacrylic acid, and maleic acid-modified polypropylene glycol.
• the thiol compound preferably contains two or more thiol groups in two molecules.
• amine compounds particularly dicyandiamide
• solid type phenolic compounds are preferred from the viewpoint of heat resistance of cured products.
• aliphatic amines and thiol compounds are preferred from the viewpoint of low temperature curing.
• the other epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, polyhydroxybenzene epoxy resin, polyhydroxynaphthalene epoxy resin, and biphenyl epoxy resin.
• Resin liquid epoxy resin such as tetramethylbiphenyl epoxy resin, brominated epoxy resin such as brominated phenol novolak epoxy resin, solid bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin Epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolac type epoxy
• an epoxy resin having an epoxy equivalent of 100 to 10,000 g/eq in combination from the viewpoint of achieving an excellent balance between curability and crosslinking density of the resulting cured product. It is preferable to use an epoxy resin which has an epoxy equivalent weight of 500 to 10,000 g/eq.
• each Ar is independently a structure having an aromatic ring that is unsubstituted or has a substituent
• X is a structural unit represented by the following formula (3-1)
• Y is a structural unit represented by the following formula (3-2)
• R 21 and R 22 are each independently a hydrogen atom, a methyl group or an ethyl group
• R' is a divalent hydrocarbon group having 2 to 12 carbon atoms
• R 23 , R 24 , R 27 and R 28 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group
• R 25 , R 26 , R 29 and R 30 are each independently a hydrogen atom or a methyl group
• n 1 is an integer from 4 to 16
• n 2 is an average value of repeating units, and is 2 to 30.
• R 31 and R 32 are each independently a glycidyl ether group or a 2-methylglycidyl ether group
• R 33 and R 34 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group
• R 35 and R 36 are hydrogen atoms or methyl groups
• m1, m2, p1, p2, q are repeated average values
• m1 and m2 are each independently from 0 to 25
• m1+m2 ⁇ 1 p1 and p2 are each independently 0 to 5
• q is 0.5 to 5.
• the bond between the structural unit X represented by the above formula (3-1) and the structural unit Y represented by the above formula (3-2) may be random or block, and one molecule
• the total number of structural units X and Y present in the structure is m1 and m2, respectively.
• an epoxy resin represented by the following formula may be used.
• p 1 , p 2 , q, m 1 and n 1 are the average values of repetition, and each independently, p 1 is 0 to 5, p 2 is 0 to 5, and q is 0. .5 to 5, m 1 is 0 to 25, n 1 is 2 to 30.
• the epoxy resin represented by the general formula (3) may be used alone in combination to form a curable resin composition, but it is also possible to impart even more flexibility to the cured product and easily exhibit easy dismantling properties. In view of this, it is also preferable to use an epoxy resin having an epoxy equivalent of 100 to 300 g/eq.
• the above-mentioned epoxy resin that can be used in combination may have an epoxy equivalent in the range of 100 to 300 g/eq, and its structure is not limited.
• bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin.
• Liquid epoxy resins such as resins, brominated epoxy resins such as brominated phenol novolac type epoxy resins, solid bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol type epoxy resin
• bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl.
• liquid epoxy resins such as type epoxy resins, it is preferable to use epoxy resins having an epoxy equivalent of 100 to 300 g/eq.
• the resins it is particularly preferable to use an epoxy resin having an epoxy equivalent of 100 to 300 g/eq.
• the ratio of the epoxy resin represented by the general formula (3) and the epoxy resin having an epoxy equivalent of 100 to 300 g/eq is not particularly limited, but from the viewpoint of easy phase separation in the cured product,
• the mass ratio of the former to the latter is 97:3 to 3:97, preferably 10:90 to 90:10, particularly preferably 80:20 to 20:80.
• Phase separation in the cured product creates a sea-island structure, which achieves both adhesion and stress relaxation ability of the cured product, exhibits particularly high adhesive strength over a wide temperature range, and is suitable for molding before and after heat curing of the resin composition. It has the effect of reducing the shrinkage rate.
• the concentration of reversible bonds in the curable resin composition of the present invention is preferably 0.10 mmol/g or more based on the total mass of curable components in the curable resin composition. According to such a configuration, both the repairability and the remoldability of the cured product obtained from the curable resin composition become even better.
• the concentration of the aforementioned reversible bond is more preferably 0.10 to 3.00 mmol/g, even more preferably 0.15 to 2.00 mmol/g.
• the concentration of the reversible bond can be appropriately selected depending on the glass transition temperature defined by the tan ⁇ peak top of the desired cured product measured by a dynamic viscoelastic analyzer (DMA).
• DMA dynamic viscoelastic analyzer
• the glass transition temperature of the cured product when using the glass transition temperature as a guideline, if the glass transition temperature of the cured product is around room temperature, sufficient repairability and remoldability functions are likely to be exhibited even at the low concentration side of the preferred range. On the other hand, if the glass transition temperature of the desired cured product exceeds 100° C., the function will be more likely to be exhibited at the higher concentration side of the preferred range. However, in the temperature range exceeding the glass transition temperature measured by DMA, molecular mobility is generally high, and sufficient repairability and remoldability functions are likely to be expressed even if the concentration of the glycidyl group-containing compound is low.
• the effects of repairability and remoldability functions can be adjusted by appropriately adjusting the aging temperature for repair or the heating temperature for remolding.
• the relationship between the glass transition temperature of the cured product and the concentration of reversible bonds is not limited to these.
• the ratio of the total glycidyl groups to the total active groups capable of reacting with the glycidyl groups in the curable resin composition of the present invention is not particularly limited, the mechanical From the viewpoint of good physical properties, etc., the amount of active groups capable of reacting with glycidyl groups is preferably 0.4 to 1.5 equivalents per total equivalent of glycidyl groups in the resin composition.
• the curable resin composition may contain a curing accelerator.
• a curing accelerator Various types of curing accelerators can be used, and examples thereof include urea compounds, phosphorus compounds, tertiary amines, imidazole, imidazolines, organic acid metal salts, Lewis acids, and amine complex salts.
• urea compounds particularly 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) are preferred because of their excellent workability and low-temperature curability.
• DCMU 3-(3,4-dichlorophenyl)-1,1-dimethylurea
• triphenylphosphine is used as a phosphorus compound, and 1,8-diazabicyclo-[ 5.4.0]-undecene is preferred.
• Examples of the phosphorus compound include alkyl phosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine; dialkylphosphines such as dimethylphosphine and dipropylphosphine; secondary phosphines such as diphenylphosphine and methylethylphosphine; trimethyl Examples include tertiary phosphines such as phosphine, triethylphosphine, and triphenylphosphine.
• alkyl phosphines such as ethylphosphine and butylphosphine
• primary phosphines such as phenylphosphine
• dialkylphosphines such as dimethylphosphine and dipropylphosphine
• secondary phosphines such as diphenylphosphine and methylethy
• imidazole examples include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4 -ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutyl Imidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl
• imidazoline compound examples include 2-methylimidazoline and 2-phenylimidazoline.
• urea compounds examples include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, N-( Examples include 3-chloro-4-methylphenyl)-N',N'-dimethylurea.
• curable resin composition of the present invention may be used in combination with other thermosetting resins or thermoplastic resins as long as the effects of the present invention are not impaired.
• thermosetting resins examples include cyanate ester resins, resins having a benzoxazine structure, active ester resins, vinylbenzyl compounds, acrylic compounds, and copolymers of styrene and maleic anhydride.
• the amount used is not particularly limited as long as it does not impede the effects of the present invention, but within the range of 1 to 50 parts by mass based on 100 parts by mass of the curable resin composition. It is preferable that there be.
• cyanate ester resin examples include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, and phenylene ether type cyanate ester resin.
• naphthylene ether type cyanate ester resin biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate Ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol condensed novolak Examples include a naphthol-cresol cocondensed novolac type cyanate ester resin, an aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resin, a biphenyl-cresol
• cyanate ester resins bisphenol A type cyanate ester resins, bisphenol F type cyanate ester resins, bisphenol E type cyanate ester resins, and polyhydroxynaphthalene type cyanate ester resins are preferred in that they yield cured products with particularly excellent heat resistance. It is preferable to use a naphthylene ether type cyanate ester resin, or a novolac type cyanate ester resin, and a dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that a cured product having excellent dielectric properties can be obtained.
• the resin having a benzoxazine structure there are no particular restrictions on the resin having a benzoxazine structure, but for example, the reaction product of bisphenol F, formalin, and aniline (F-a type benzoxazine resin), the reaction product of diaminodiphenylmethane, formalin, and phenol (P- d-type benzoxazine resin), reaction product of bisphenol A, formalin and aniline, reaction product of dihydroxydiphenyl ether, formalin and aniline, reaction product of diaminodiphenyl ether, formalin and phenol, dicyclopentadiene-phenol addition type resin and formalin and aniline, a reaction product of phenolphthalein, formalin and aniline, and a reaction product of diphenyl sulfide, formalin and aniline.
• F-a type benzoxazine resin the reaction product of bisphenol F, formalin, and aniline
• P- d-type benzoxazine resin the reaction product of bis
• the active ester resin is not particularly limited, but generally contains ester groups with high reactivity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. Compounds having two or more are preferably used.
• the active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound.
• active ester resins obtained from a carboxylic acid compound or its halide and a hydroxy compound are preferred, and active ester resins obtained from a carboxylic acid compound or its halide and a phenol compound and/or a naphthol compound are preferred. More preferred.
• the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and halides thereof.
• Phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m -Cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin , benzenetriol, dicyclopentadiene-phenol addition type resin, etc.
• active ester resins include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins that are acetylated phenol novolacs, and active ester resins that are benzoylated phenol novolacs. Ester resins are preferred, and among them, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred since they are excellent in improving peel strength.
• novolac resins addition polymerized resins of alicyclic diene compounds such as dicyclopentadiene and phenol compounds, modified novolac resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenolic aralkyl resins (Zyrock resins) ), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, and various vinyl polymers may be used in combination.
• the various novolak resins are produced by combining phenolic hydroxyl group-containing compounds such as phenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, and dihydroxynaphthalene, and aldehyde compounds with an acid catalyst.
• phenolic hydroxyl group-containing compounds such as phenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, and dihydroxynaphthalene
• aldehyde compounds with an acid catalyst.
• examples include polymers obtained by reacting under certain conditions.
• the various vinyl polymers include polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly( Examples include homopolymers of vinyl compounds such as meth)acrylates and copolymers thereof.
• Thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin
• the blending ratio of the glycidyl group-containing compound of the present invention and other resins can be arbitrarily set depending on the application, but this may hinder the repairability and remolding properties of the present invention. From the viewpoint of preventing this from occurring, it is preferable that the proportion of the other resin is 0.5 to 100 parts by mass based on 100 parts by mass of the glycidyl group-containing compound of the present invention.
• a non-halogen flame retardant containing substantially no halogen atoms may be blended.
• non-halogen flame retardants examples include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc., and there are no restrictions on their use. It is also possible to use a single flame retardant, a plurality of flame retardants of the same type, or a combination of flame retardants of different types.
• the phosphorus flame retardant can be either inorganic or organic.
• inorganic compounds include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide. .
• the red phosphorus is subjected to a surface treatment for the purpose of preventing hydrolysis, etc.
• surface treatment methods include, for example, (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; (iii) a method of coating with a mixture of thermosetting resins such as phenolic resin; (iii) a method of coating with a mixture of thermosetting resins such as phenolic resin; Examples include a method of double coating with resin.
• organic phosphorus compounds examples include general-purpose organic phosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7- Examples include cyclic organic phosphorus compounds such as (dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.
• general-purpose organic phosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds
• the blending amount of these phosphorus-based flame retardants is appropriately selected depending on the type of phosphorus-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy.
• red phosphorus is used as a non-halogen flame retardant, it is blended in the range of 0.1 parts by mass to 2.0 parts by mass in 100 parts by mass of the resin composition containing all other fillers and additives.
• organic phosphorus compound is used, it is preferably blended in a range of 0.1 parts by mass to 10.0 parts by mass, and preferably blended in a range of 0.5 parts by mass to 6.0 parts by mass. It is more preferable to do so.
• hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. may be used in combination with the phosphorus-based flame retardant. good.
• nitrogen-based flame retardant examples include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, etc., with triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds being preferred.
• the triazine compounds include, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and also (1) guanylmelamine sulfate, melem sulfate, melam sulfate.
• sulfuric acid aminotriazine compounds such as (2) cocondensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, and melamines such as melamine, benzoguanamine, acetoguanamine, and formguanamine, and formaldehyde; (3) the above-mentioned (2) A mixture of the co-condensate and a phenol resin such as a phenol-formaldehyde condensate; (4) a mixture of the above-mentioned (2) and (3) further modified with tung oil, isomerized linseed oil, etc., and the like.
• cyanuric acid compound examples include cyanuric acid, melamine cyanurate, and the like.
• the blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferably blended in the range of 0.05 to 10 parts by mass, and preferably blended in the range of 0.1 to 5 parts by mass in 100 parts by mass of the resin composition containing all other fillers and additives. It is more preferable to do so.
• metal hydroxides, molybdenum compounds, etc. may be used in combination.
• the silicone flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples include silicone oil, silicone rubber, and silicone resin.
• the amount of the silicone flame retardant to be blended is appropriately selected depending on the type of silicone flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferable to blend the filler and other fillers and additives in an amount of 0.05 to 20 parts by mass in 100 parts by mass of the resin composition.
• a molybdenum compound, alumina, etc. may be used in combination.
• inorganic flame retardant examples include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass.
• metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.
• the metal oxides include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.
• metal carbonate compounds examples include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate, and the like.
• metal powder examples include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.
• Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.
• low melting point glass examples include Sheeply (BOXI BROWN), hydrated glass SiO 2 -MgO-H 2 O, PbO-B 2 O 3- based, ZnO-P 2 O 5 -MgO-based, P 2 O 5 Glassy compounds such as -B 2 O 3 -PbO-MgO series, P-Sn-O-F series, PbO-V 2 O 5 -TeO 2 series, Al 2 O 3 -H 2 O series, lead borosilicate series, etc. can be mentioned.
• the amount of the inorganic flame retardant to be blended is appropriately selected depending on the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferably blended in the range of 0.05 parts by mass to 20 parts by mass, and preferably in the range of 0.5 parts by mass to 15 parts by mass, in 100 parts by mass of the resin composition containing all other fillers and additives. It is more preferable to mix it with
• the organic metal salt flame retardant is, for example, ferrocene, an acetylacetonate metal complex, an organic metal carbonyl compound, an organic cobalt salt compound, an organic sulfonic acid metal salt, a metal atom and an aromatic compound or a heterocyclic compound having an ionic bond or an arrangement. Examples include compounds with position bonding.
• the amount of the organic metal salt flame retardant to be blended is appropriately selected depending on the type of the organic metal salt flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferably blended in an amount of 0.005 parts by mass to 10 parts by mass in 100 parts by mass of the resin composition containing all the halogenated flame retardants and other fillers and additives.
• the curable resin composition of the present invention may contain a filler.
• fillers include inorganic fillers and organic fillers.
• examples of the inorganic filler include inorganic fine particles.
• Examples of inorganic fine particles with excellent heat resistance include alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine amorphous powder)
• Examples of materials with excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc.
• materials with excellent conductivity include single metals or alloys ( For example, metal fillers and/or metal-coated fillers using iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.
• Examples of materials with excellent barrier properties include mica, clay, kaolin, Minerals such as talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate
• silica fine particles such as powdered silica and colloidal silica
• known silica fine particles such as powdered silica and colloidal silica
• powdered silica fine particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silica Kogyo Co., Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., and SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
• colloidal silica includes, for example, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, Examples include ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, and the like.
• silica fine particles may be used; for example, the silica fine particles may be surface-treated with a reactive silane coupling agent having a hydrophobic group, or modified with a compound having a (meth)acryloyl group.
• a reactive silane coupling agent having a hydrophobic group or modified with a compound having a (meth)acryloyl group.
• Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd.; commercially available colloidal silica modified with a compound having a (meth)acryloyl group include: Examples include MIBK-SD manufactured by Nissan Chemical Industries, Ltd.
• the shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous, or irregularly shaped particles can be used. Further, the primary particle diameter is preferably in the range of 5 to 200 nm.
• titanium oxide fine particles not only extender pigments but also ultraviolet light-responsive photocatalysts can be used, such as anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, etc. Furthermore, particles designed to respond to visible light by doping a different element into the crystal structure of titanium oxide can also be used.
• the element to be doped into titanium oxide anion elements such as nitrogen, sulfur, carbon, fluorine, and phosphorus, and cation elements such as chromium, iron, cobalt, and manganese are suitably used.
• a powder, a sol or a slurry dispersed in an organic solvent or water can be used.
• Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd. and ATM-100 manufactured by Teika Co., Ltd. Furthermore, examples of commercially available titanium oxide fine particles in the form of slurry include TKD-701 manufactured by Teika Corporation.
• the curable resin composition of the present invention may further contain a fibrous matrix.
• the fibrous substrate is not particularly limited, but it is preferably one used for fiber reinforced resins, including inorganic fibers and organic fibers.
• Inorganic fibers include inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, and silicon carbide fiber, as well as carbon fiber, activated carbon fiber, graphite fiber, tungsten carbide fiber, silicon carbide fiber (silicon carbide fiber), and ceramics.
• Examples include fibers, natural fibers, mineral fibers such as basalt, boron nitride fibers, boron carbide fibers, and metal fibers.
• the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.
• Organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylenebenzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, polyarylate, cellulose, pulp, Examples include natural fibers such as cotton, wool, and silk, and regenerated fibers such as proteins, polypeptides, and alginic acid.
• resin materials such as polybenzazole, aramid, PBO (polyparaphenylenebenzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, polyarylate, cellulose, pulp, Examples include natural fibers such as cotton, wool, and silk, and regenerated fibers such as proteins, polypeptides, and alginic acid.
• carbon fibers and glass fibers are preferred because they have a wide range of industrial applications. Among these, only one type may be used, or a plurality of types may be used simultaneously.
• the fibrous substrate may be an aggregate of fibers, and the fibers may be continuous or discontinuous, and may be woven or nonwoven. Further, it may be a fiber bundle in which the fibers are aligned in one direction, or it may be in the form of a sheet in which the fiber bundles are arranged. Alternatively, the fiber aggregate may have a three-dimensional shape with a thickness.
• a dispersion medium may be used in the curable resin composition of the present invention for the purpose of adjusting the solid content and viscosity of the resin composition.
• the dispersion medium may be any liquid medium that does not impair the effects of the present invention, and includes various organic solvents, liquid organic polymers, and the like.
• organic solvent examples include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF), and dioxolane, and esters such as methyl acetate, ethyl acetate, and butyl acetate.
• ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK)
• cyclic ethers such as tetrahydrofuran (THF)
• dioxolane examples of the organic solvent
• esters such as methyl acetate, ethyl acetate, and butyl acetate.
• aromatics such as toluene and xylene
• alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether.
• the liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, such as acrylic polymer (Floren WK-20: Kyoeisha), amine salt of specially modified phosphoric acid ester (HIPLAAD ED-251: Kusumoto Kasei), modified Examples include acrylic block copolymers (DISPERBYK2000; BYK Chemie).
• the resin composition of the present invention may contain other ingredients.
• catalysts polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, Examples include antioxidants, flame retardants, plasticizers, and reactive diluents.
• a cured product can be obtained by curing the resin composition of the present invention.
• curing may be performed at room temperature or by heating.
• thermal curing it may be cured by one heating process or may be cured through a multi-step heating process.
• the curable resin composition of the present invention can also be cured with active energy rays.
• a photocationic polymerization initiator may be used as the polymerization initiator.
• the active energy ray visible light, ultraviolet rays, X-rays, electron beams, etc. can be used.
• photocationic polymerization initiator examples include aryl-sulfonium salts, aryl-iodonium salts, etc. Specifically, arylsulfonium hexafluorophosphate, arylsulfonium hexafluoroantimonate, arylsulfonium tetrakis(pentafluoro)borate , tri(alkylphenyl)sulfonium hexafluorophosphate, etc. can be used.
• the photocationic polymerization initiators may be used alone or in combination of two or more.
• the curable resin composition of the present invention can be prepared by uniformly mixing the above-mentioned components, and the method is not particularly limited.
• it can be prepared by uniformly mixing using a pot mill, ball mill, bead mill, roll mill, homogenizer, super mill, homodisper, all-purpose mixer, Banbury mixer, kneader, or the like.
• the curable resin composition of the present invention comprises the above-mentioned glycidyl group-containing compound of the present invention and the compound (I) that is reactive with the glycidyl group-containing compound, and if necessary, the above-mentioned curing agent and filler that can be used in combination.
• the fibrous matrix, the dispersion medium, and the resin other than the various compounds described above are dissolved in the dispersion medium such as the organic solvent described above. After dissolution, a curable resin composition can be obtained by distilling off the solvent and drying under reduced pressure using a vacuum oven or the like. Further, the curable resin composition of the present invention may be in a state in which the above-mentioned constituent materials are uniformly mixed.
• each constituent material can be adjusted as appropriate depending on the desired properties of the cured product, such as mechanical strength, heat resistance, repairability, and remoldability. Further, in preparing the curable resin composition, there are no particular limitations on the order in which the specific constituent materials are mixed.
• the cured product of the present invention is obtained by curing the compound (I) that is reactive with the glycidyl group-containing compound using the glycidyl group-containing compound of the present invention.
• a known method can be appropriately selected and employed depending on the properties of the compound (I) that is reactive with the glycidyl group-containing compound used.
• the cured product of the present invention is cured with the glycidyl group-containing compound of the present invention as described above, it can maintain good mechanical strength by developing an appropriate crosslink density. Furthermore, when the cured product of the present invention is scratched or subjected to mechanical energy such as an external force, the reversible bond is broken, but the equilibrium shifts in the bonding direction, so that an adduct is formed again, which can be used to repair scratches or It is thought that remolding becomes possible.
• the structure of the obtained cured product can be confirmed by infrared absorption (IR) spectroscopy using Fourier transform infrared spectroscopy (FT-IR), elemental analysis, X-ray scattering, etc.
• IR infrared absorption
• FT-IR Fourier transform infrared spectroscopy
• elemental analysis X-ray scattering, etc.
• the cured product that is an embodiment of the present invention can be obtained by using the glycidyl group-containing compound of the present invention as a component of a curable resin composition, but the cured product is an intermediate of the glycidyl group-containing compound.
• a conjugated diene having one or more glycidyl groups as described above and a parent diene a cured product can be obtained while forming the glycidyl group-containing compound during the curing process (synthesizing in situ).
• the curable resin composition of the present invention and the cured product produced from the curable resin composition have easy disassembly, repairability, and remolding properties, and are useful for the following uses.
• the cured resin of the present invention can be laminated with a base material to form a laminate.
• the base material for the laminate may be an inorganic material such as metal or glass, or an organic material such as plastic or wood, depending on the purpose, and may be in the form of a laminate, such as a flat plate, sheet, or tertiary It may have an original structure or may be three-dimensional. It may have any shape depending on the purpose, such as having curvature on the entire surface or in part. Furthermore, there are no restrictions on the hardness, thickness, etc. of the base material. Alternatively, it may be a multilayer laminate in which the first base material, a layer made of a cured product of the curable resin composition of the present invention, and the second base material are laminated in this order.
• the curable resin composition of this embodiment has excellent adhesive properties, it can be suitably used as an adhesive for bonding a first base material and a second base material. Further, the cured resin of the present invention may be used as a base material, and the cured product of the present invention may be further laminated.
• the cured resin of the present invention can relieve stress, it can be particularly suitably used for bonding different materials.
• the base material is a metal and/or metal oxide and the second base material is a laminate of different materials such as a plastic layer, the adhesive strength will be improved due to the stress relaxation ability of the cured product of the present invention. maintained.
• the layer containing the cured product may be formed by direct coating or molding on the base material, or may be formed by laminating already molded products.
• direct coating there are no particular limitations on the coating method, including spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, Examples include screen printing method, inkjet method, and the like.
• direct molding examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, and the like.
• uncured or semi-cured composition layers may be laminated and then cured, or a layer containing a completely cured composition may be laminated on the base material. It's okay.
• the cured product of the present invention may be laminated by coating and curing a precursor that can serve as a base material, or if the precursor that can serve as a base material or the composition of the present invention is uncured or semi-cured. It may be hardened after adhering in this state.
• the precursor that can serve as the base material and examples include various curable resin compositions.
• the cured product obtained using the curable resin composition of the present invention has particularly high adhesion to metals and/or metal oxides, so it can be used particularly well as a primer for metals.
• metals include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and composite materials of these metals
• metal oxides include single oxides and materials of these metals. /or composite oxides. In particular, it has excellent adhesive strength to iron, copper, and aluminum, so it can be used satisfactorily as an adhesive for iron, copper, and aluminum.
• the curable resin composition of the present invention can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and space industries. Even when the adhesive is used to bond different materials, such as between metal and non-metal, it can maintain high adhesion without being affected by changes in temperature environment, and is unlikely to peel off.
• the adhesive can also be used for general office use, medical use, carbon fiber, storage battery cells, modules, and cases, as well as adhesive for joining optical parts and bonding optical discs. adhesives for semiconductors such as adhesives for mounting printed wiring boards, die bonding adhesives, underfills, underfills for BGA reinforcement, anisotropic conductive films, anisotropic conductive pastes, etc. It can be used as an agent.
• the curable resin composition of the present invention has a fibrous matrix and the fibrous matrix is a reinforcing fiber
• the curable resin composition containing the fibrous matrix can be used as a fiber-reinforced resin.
• the method for incorporating the fibrous matrix into the composition is not particularly limited as long as it does not impair the effects of the present invention, and methods such as kneading, coating, impregnating, injecting, and pressing the fibrous matrix and the composition may be used. The method can be selected appropriately depending on the form of the fiber and the use of the fiber-reinforced resin.
• the method for molding the fiber reinforced resin is not particularly limited. If a plate-shaped product is to be manufactured, extrusion molding is generally used, but flat pressing is also possible. In addition, extrusion molding, blow molding, compression molding, vacuum molding, injection molding, and the like can be used. If a film-shaped product is to be manufactured, a solution casting method can be used in addition to the melt extrusion method, and when using the melt molding method, there are blown film molding, cast molding, extrusion lamination molding, calendar molding, and sheet molding. , fiber molding, blow molding, injection molding, rotational molding, coating molding, etc. Further, in the case of a resin that is cured by active energy rays, a cured product can be produced using various curing methods using active energy rays.
• thermosetting resin is the main component of the matrix resin
• thermosetting resin is the main component of the matrix resin
• thermosetting resin there is a molding method in which the molding material is made into prepreg and heated under pressure in a press or autoclave.
• RTM Resin Transfer Molding
• examples include VaRTM (Vacuum Assist Resin Transfer Molding) molding, lamination molding, hand lay-up molding, and the like.
• the curable resin composition of the present invention has repairability, remoldability, and easy disassembly properties, so it can be used in large cases, motor housings, casting materials inside cases, gears, and pulleys. It can be used for molding materials such as These may be cured products of resin alone or fiber-reinforced cured products such as glass chips.
• the fiber-reinforced resin can form an uncured or semi-cured prepreg. After distributing the product in the prepreg state, final curing may be performed to form a cured product. When forming a laminate, it is preferable to form a prepreg, laminate other layers, and then perform final curing, since it is possible to form a laminate in which each layer is in close contact with each other.
• the mass ratio of the composition and the fibrous substrate used at this time is not particularly limited, but it is usually preferable to prepare the prepreg so that the resin content is 20 to 60% by mass.
• the cured product of the present invention has repairability, easy disassembly, and remoldability, and can be used as a heat-resistant material and an electronic material, especially when a combination with a high dissociation temperature is used.
• it can be suitably used for semiconductor sealing materials, circuit boards, build-up films, build-up substrates, adhesives, and resist materials.
• It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a highly heat-resistant prepreg.
• the heat-resistant components and electronic components thus obtained can be suitably used for various purposes, such as industrial mechanical parts, general mechanical parts, automobile/railway/vehicle parts, space/aviation related parts, electronic/electrical parts, etc. Examples include, but are not limited to, building materials, containers/packaging members, household goods, sports/leisure goods, wind power generation casing members, etc.
• the adhesive of the present invention can maintain high adhesive properties even when used to bond different materials, such as between metal and non-metal.
• the adhesive of the present invention can also be used as an adhesive for general office, medical, carbon fiber, storage battery cells, modules, and cases, and as an adhesive for bonding optical parts and optical discs.
• Mounting adhesives for bonding adhesives for mounting, adhesives for mounting printed wiring boards, die bonding adhesives, semiconductor adhesives such as underfill, underfill for reinforcing BGA, anisotropic conductive films, anisotropic conductive pastes, etc. Examples include adhesives for
• the resin composition and compounding agents such as a curing accelerator and an inorganic filler are mixed in an extruder, a kneader, etc. as necessary. Examples include a method of sufficiently melting and mixing using a roller, roller, etc. until the mixture becomes uniform.
• fused silica is usually used as the inorganic filler, but when used as a highly thermally conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, nitride, etc., which have higher thermal conductivity than fused silica, It is preferable to use highly filled silicon or the like, or use fused silica, crystalline silica, alumina, silicon nitride, or the like.
• the filling rate is preferably 30 to 95% by mass of the inorganic filler per 100 parts by mass of the curable resin composition. In order to reduce the amount, the amount is more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.
• the semiconductor encapsulating material is molded using a casting, transfer molding machine, injection molding machine, etc., and then heated at 50 to 250°C. A method of heating for 2 to 10 hours is mentioned.
• Printed circuit board A method for obtaining a printed circuit board from the composition of the present invention is to laminate the prepregs described above by a conventional method, overlay copper foil as appropriate, and then under a pressure of 1 to 10 MPa at 170 to 300°C for 10 minutes to A method of heat-pressing for 3 hours may be mentioned.
• a method for manufacturing a flexible board from the crosslinkable resin composition of the present invention includes a method comprising the following three steps.
• the first step is a step of applying a crosslinkable resin composition containing a resin component, an organic solvent, etc. to an electrically insulating film using a coating machine such as a reverse roll coater or a comma coater.
• a coating machine such as a reverse roll coater or a comma coater.
• the electrically insulating film coated with the crosslinkable resin composition is heated at 60 to 170°C for 1 to 15 minutes using a heating machine, and the solvent is evaporated from the electrically insulating film.
• the third step is to B-stage the composition, and the third step is to heat the adhesive with metal foil using a heating roll or the like on the electrically insulating film in which the crosslinkable resin composition has been B-staged.
• This is a step of crimping (the crimping pressure is preferably 2 to 200 N/cm, and the crimping temperature is preferably 40 to 200°C). If sufficient adhesion performance is obtained by going through the above three steps, you can finish the process here, but if complete adhesion performance is required, an additional 1 to 24 hours at 100 to 200°C is required. It is preferable to post-cure with.
• the thickness of the resin composition layer after final curing is preferably in the range of 5 to 100 ⁇ m.
• a method for obtaining a buildup substrate from the composition of the present invention includes, for example, the following steps. First, the above-mentioned composition containing rubber, filler, etc. as appropriate is applied to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured (step 1). After that, after drilling a predetermined through-hole section as necessary, the surface is treated with a roughening agent, and the surface is washed with hot water to form unevenness, and the process of plating metal such as copper (process 2). A step (step 3) of repeatedly repeating such operations as desired to alternately build up and form a resin insulating layer and a conductor layer of a predetermined circuit pattern.
• the through-hole portions are formed after the outermost resin insulating layer is formed.
• the build-up board of the present invention is produced by heat-pressing a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil at 170 to 300°C onto a wiring board on which a circuit is formed. It is also possible to fabricate a build-up board by omitting the steps of forming a chemical surface and plating.
• a method for obtaining a build-up film from the composition of the present invention is to apply the above-mentioned composition onto the surface of the support film (Y) as a base material, and then apply an organic solvent by heating or blowing hot air. It can be manufactured by drying to form the layer (X) of the composition.
• organic solvent used here examples include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. It is preferable to use carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use them in a proportion such that the nonvolatile content is 30 to 60% by mass. preferable.
• ketones such as acetone, methyl ethyl ketone, and cyclohexanone
• acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glyco
• the thickness of the layer (X) to be formed is usually greater than or equal to the thickness of the conductor layer. Since the thickness of a conductor layer included in a circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer is preferably in the range of 10 to 100 ⁇ m.
• the layer (X) of the said composition in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and from scratching it.
• the supporting film and protective film described above are made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and even release materials. Examples include paper patterns and metal foils such as copper foil and aluminum foil.
• PET polyethylene terephthalate
• the support film and the protective film may be subjected to a release treatment in addition to a matte treatment and a corona treatment.
• the thickness of the support film is not particularly limited, but is usually 10 to 150 ⁇ m, preferably 25 to 50 ⁇ m. Further, the thickness of the protective film is preferably 1 to 40 ⁇ m.
• the support film (Y) described above is peeled off after being laminated onto the circuit board or after forming an insulating layer by heating and curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film is cured by heating, it is possible to prevent dust and the like from adhering during the curing process. When peeling is performed after curing, the support film is usually subjected to a mold release treatment in advance.
• a multilayer printed circuit board can be manufactured using the build-up film obtained as described above.
• the layer (X) is protected by a protective film, after peeling off these layers, the layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method.
• the lamination method may be a batch method or a continuous method using rolls.
• the build-up film and the circuit board may be heated (preheated) before lamination.
• the pressure bonding temperature (laminate temperature) is 70 to 140°C, and the pressure bonding pressure is 1 to 11 kgf/cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N/m 2 ). It is preferable that the lamination is carried out under a reduced air pressure of 20 mmHg (26.7 hPa) or less.
• Conductive Paste A method for obtaining a conductive paste from the composition of the present invention includes, for example, a method of dispersing conductive particles in the composition.
• the above-mentioned conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used.
• GPC “HLC-8320GPC” manufactured by Tosoh Corporation Column: Tosoh Corporation "TSK-GEL G2000HXL” + “TSK-GEL G3000HXL” + “TSK-GEL G4000HXL” Detector: RI (differential refractometer) Measurement conditions: 40°C Mobile phase: Tetrahydrofuran Flow rate: 1ml/min Standard: "PStQuick A", "PStQuick B", “PStQuick E”, "PStQuick F” manufactured by Tosoh Corporation
• the epoxy equivalent of the synthesized epoxy resin was measured in accordance with JIS K7236, and the epoxy equivalent (g/eq) was calculated.
• Examples of methods for calculating the number of repeating units include GPC molecular weight measurement and calculation from the results of various appropriate instrumental analyzes such as FD-MS and NMR.
• Synthesis example 1 A flask equipped with a thermometer and a stirrer was charged with 151 g (1.0 mol) of 4-hydroxyacetanilide, 300 g of acetone, and 166 g (1.2 mol) of potassium carbonate, and the temperature was raised to the reflux temperature. Thereafter, 144 g (1.2 mol) of allyl bromide was added dropwise, and the reaction was further continued for 7 hours. After cooling to room temperature, potassium carbonate was removed by filtration, and acetone and excess allyl bromide in the filtrate were distilled off under reduced pressure using an evaporator.
• the obtained solid was dissolved in 222 g of ethanol, 417 g (4.0 mol) of a 35% aqueous hydrochloric acid solution was added dropwise, and the mixture was reacted at 60 to 65° C. for 12 hours. After cooling to room temperature, the mixture was neutralized with 880 g (4.4 mol) of 20% aqueous sodium hydroxide solution, and liquid separation was performed three times with 373 g of ethyl acetate. After dehydrating the organic layer over sodium sulfate, ethyl acetate was distilled off under reduced pressure using an evaporator to obtain 113 g (0.76 mol, yield 76%) of 4-allyloxyaniline.
• Synthesis example 2 In a flask equipped with a thermometer, dropping funnel, cooling tube, and stirrer, 38.8 g (0.20 mol) of 9-anthrone was added to 180 ml of dimethylacetamide while immersed in an ice water bath under a nitrogen atmosphere to form a slurry. 110 g (0.22 mol) of 8.09% aqueous sodium hydroxide solution was added. Then, 27.7 g (0.20 mol) of epibromohydrin dissolved in 40 ml of dimethylacetamide was added dropwise.
• Synthesis example 3 9-(4-Hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (manufactured by Asahi Yokuzai Co., Ltd.) was added to a flask equipped with a thermometer, dropping funnel, cooling tube, and stirrer while purging with nitrogen gas.
• BIP-ANT 18.8 g (hydroxyl equivalent: 188 g/eq), 92.5 g (1.0 mol) of epichlorohydrin, and 23 g of n-butanol were charged and dissolved.
• Synthesis example 4 18.8 g of 9-(4-hydroxybenzyl)-10-(4-hydroxyphenyl)anthracene (manufactured by Asahi Yokuzai Co., Ltd.: product name BIP-ANT: hydroxyl equivalent: 188 g/eq) of Synthesis Example 3 was converted into 2-aminoanthracene. The same operation as in Synthesis Example 3 was performed except that the amount was changed to 9.65 g, and 12.2 g of a glycidyl group-containing anthracene compound (A-3) was obtained. The epoxy equivalent was 183 g/eq.
• A-3) was confirmed to contain the following structural formula.
• Example 1 In a flask equipped with a thermometer, a stirrer, and a cooling tube, 30.4 g (0.12 mol) of (M-1) obtained in Synthesis Example 1 and (A-1) obtained in Synthesis Example 2 were added. 26.5 g (0.1 mol) of 180 g of toluene and 180 g of methyl isobutyl ketone were charged, and the mixture was reacted at 80° C. for 12 hours. Thereafter, the mixture was cooled to room temperature, and the precipitate was collected by suction filtration and dried under reduced pressure to obtain a glycidyl group-containing compound (D-1) which is a Diels-Alder reaction adduct. The epoxy equivalent was 337 g/eq, the yield was 38.9 g, and the yield was 75%.
• Example 2 In a flask equipped with a thermometer, a stirrer, and a cooling tube, 30.4 g (0.12 mol) of (M-1) obtained in Synthesis Example 1 and (A-2) obtained in Synthesis Example 3 were added. 51.4 g (0.1 mol) of 200 g (0.1 mole), 200 g of toluene, and 200 g of methyl isobutyl ketone were charged, and the mixture was reacted at 80° C. for 12 hours. Thereafter, the mixture was cooled to room temperature, and the precipitate was collected by suction filtration and dried under reduced pressure to obtain a glycidyl group-containing compound (D-2) which is a Diels-Alder reaction adduct. The epoxy equivalent was 307 g/eq, the yield was 61.4 g, and the yield was 80%.
• Example 3 In a flask equipped with a thermometer, a stirrer, and a cooling tube, 30.4 g (0.12 mol) of (M-1) obtained in Synthesis Example 1 and 15.0 g (0.12 mol) of furfuryl glycidyl ether (Merck reagent) were added. 4 g (0.1 mol), 180 g of toluene, and 180 g of methyl isobutyl ketone were charged, and reacted at 80° C. for 12 hours.
• Example 4 In a flask equipped with a thermometer, a stirrer, and a cooling tube, 30.4 g (0.12 mol) of (M-1) obtained in Synthesis Example 1 and (A-4) obtained in Synthesis Example 4 were added. 36.6 g (0.1 mole), 200 g of toluene, and 200 g of methyl isobutyl ketone were charged, and the mixture was reacted at 80° C. for 12 hours. Thereafter, the precipitate was cooled to room temperature, collected by suction filtration, and dried under reduced pressure to obtain a mixture of glycidyl group-containing compounds (D-4) and (D'-4), which are Diels-Alder reaction adducts. Ta. The epoxy equivalent was 210 g/eq, the yield was 57.0 g, and the yield was 85%.
• Comparative example 1 In a flask equipped with a thermometer, a stirrer, and a cooling tube, add 43.0 g (0.12 mol) of BMI-1000 (4,4'-diphenylmethane bismaleimide manufactured by Daiwa Kasei Kogyo) and furfuryl glycidyl ether (manufactured by Merck). 30.8 g (0.2 mol) of reagent), 200 g of toluene, and 200 g of methyl isobutyl ketone were charged, and the mixture was reacted at 80° C. for 12 hours.
• BMI-1000 4,4'-diphenylmethane bismaleimide manufactured by Daiwa Kasei Kogyo
• furfuryl glycidyl ether manufactured by Merck
• Synthesis example 5 In a flask equipped with a thermometer and a stirrer, 445 g (0.5 mol) of diglycidyl ether of polytetramethylene glycol ("Denacol EX-991L" manufactured by Nagase ChemteX: epoxy equivalent 445 g/eq) and bisphenol A (hydroxyl equivalent After adding 171 g (0.75 mol) of 114 g/eq) and raising the temperature to 140° C. over 30 minutes, 3.1 g of 4% aqueous sodium hydroxide solution was added. Thereafter, the temperature was raised to 150°C over 30 minutes, and the reaction was further carried out at 150°C for 16 hours.
• a neutralizing amount of sodium phosphate was added to obtain 616 g of a hydroxy compound represented by the following formula (Ph-1).
• the hydroxy compound was of the PTMG ( polytetramethylene ether glycol ) type (BPA : It was confirmed that it contained a hydroxy compound of bisphenol A).
• the hydroxyl equivalent of this hydroxy compound (Ph-1) calculated by GPC was 1080 g/eq, the average value of n 1 was 10.6, and the average value of m 1 was 0.76.
• Synthesis example 6 In a flask equipped with a thermometer, dropping funnel, cooling tube, and stirrer, while purging with nitrogen gas, 200 g of the hydroxy compound (Ph-1) obtained in Synthesis Example 5, 437 g (4.72 mol) of epichlorohydrin, n -118 g of butanol was added and dissolved. After raising the temperature to 65° C., the pressure was reduced to an azeotropic pressure, and 6.66 g (0.08 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Next, stirring was continued for 0.5 hour under the same conditions.
• Ep-1 epoxy resin (Ep-1)
• the epoxy equivalent of the obtained epoxy resin (Ep-1) was 1192 g/eq.
• composition and cured product 1 Each compound was blended according to the table (numbers in the table are based on mass) and melt-kneaded using two rolls at a temperature of 100° C. for 10 minutes to obtain a curable resin composition.
• This curable resin composition was press-molded at 180°C for 60 minutes, and then further cured at 180°C for 5 hours to obtain a cured product with a thickness of 0.7 mm.
• ⁇ Remolding test-1> The produced cured product was freeze-pulverized. 0.07 g of the pulverized cured product was placed in a mold of 10 mm square and 0.5 mm thick and vacuum pressed at 150° C. for 3 hours. The appearance of the obtained cured product and the contamination status of the press mirror surface were visually observed. The judgment criteria are as follows.
• Contamination status of the press mirror surface A No contamination B: There is a slight amount of contamination that can be removed C: There is contamination that cannot be removed without using a solvent
• ⁇ Repair test> The produced cured product was cut with a razor, the resulting fractured surfaces were brought into contact, and then aged at 150° C. for 24 hours in a dryer. After taking it out from the dryer, the presence or absence of bonding between the cross sections of the cured product was visually confirmed. The judgment criteria are as follows. A: Even after joining and bending the cured product by 90 degrees, the joint does not separate. B: When the cured product is joined and bent, the joint does not separate. C: Not bonded.
• test piece was suspended in a dryer at 120° C., and a load of 500 g was applied to one side of the base material. This state was allowed to stand for 30 minutes, and the adhesion state of the base material was evaluated.
• the judgment criteria are as follows. A: The adhesive portion shifted, and the adhesive base material on the side to which the load was applied fell. B: Misalignment of the bonded portion occurred. C: No change occurred in the base material.
• composition and cured product 2 Blend each compound according to the formulation according to the table (numbers in the table are based on mass), add 0.5% by mass of 2-ethyl-4methyl-imidazole based on the total mass of the epoxy resin and curing agent, and add methyl ethyl ketone. The nonvolatile content was adjusted to 58% by mass to obtain a curable resin composition.
• a glass cloth manufactured by Nitto Boseki Co., Ltd., type 2116, width 210 mm x length 280 mm x thickness 100 ⁇ m
• was impregnated with it was impregnated with it, and then dried at 160° C. for 2 minutes to volatilize the solvent to obtain a prepreg.
• Six sheets of this prepreg were laminated and press-molded at 200° C. for 90 minutes to obtain a laminated cured product.
• Appearance of cured product A A cured product was obtained that was molded according to the mold without any cracks. B: Although cracks were partially visible, a cured product was obtained that was molded according to the mold. C: Cracks occurred due to failure to follow deformation.
• EPICLON850-S BPA type liquid epoxy resin, epoxy equivalent 188g/eq
• DICY dicyandiamide
• DCMU 3-(3,4-dichlorophenyl)-1,1-dimethylurea
• TD2131 Phenol novolac resin, hydroxyl equivalent weight 104g/eq 2E4MZ: 2-ethyl-4-methyl-imidazole

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• 2023
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