WO2018193983A1 - Imide oligomer, curing agent, adhesive and method for producing imide oligomer - Google Patents

Imide oligomer, curing agent, adhesive and method for producing imide oligomer Download PDF

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Publication number
WO2018193983A1
WO2018193983A1 PCT/JP2018/015524 JP2018015524W WO2018193983A1 WO 2018193983 A1 WO2018193983 A1 WO 2018193983A1 JP 2018015524 W JP2018015524 W JP 2018015524W WO 2018193983 A1 WO2018193983 A1 WO 2018193983A1
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Prior art keywords
imide oligomer
oligomer
adhesive
imide
curing agent
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PCT/JP2018/015524
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French (fr)
Japanese (ja)
Inventor
幸平 竹田
さやか 脇岡
努 安藤
誠実 新土
悠太 大當
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201880019956.2A priority Critical patent/CN110461818B/en
Priority to KR1020197009277A priority patent/KR102556129B1/en
Priority to JP2018522818A priority patent/JP7103940B2/en
Publication of WO2018193983A1 publication Critical patent/WO2018193983A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds

Definitions

  • the present invention relates to an imide oligomer that can be used for a cured product having excellent long-term heat resistance.
  • the present invention also relates to a curing agent comprising the imide oligomer, and an adhesive using the curing agent. Furthermore, this invention relates to the manufacturing method of this imide oligomer.
  • Curable resins such as epoxy resins that have low shrinkage and are excellent in adhesion, insulation, and chemical resistance are used in many industrial products.
  • curable resin compositions are used that can give good results in a solder reflow test for short-term heat resistance and a thermal cycle test for repeated heat resistance.
  • Patent Document 1 discloses an imide oligomer curing agent having an acid anhydride structure at both ends, but has compatibility with a curable resin such as an epoxy resin. Since it was insufficient, there was a problem that the obtained curable resin composition had poor long-term heat resistance.
  • Patent Documents 2 and 3 disclose a curable resin composition using a polyimide having a flexible silicone skeleton or an alicyclic skeleton introduced as a curing agent in order to improve compatibility with the curable resin. Yes. However, when a silicone skeleton or an alicyclic skeleton is introduced, the glass transition temperature of the resulting cured product is likely to decrease, resulting in inferior mechanical strength and long-term heat resistance at the operating temperature of ECUs, power devices, etc. was there. Patent Document 4 discloses that the adhesiveness and heat resistance of the thermosetting resin composition are improved by using a specific imide oligomer having a phenolic hydroxyl group at both ends as a curing agent. However, even when such an imide oligomer is used, the long-term heat resistance may decrease.
  • An object of this invention is to provide the imide oligomer which can be used for the hardened
  • Another object of the present invention is to provide a curing agent comprising the imide oligomer, and an adhesive using the curing agent. Furthermore, this invention aims at providing the manufacturing method of this imide oligomer.
  • the present invention is an imide oligomer having a phenolic hydroxyl group, and the content ratio of the imide oligomer having an ester bond is 7% or less.
  • the present invention is described in detail below.
  • an imide oligomer having a phenolic hydroxyl group having an ester bond has a poor effect of improving the long-term heat resistance of the cured product when used as a curing agent, and has a phenolic hydroxyl group. Then, the use of an imide oligomer having no ester bond was studied. However, even when an imide oligomer having a phenolic hydroxyl group and having no ester bond is used, the long-term heat resistance of the cured product cannot be sufficiently improved.
  • the inventors of the present invention were unable to sufficiently improve the long-term heat resistance of the cured product because the ester bond as an impurity was incorporated into the imide oligomer having a phenolic hydroxyl group used as having no ester bond. It was thought that this was because a slight amount of imide oligomer was present.
  • the present inventors obtained a cured product having excellent long-term heat resistance by using an imide oligomer having a phenolic hydroxyl group in which the content ratio of an imide oligomer having an ester bond as an impurity is 7% or less. As a result, the present invention has been completed.
  • the imide oligomer of the present invention has a phenolic hydroxyl group.
  • the content ratio of the imide oligomer having an ester bond is 7% or less.
  • the imide oligomer of the present invention is excellent in the effect of improving the long-term heat resistance of a cured product obtained when used as a curing agent.
  • the content ratio of the imide oligomer having an ester bond is preferably 5% or less, and most preferably 0%, that is, not containing the imide oligomer having an ester bond.
  • the content ratio of the imide oligomer having an ester bond is derived from the ester bond by Fourier transform infrared spectroscopy (FT-IR) after fractionating each peak using gel permeation chromatography (GPC). It can be determined from the weight ratio of the compound having absorption. Specifically, first, tetrahydrofuran (THF) was used as a free liquid, and a recycle preparative HPLC (manufactured by Nippon Analytical Industrial Co., Ltd.) equipped with a GPC column (for example, “JAIGEL-2H” manufactured by Nippon Analytical Industrial Co., Ltd.) Use to separate each peak.
  • FT-IR Fourier transform infrared spectroscopy
  • GPC gel permeation chromatography
  • the compound obtained by removing the free liquid by heating or the like is measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (for example, “UMA600” manufactured by Agilent Technologies). I do. From the obtained measurement results, it can be derived by determining the weight ratio of the compound having a peak (1159 cm ⁇ 1 ) derived from an ester bond to the total peak compound.
  • ATR method total reflection measurement method
  • UMA600 Fourier transform infrared spectrophotometer
  • the imide oligomer of the present invention preferably has a phenolic hydroxyl group at the ends of the main chain, and more preferably at both ends.
  • the minimum with a preferable number average molecular weight of the imide oligomer of this invention is 400, and a preferable upper limit is 4200.
  • a cured product obtained when the imide oligomer of the present invention is used as a curing agent has excellent long-term heat resistance.
  • the more preferable lower limit of the number average molecular weight of the imide oligomer of the present invention is 420, and the more preferable upper limit is 4000.
  • the “number average molecular weight” is a value determined by gel conversion chromatography (GPC) using tetrahydrofuran as a solvent and converted to polystyrene. Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Nippon Analytical Industrial Co., Ltd.).
  • the imide oligomer of the present invention preferably contains as a main component an imide oligomer represented by the following formula (1-1) and / or an imide oligomer represented by the following formula (1-2).
  • the “main component” means that the content ratio is 60 mol% or more.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group, Is a bond, an oxygen atom, or a divalent hydrocarbon group that may be substituted.
  • Y is a bond, an oxygen atom, or may be substituted. It is a divalent hydrocarbon group.
  • a method for producing the imide oligomer of the present invention a method in which the amount of monoamine having a phenolic hydroxyl group used as a raw material is excessive is preferably used.
  • a step of reacting a compound having an acid anhydride group with a monoamine having a phenolic hydroxyl group, wherein the amount of the monoamine having a phenolic hydroxyl group is used relative to the acid anhydride group of the compound having the acid anhydride group A method for producing an imide oligomer having 1.5 equivalents or more is also one aspect of the present invention.
  • the imide oligomer of the present invention in which the content ratio of the imide oligomer having an ester bond generated as a by-product is 7% or less can be easily produced.
  • a monoamine having a phenolic hydroxyl group is dissolved in advance in a solvent in which an amic acid oligomer obtained by the reaction is soluble (for example, N, N-dimethylformamide, etc.), and acid dianhydride is added to the resulting solution.
  • an amic acid oligomer solution is obtained.
  • the obtained amic acid oligomer solution is added to hydrochloric acid or the like, and the operation of collecting the precipitate is performed several times.
  • An imide oligomer having a phenolic hydroxyl group can be obtained by heating the obtained precipitate to advance an imidization reaction.
  • the content of the imide oligomer having an ester bond is determined by setting the amount of the monoamine having a phenolic hydroxyl group to 1.5 equivalents or more based on the acid anhydride group of the acid dianhydride. Can be made 7% or less.
  • diamine is dissolved in advance in a solvent in which the amic acid oligomer obtained by the reaction is soluble (for example, N, N-dimethylformamide and the like), and acid dianhydride is added to the resulting solution to cause reaction.
  • a solution of the amic acid oligomer (A) having acid anhydride groups at both ends is obtained.
  • a monoamine having a phenolic hydroxyl group is added to the obtained solution of the amic acid oligomer (A) and reacted to obtain a solution of the amic acid oligomer (B).
  • the solution of the obtained amic acid oligomer (B) is added to hydrochloric acid or the like, and the operation of collecting the precipitate is performed several times.
  • An imide oligomer having a phenolic hydroxyl group can be obtained by heating the obtained precipitate to advance an imidization reaction.
  • the amount of the monoamine having a phenolic hydroxyl group is 1.5 equivalents or more with respect to the acid anhydride group of the amic acid oligomer (A), whereby the imide oligomer having an ester bond is used.
  • the content ratio can be 7% or less.
  • the monoamine having a phenolic hydroxyl group a compound represented by the following formula (2) is preferably used.
  • Specific examples of the monoamine having a phenolic hydroxyl group include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2,3- Xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4-amino- Examples include 2,6-diphenylphenol. Among them, a cured product having excellent availability and storage stability and a high glass transition temperature can be obtained, so that 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o- Cresol is preferred.
  • Ar is a divalent aromatic group which may be substituted
  • R 3 and R 4 are each independently a hydrogen atom or a monovalent hydrocarbon group which may be substituted. It is.
  • the compound represented by following formula (3) is used suitably.
  • Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, and 4,4′-oxydiphthalic acid.
  • Dianhydrides 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 4,4'-bis (3,4-dicarboxylphenoxy) diphenyl ether, p-phenylenebis (trimellitate anhydride) ), 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-carbonyldiphthalic dianhydride Etc.
  • A is a tetravalent group represented by the following formula (4-1) or the following formula (4-2).
  • * represents a bonding position
  • Z represents a bond, an oxygen atom, a carbonyl group, or may be substituted. It is a divalent hydrocarbon group that may have an oxygen atom at the bonding position.
  • the hydrogen atom of the aromatic ring in formula (4-1) and formula (4-2) may be substituted.
  • the compound represented by following formula (5) is used suitably.
  • the diamine include, for example, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenyl ether, 3,4′- Diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, Bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 1,3-bis (3-aminophenoxy) benzene, 1,3-
  • B is a divalent group represented by the following formula (6-1) or the following formula (6-2), and R 5 to R 8 are each independently a hydrogen atom or 1 Valent hydrocarbon group.
  • a preferable lower limit of the imidization ratio of the imide oligomer of the present invention is 70%.
  • the imidation ratio is 70% or more, a cured product excellent in mechanical strength at high temperature and long-term heat resistance can be obtained when used as a curing agent.
  • a more preferable lower limit of the imidization ratio is 75%, and a more preferable lower limit is 80%.
  • the “imidation ratio” can be determined by Fourier transform infrared spectroscopy (FT-IR).
  • measurement is performed by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (for example, “UMA600” manufactured by Agilent Technologies), and is derived from a carbonyl group of an amic acid. It can be derived from the peak absorbance area around 1660 cm ⁇ 1 by the following equation.
  • the imide oligomer of the present invention can provide a cured product having excellent long-term heat resistance when used as a curing agent.
  • the curing agent comprising the imide oligomer of the present invention is also one aspect of the present invention.
  • curing agent of this invention is also one of this invention.
  • the content of the curing agent of the present invention in the adhesive of the present invention is preferably 50 parts by weight with a preferred lower limit and 500 parts by weight with respect to 100 parts by weight of the curable resin.
  • a cured product of the obtained adhesive is superior in long-term heat resistance.
  • curing agent of this invention is 70 weight part, and a more preferable upper limit is 400 weight part.
  • the adhesive of the present invention may contain other curing agents in addition to the curing agent of the present invention as long as the object of the present invention is not impaired, for example, in order to improve processability in an uncured state.
  • the other curing agents include phenolic curing agents, thiol curing agents, amine curing agents, acid anhydride curing agents, cyanate curing agents, and active ester curing agents. Of these, phenolic curing agents, acid anhydride curing agents, cyanate curing agents, and active ester curing agents are preferred.
  • the preferable upper limit of the content of the other curing agent in the entire curing agent is 70% by weight, the more preferable upper limit is 50% by weight, and the more preferable upper limit is 30. % By weight.
  • the adhesive of the present invention contains a curable resin.
  • the curable resin is preferably liquid at 25 ° C. from the viewpoint of fluidity and workability of the resulting adhesive.
  • An epoxy resin is preferably used as the curable resin.
  • the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, and hydrogenated bisphenol type epoxy resin.
  • the adhesive of the present invention may contain a curing accelerator.
  • a curing accelerator By containing the said hardening accelerator, hardening time can be shortened and productivity can be improved.
  • curing accelerator examples include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, photobase generators, sulfonium salt-based curing accelerators, and the like. Of these, imidazole curing accelerators are preferable.
  • the content of the curing accelerator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the curing accelerator is within this range, the effect of shortening the curing time is maintained while maintaining excellent adhesiveness and the like.
  • the minimum with more preferable content of the said hardening accelerator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
  • the adhesive of the present invention may contain an organic filler for the purpose of stress relaxation, toughness imparting, flame retardancy imparting and the like.
  • organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof. Of these, polyamide particles, polyamideimide particles, and polyimide particles are preferable.
  • the content of the organic filler is preferably 10 parts by weight and preferably 500 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the organic filler is within this range, the obtained cured product is excellent in toughness and the like while maintaining excellent adhesiveness and the like.
  • the minimum with more preferable content of the said organic filler is 30 weight part, and a more preferable upper limit is 400 weight part.
  • the adhesive of the present invention contains an inorganic filler for the purpose of reducing warpage by reducing the linear expansion coefficient after curing, imparting flame retardancy, improving adhesion reliability, and the like. Also good.
  • examples of the inorganic filler include silica such as colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, aluminum hydroxide, magnesium hydroxide, glass powder, glass frit, glass fiber, carbon fiber, and inorganic ion exchange. Examples include the body.
  • the content of the inorganic filler is such that the preferred lower limit is 10 parts by weight and the preferred upper limit is 1000 parts by weight with respect to 100 parts by weight of the curable resin.
  • the adhesive reliability is improved while maintaining excellent processability and the like.
  • the minimum with more preferable content of the said inorganic filler is 20 weight part, and a more preferable upper limit is 900 weight part.
  • the inorganic filler can also be used as a flow regulator for the purpose of improving the paintability and shape retention in a short time on the adherend.
  • inorganic filler used as the flow regulator examples include fumed silica and layered silicate.
  • the content of the inorganic filler used as the flow regulator is preferably 0.1 parts by weight and preferably 50 parts by weight with respect to 100 parts by weight of the curable resin.
  • the minimum with more preferable content of the inorganic filler used as the said flow regulator is 0.5 weight part, and a more preferable upper limit is 30 weight part.
  • the adhesive of the present invention may contain a polymer compound as long as the object of the present invention is not impaired.
  • the polymer compound serves as a film forming component.
  • the polymer compound may have a reactive functional group.
  • the reactive functional group include an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, and an epoxy group.
  • the polymer compound may form a phase separation structure in the cured product or may not form a phase separation structure.
  • the polymer compound is superior in mechanical strength at high temperatures, long-term heat resistance, and moisture resistance.
  • a polymer compound having an epoxy group is preferred.
  • the adhesive of the present invention may contain a reactive diluent as long as the object of the present invention is not impaired.
  • a reactive diluent a reactive diluent having two or more reactive functional groups in one molecule is preferable from the viewpoint of adhesion reliability.
  • a reactive functional group which the said reactive diluent has the thing similar to the reactive functional group which the high molecular compound mentioned above has is mentioned.
  • the adhesive of the present invention may further contain additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, a bleed inhibitor, a flux agent, and a liquid flame retardant.
  • additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, a bleed inhibitor, a flux agent, and a liquid flame retardant.
  • the adhesive of the present invention for example, using a mixer such as a homodisper, a universal mixer, a Banbury mixer, a kneader, etc., a curable resin, the curing agent of the present invention and, if necessary, are added. Examples thereof include a method of mixing with other curing agents and curing accelerators.
  • the adhesive film which consists of an adhesive agent of this invention can be obtained by apply
  • the adhesive of the present invention can be used for a wide range of applications, but can be suitably used for electronic materials that require particularly high heat resistance.
  • it can be used for die attach agents in aviation, in-vehicle electric control unit (ECU) applications, power device applications using SiC, and GaN.
  • ECU electric control unit
  • it can be used as an adhesive for power overlay packages, an adhesive for printed wiring boards, an adhesive for coverlays of flexible printed circuit boards, an adhesive for semiconductor bonding, an adhesive for structural materials, and the like.
  • the curable composition can be used, for example, as a sealant, a copper clad laminate, a semiconductor bonding adhesive, an interlayer insulating film, a prepreg, and the like.
  • the imide oligomer which can be used for the hardened
  • the obtained amic acid oligomer solution was added to 2 L of 1 mol / L hydrochloric acid to collect precipitates.
  • the obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid to collect the precipitate.
  • the obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid to collect the precipitate.
  • the obtained precipitate was heated at 180 ° C. for 2 hours and then reacted under imidization conditions of heating at 300 ° C.
  • the imide oligomer A was confirmed to contain the imide oligomer represented by the above formula (1-1) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer having an ester bond in the imide oligomer A was 5.5%. Furthermore, the number average molecular weight of the imide oligomer A was 506.
  • the content ratio of the imide oligomer C having an ester bond in the imide oligomer C was 4.7%. Furthermore, the number average molecular weight of the imide oligomer C was 506.
  • the content ratio of the imide oligomer D having an ester bond in the imide oligomer D was 5.3%. Furthermore, the number average molecular weight of the imide oligomer D was 531.
  • the imide oligomer E was confirmed to contain the imide oligomer represented by the above formula (1-1) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer E having an ester bond was 5.4%. Furthermore, the number average molecular weight of the imide oligomer E was 712.
  • the obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid to collect the precipitate.
  • the obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid to collect the precipitate.
  • About the obtained deposit after heating at 180 degreeC for 2 hours, it was made to react on the imidation conditions heated at 300 degreeC for 2 hours, and the imide oligomer F (imidation rate 92%) which has a phenolic hydroxyl group was obtained. .
  • the imide oligomer F was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer F having an ester bond in the imide oligomer F was 5.5%. Furthermore, the number average molecular weight of the imide oligomer F was 1548.
  • the imide oligomer G was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC fractionation and FT-IR analysis that the imide oligomer G had a content of imide oligomer having an ester bond of 5.4%. Furthermore, the number average molecular weight of the imide oligomer G was 1126.
  • amic acid oligomer solution (A) 32.74 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.5% with respect to the acid anhydride group of the amic acid oligomer (A) to be reacted) Equivalent) was added and stirred at 25 ° C. for 2 hours for reaction to obtain an amic acid oligomer solution (B).
  • the solution of the obtained amic acid oligomer (B) was added to 2 L of 1 mol / L hydrochloric acid to collect the precipitate.
  • the obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid to collect the precipitate.
  • the obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid to collect the precipitate.
  • About the obtained deposit after heating at 180 degreeC for 2 hours, it was made to react on the imidation conditions heated at 300 degreeC for 2 hours, and the imide oligomer H (imidation rate 92%) which has a phenolic hydroxyl group was obtained. .
  • the imide oligomer H was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content of the imide oligomer having an ester bond in the imide oligomer H was 5.5%. Furthermore, the number average molecular weight of the imide oligomer H was 2720.
  • the content ratio of the imide oligomer I having an ester bond in the imide oligomer I was 5.4%. Furthermore, the number average molecular weight of the imide oligomer I was 1490.
  • the content ratio of the imide oligomer having an ester bond in the imide oligomer J was 8.2%. Furthermore, the number average molecular weight of the imide oligomer J was 543.
  • Imide oligomer K (imidation ratio: 44%) was obtained in the same manner as in Synthesis Example 10 except that the imidization conditions of the precipitate were changed to heating at 200 ° C. and 5 mmHg for 3 hours using a vacuum drying oven. Obtained.
  • the imide oligomer K was confirmed to contain the imide oligomer represented by the above formula (1-1) by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC fractionation and FT-IR analysis that the content ratio of the imide oligomer having an ester bond in the imide oligomer K was 8.2%. Furthermore, the number average molecular weight of the imide oligomer K was 556.
  • the content ratio of the imide oligomer L having an ester bond in the imide oligomer L was 8.0%. Furthermore, the number average molecular weight of the imide oligomer L was 1710.
  • the content ratio of the imide oligomer M having an ester bond in the imide oligomer M was 8.1%. Furthermore, the number average molecular weight of the imide oligomer M was 1241.
  • the content ratio of the imide oligomer N having an ester bond in the imide oligomer N was 8.4%. Furthermore, the number average molecular weight of the imide oligomer N was 1571.
  • Examples 1 to 9, Comparative Examples 1 to 5 According to the blending ratios described in Tables 1 and 2, the materials were stirred and mixed to prepare adhesives of Examples 1 to 9 and Comparative Examples 1 to 5.
  • Kapton Long-term heat resistance (adhesive strength) 50 ⁇ m thick Kapton (registered trademark) was laminated on both sides of each adhesive obtained in the examples and comparative examples, and cured and adhered by heating at 190 ° C. for 1 hour, and then cut into 1 cm wide strips. A test piece was obtained. The obtained test piece was heat-treated at 175 ° C. for 1000 hours. About the test piece after heat processing, the adhesive force was measured on conditions with a peeling speed of 20 mm / min using the tensile tester (the product made by ORIENTEC, "UCT-500").
  • the imide oligomer which can be used for the hardened

Abstract

A purpose of the present invention is to provide an imide oligomer which is able to be used for a cured product that has excellent long-term heat resistance. Another purpose of the present invention is to provide: a curing agent which is composed of the imide oligomer; and an adhesive which is obtained using the curing agent. Another purpose of the present invention is to provide a method for producing the imide oligomer. The present invention is an imide oligomer which has a phenolic hydroxyl group, and wherein the content ratio of an imide oligomer having an ester bond is 7% or less.

Description

イミドオリゴマー、硬化剤、接着剤、及び、イミドオリゴマーの製造方法Imide oligomer, curing agent, adhesive, and method for producing imide oligomer
本発明は、長期耐熱性に優れる硬化物に用いることができるイミドオリゴマーに関する。また、本発明は、該イミドオリゴマーからなる硬化剤、及び、該硬化剤を用いてなる接着剤に関する。更に、本発明は、該イミドオリゴマーの製造方法に関する。 The present invention relates to an imide oligomer that can be used for a cured product having excellent long-term heat resistance. The present invention also relates to a curing agent comprising the imide oligomer, and an adhesive using the curing agent. Furthermore, this invention relates to the manufacturing method of this imide oligomer.
低収縮であり、接着性、絶縁性、及び、耐薬品性に優れるエポキシ樹脂等の硬化性樹脂は、多くの工業製品に使用されている。特に電子機器用途では、短時間の耐熱性に関するはんだリフロー試験や繰り返しの耐熱性に関する冷熱サイクル試験において良好な結果が得られる硬化性樹脂組成物が多く用いられている。 Curable resins such as epoxy resins that have low shrinkage and are excellent in adhesion, insulation, and chemical resistance are used in many industrial products. In particular, in electronic equipment applications, many curable resin compositions are used that can give good results in a solder reflow test for short-term heat resistance and a thermal cycle test for repeated heat resistance.
近年、車載用電気制御ユニット（ＥＣＵ）や、ＳｉＣ、ＧａＮを用いたパワーデバイス等が注目されているが、これらの用途において用いられる硬化性樹脂組成物には、短時間や繰り返しの耐熱性ではなく、連続して長期間高温に曝された際の耐熱性（長期耐熱性）が求められる。 Recently, in-vehicle electric control units (ECUs), power devices using SiC, GaN, and the like have attracted attention. However, curable resin compositions used in these applications have a short time or repeated heat resistance. However, heat resistance (long-term heat resistance) when continuously exposed to a high temperature for a long time is required.
硬化性樹脂組成物に用いられる硬化剤として、特許文献１には、両末端に酸無水物構造を有するイミドオリゴマー硬化剤が開示されているが、エポキシ樹脂等の硬化性樹脂との相溶性が不充分であるため、得られる硬化性樹脂組成物が長期耐熱性に劣るものとなるという問題があった。 As a curing agent used in the curable resin composition, Patent Document 1 discloses an imide oligomer curing agent having an acid anhydride structure at both ends, but has compatibility with a curable resin such as an epoxy resin. Since it was insufficient, there was a problem that the obtained curable resin composition had poor long-term heat resistance.
一方、特許文献２、３には、硬化性樹脂との相溶性を向上させるため、柔軟なシリコーン骨格や脂環式骨格を導入したポリイミドを硬化剤として用いた硬化性樹脂組成物が開示されている。しかしながら、シリコーン骨格や脂環式骨格を導入すると、得られる硬化物のガラス転移温度が低下しやすく、ＥＣＵやパワーデバイス等の動作温度での機械的強度や長期耐熱性に劣るものとなるという問題があった。また、特許文献４には、両末端にフェノール性水酸基等を有する特定のイミドオリゴマーを硬化剤として用いることにより、熱硬化性樹脂組成物の接着性や耐熱性等を向上させることが開示されているが、このようなイミドオリゴマーを用いた場合も、長期耐熱性が低下することがあった。 On the other hand, Patent Documents 2 and 3 disclose a curable resin composition using a polyimide having a flexible silicone skeleton or an alicyclic skeleton introduced as a curing agent in order to improve compatibility with the curable resin. Yes. However, when a silicone skeleton or an alicyclic skeleton is introduced, the glass transition temperature of the resulting cured product is likely to decrease, resulting in inferior mechanical strength and long-term heat resistance at the operating temperature of ECUs, power devices, etc. was there. Patent Document 4 discloses that the adhesiveness and heat resistance of the thermosetting resin composition are improved by using a specific imide oligomer having a phenolic hydroxyl group at both ends as a curing agent. However, even when such an imide oligomer is used, the long-term heat resistance may decrease.
特開昭６１－２７０８５２号公報Japanese Patent Laid-Open No. 61-270852 特開２０１６－２０４３７号公報JP 2016-20437 A 特開２０１２－２２７５３４号公報JP 2012-227534 A 国際公開第２００５／１００４３３号International Publication No. 2005/100433
本発明は、長期耐熱性に優れる硬化物に用いることができるイミドオリゴマーを提供することを目的とする。また、本発明は、該イミドオリゴマーからなる硬化剤、及び、該硬化剤を用いてなる接着剤を提供することを目的とする。更に、本発明は、該イミドオリゴマーの製造方法を提供することを目的とする。 An object of this invention is to provide the imide oligomer which can be used for the hardened | cured material which is excellent in long-term heat resistance. Another object of the present invention is to provide a curing agent comprising the imide oligomer, and an adhesive using the curing agent. Furthermore, this invention aims at providing the manufacturing method of this imide oligomer.
本発明は、フェノール性水酸基を有するイミドオリゴマーであって、エステル結合を有するイミドオリゴマーの含有割合が７％以下であるイミドオリゴマーである。
以下に本発明を詳述する。 The present invention is an imide oligomer having a phenolic hydroxyl group, and the content ratio of the imide oligomer having an ester bond is 7% or less.
The present invention is described in detail below.
本発明者らは、フェノール性水酸基を有するイミドオリゴマーのうちエステル結合を有するものは、硬化剤として用いた場合に硬化物の長期耐熱性を向上させる効果に乏しいことを見出し、フェノール性水酸基を有しエステル結合を有さないイミドオリゴマーを用いることを検討した。しかしながら、フェノール性水酸基を有しエステル結合を有さないイミドオリゴマーを用いた場合でも硬化物の長期耐熱性を充分に向上させることができなかった。本発明者らは、硬化物の長期耐熱性を充分に向上させることができなかった原因は、エステル結合を有さないものとして用いたフェノール性水酸基を有するイミドオリゴマー中に、不純物としてエステル結合を有するイミドオリゴマーが僅かに存在していたためであると考えた。そこで本発明者らは鋭意検討した結果、不純物であるエステル結合を有するイミドオリゴマーの含有割合を７％以下としたフェノール性水酸基を有するイミドオリゴマーを用いることにより、長期耐熱性に優れる硬化物を得ることができることを見出し、本発明を完成させるに至った。 The present inventors have found that an imide oligomer having a phenolic hydroxyl group having an ester bond has a poor effect of improving the long-term heat resistance of the cured product when used as a curing agent, and has a phenolic hydroxyl group. Then, the use of an imide oligomer having no ester bond was studied. However, even when an imide oligomer having a phenolic hydroxyl group and having no ester bond is used, the long-term heat resistance of the cured product cannot be sufficiently improved. The inventors of the present invention were unable to sufficiently improve the long-term heat resistance of the cured product because the ester bond as an impurity was incorporated into the imide oligomer having a phenolic hydroxyl group used as having no ester bond. It was thought that this was because a slight amount of imide oligomer was present. Thus, as a result of intensive studies, the present inventors obtained a cured product having excellent long-term heat resistance by using an imide oligomer having a phenolic hydroxyl group in which the content ratio of an imide oligomer having an ester bond as an impurity is 7% or less. As a result, the present invention has been completed.
本発明のイミドオリゴマーは、フェノール性水酸基を有する。
本発明のイミドオリゴマーは、エステル結合を有するイミドオリゴマーの含有割合が７％以下である。上記エステル結合を有するイミドオリゴマーの含有割合が７％以下であることにより、本発明のイミドオリゴマーは、硬化剤として用いた際に得られる硬化物の長期耐熱性を向上させる効果に優れるものとなる。上記エステル結合を有するイミドオリゴマーの含有割合は、５％以下であることが好ましく、０％であること、即ち、上記エステル結合を有するイミドオリゴマーを含有しないことが最も好ましい。
なお、上記エステル結合を有するイミドオリゴマーの含有割合は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて各ピークを分取した後、フーリエ変換赤外分光法（ＦＴ－ＩＲ）によりエステル結合に由来する吸収をもつ化合物の重量比率から求めることができる。具体的には、まず、遊離液にテトラヒドロフラン（ＴＨＦ）を用い、ＧＰＣカラム（例えば、日本分析工業社製、「ＪＡＩＧＥＬ－２Ｈ」等）を装着したリサイクル分取ＨＰＬＣ（日本分析工業社製）を用いて各ピークを分取する。その後、遊離液を加熱等により除去することで得られる化合物をフーリエ変換赤外分光光度計（例えば、Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製、「ＵＭＡ６００」等）を用いて全反射測定法（ＡＴＲ法）にて測定を行う。得られた測定結果から、エステル結合に由来するピーク（１１５９ｃｍ－１）を有する化合物の重量の、全ピーク化合物に対する重量比率を求めることにより導出することができる。 The imide oligomer of the present invention has a phenolic hydroxyl group.
In the imide oligomer of the present invention, the content ratio of the imide oligomer having an ester bond is 7% or less. When the content ratio of the imide oligomer having an ester bond is 7% or less, the imide oligomer of the present invention is excellent in the effect of improving the long-term heat resistance of a cured product obtained when used as a curing agent. . The content ratio of the imide oligomer having an ester bond is preferably 5% or less, and most preferably 0%, that is, not containing the imide oligomer having an ester bond.
The content ratio of the imide oligomer having an ester bond is derived from the ester bond by Fourier transform infrared spectroscopy (FT-IR) after fractionating each peak using gel permeation chromatography (GPC). It can be determined from the weight ratio of the compound having absorption. Specifically, first, tetrahydrofuran (THF) was used as a free liquid, and a recycle preparative HPLC (manufactured by Nippon Analytical Industrial Co., Ltd.) equipped with a GPC column (for example, “JAIGEL-2H” manufactured by Nippon Analytical Industrial Co., Ltd.) Use to separate each peak. Thereafter, the compound obtained by removing the free liquid by heating or the like is measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (for example, “UMA600” manufactured by Agilent Technologies). I do. From the obtained measurement results, it can be derived by determining the weight ratio of the compound having a peak (1159 cm −1 ) derived from an ester bond to the total peak compound.
本発明のイミドオリゴマーは、得られる硬化物の長期耐熱性の観点から、フェノール性水酸基を主鎖の末端に有することが好ましく、両末端に有することがより好ましい。 From the viewpoint of long-term heat resistance of the resulting cured product, the imide oligomer of the present invention preferably has a phenolic hydroxyl group at the ends of the main chain, and more preferably at both ends.
本発明のイミドオリゴマーの数平均分子量の好ましい下限は４００、好ましい上限は４２００である。上記数平均分子量がこの範囲であることにより、本発明のイミドオリゴマーを硬化剤として用いた場合に得られる硬化物が長期耐熱性に優れるものとなる。本発明のイミドオリゴマーの数平均分子量のより好ましい下限は４２０、より好ましい上限は４０００である。
なお、本明細書において上記「数平均分子量」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で溶媒としてテトラヒドロフランを用いて測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による数平均分子量を測定する際に用いるカラムとしては、例えば、ＪＡＩＧＥＬ－２Ｈ－Ａ（日本分析工業社製）等が挙げられる。 The minimum with a preferable number average molecular weight of the imide oligomer of this invention is 400, and a preferable upper limit is 4200. When the number average molecular weight is within this range, a cured product obtained when the imide oligomer of the present invention is used as a curing agent has excellent long-term heat resistance. The more preferable lower limit of the number average molecular weight of the imide oligomer of the present invention is 420, and the more preferable upper limit is 4000.
In the present specification, the “number average molecular weight” is a value determined by gel conversion chromatography (GPC) using tetrahydrofuran as a solvent and converted to polystyrene. Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Nippon Analytical Industrial Co., Ltd.).
本発明のイミドオリゴマーは、具体的には、下記式（１－１）で表されるイミドオリゴマー及び／又は下記式（１－２）で表されるイミドオリゴマーを主成分として含有することが好ましい。
なお、本明細書において上記「主成分」は、含有割合が６０モル％以上であることを意味する。 Specifically, the imide oligomer of the present invention preferably contains as a main component an imide oligomer represented by the following formula (1-1) and / or an imide oligomer represented by the following formula (1-2). .
In the present specification, the “main component” means that the content ratio is 60 mol% or more.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
式（１－１）及び（１－２）中、Ｒ１及びＲ２は、それぞれ独立して、水素原子、ハロゲン原子、又は、置換されていてもよい１価の炭化水素基であり、Ｘは、結合手、酸素原子、又は、置換されていてもよい２価の炭化水素基であり、式（１－２）中、Ｙは、結合手、酸素原子、又は、置換されていてもよい２価の炭化水素基である。 In formulas (1-1) and (1-2), R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group, Is a bond, an oxygen atom, or a divalent hydrocarbon group that may be substituted. In formula (1-2), Y is a bond, an oxygen atom, or may be substituted. It is a divalent hydrocarbon group.
本発明のイミドオリゴマーを製造する方法としては、原料として用いるフェノール性水酸基を有するモノアミンの量を過剰量とする方法が好ましく用いられる。
酸無水物基を有する化合物とフェノール性水酸基を有するモノアミンとを反応させる工程を有し、上記フェノール性水酸基を有するモノアミンの使用量が上記酸無水物基を有する化合物の酸無水物基に対して１．５当量以上であるイミドオリゴマーの製造方法もまた、本発明の１つである。本発明のイミドオリゴマーの製造方法によれば、副生物として発生するエステル結合を有するイミドオリゴマーの含有割合を７％以下とした本発明のイミドオリゴマーを容易に製造することができる。 As a method for producing the imide oligomer of the present invention, a method in which the amount of monoamine having a phenolic hydroxyl group used as a raw material is excessive is preferably used.
A step of reacting a compound having an acid anhydride group with a monoamine having a phenolic hydroxyl group, wherein the amount of the monoamine having a phenolic hydroxyl group is used relative to the acid anhydride group of the compound having the acid anhydride group A method for producing an imide oligomer having 1.5 equivalents or more is also one aspect of the present invention. According to the method for producing an imide oligomer of the present invention, the imide oligomer of the present invention in which the content ratio of the imide oligomer having an ester bond generated as a by-product is 7% or less can be easily produced.
本発明のイミドオリゴマーの製造方法の具体例を以下に示す。
まず、予めフェノール性水酸基を有するモノアミンを、反応により得られるアミック酸オリゴマーが可溶な溶媒（例えば、Ｎ，Ｎ－ジメチルホルムアミド等）に溶解させ、得られた溶液に酸二無水物を添加して反応させてアミック酸オリゴマー溶液を得る。次いで、得られたアミック酸オリゴマー溶液を塩酸等に加え、析出物を回収する操作を数回行う。得られた析出物を加熱してイミド化反応を進行させることにより、フェノール性水酸基を有するイミドオリゴマーを得ることができる。この方法を用いる場合、上記フェノール性水酸基を有するモノアミンの使用量を上記酸二無水物の有する酸無水物基に対して１．５当量以上とすることにより、エステル結合を有するイミドオリゴマーの含有割合を７％以下とすることができる。 The specific example of the manufacturing method of the imide oligomer of this invention is shown below.
First, a monoamine having a phenolic hydroxyl group is dissolved in advance in a solvent in which an amic acid oligomer obtained by the reaction is soluble (for example, N, N-dimethylformamide, etc.), and acid dianhydride is added to the resulting solution. To obtain an amic acid oligomer solution. Next, the obtained amic acid oligomer solution is added to hydrochloric acid or the like, and the operation of collecting the precipitate is performed several times. An imide oligomer having a phenolic hydroxyl group can be obtained by heating the obtained precipitate to advance an imidization reaction. When using this method, the content of the imide oligomer having an ester bond is determined by setting the amount of the monoamine having a phenolic hydroxyl group to 1.5 equivalents or more based on the acid anhydride group of the acid dianhydride. Can be made 7% or less.
また、本発明のイミドオリゴマーの製造方法の別の具体例を以下に示す。
まず、予めジアミンを、反応により得られるアミック酸オリゴマーが可溶な溶媒（例えば、Ｎ，Ｎ－ジメチルホルムアミド等）に溶解させ、得られた溶液に酸二無水物を添加して反応させて、両末端に酸無水物基を有するアミック酸オリゴマー（Ａ）の溶液を得る。得られたアミック酸オリゴマー（Ａ）の溶液に、フェノール性水酸基を有するモノアミンを添加して反応させてアミック酸オリゴマー（Ｂ）の溶液を得る。次いで、得られたアミック酸オリゴマー（Ｂ）の溶液を塩酸等に加え、析出物を回収する操作を数回行う。得られた析出物を加熱してイミド化反応を進行させることにより、フェノール性水酸基を有するイミドオリゴマーを得ることができる。この方法を用いる場合、上記フェノール性水酸基を有するモノアミンの使用量を、上記アミック酸オリゴマー（Ａ）の酸無水物基に対して１．５当量以上とすることにより、エステル結合を有するイミドオリゴマーの含有割合を７％以下とすることができる。 Moreover, another specific example of the manufacturing method of the imide oligomer of this invention is shown below.
First, diamine is dissolved in advance in a solvent in which the amic acid oligomer obtained by the reaction is soluble (for example, N, N-dimethylformamide and the like), and acid dianhydride is added to the resulting solution to cause reaction. A solution of the amic acid oligomer (A) having acid anhydride groups at both ends is obtained. A monoamine having a phenolic hydroxyl group is added to the obtained solution of the amic acid oligomer (A) and reacted to obtain a solution of the amic acid oligomer (B). Subsequently, the solution of the obtained amic acid oligomer (B) is added to hydrochloric acid or the like, and the operation of collecting the precipitate is performed several times. An imide oligomer having a phenolic hydroxyl group can be obtained by heating the obtained precipitate to advance an imidization reaction. When using this method, the amount of the monoamine having a phenolic hydroxyl group is 1.5 equivalents or more with respect to the acid anhydride group of the amic acid oligomer (A), whereby the imide oligomer having an ester bond is used. The content ratio can be 7% or less.
上記フェノール性水酸基を有するモノアミンとしては、下記式（２）で表される化合物が好適に用いられる。
上記フェノール性水酸基を有するモノアミンとしては、具体的には例えば、３－アミノフェノール、４－アミノフェノール、４－アミノ－ｏ－クレゾール、５－アミノ－ｏ－クレゾール、４－アミノ－２，３－キシレノール、４－アミノ－２，５－キシレノール、４－アミノ－２，６－キシレノール、４－アミノ－１－ナフトール、５－アミノ－２－ナフトール、６－アミノ－１－ナフトール、４－アミノ－２，６－ジフェニルフェノール等が挙げられる。なかでも、入手性及び保存安定性に優れ、高いガラス転移温度を有する硬化物が得られることから、３－アミノフェノール、４－アミノフェノール、４－アミノ－ｏ－クレゾール、５－アミノ－ｏ－クレゾールが好ましい。 As the monoamine having a phenolic hydroxyl group, a compound represented by the following formula (2) is preferably used.
Specific examples of the monoamine having a phenolic hydroxyl group include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-2,3- Xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amino-2-naphthol, 6-amino-1-naphthol, 4-amino- Examples include 2,6-diphenylphenol. Among them, a cured product having excellent availability and storage stability and a high glass transition temperature can be obtained, so that 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o- Cresol is preferred.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
式（２）中、Ａｒは、置換されていてもよい２価の芳香族基であり、Ｒ３及びＲ４は、それぞれ独立に、水素原子又は置換されていてもよい１価の炭化水素基である。 In formula (2), Ar is a divalent aromatic group which may be substituted, and R 3 and R 4 are each independently a hydrogen atom or a monovalent hydrocarbon group which may be substituted. It is.
上記酸二無水物としては、下記式（３）で表される化合物が好適に用いられる。
上記酸二無水物としては、具体的には例えば、ピロメリット酸二無水物、３，３’－オキシジフタル酸二無水物、３，４’－オキシジフタル酸二無水物、４，４’－オキシジフタル酸二無水物、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、４，４’－ビス（３，４－ジカルボキシルフェノキシ）ジフェニルエーテル、ｐ－フェニレンビス（トリメリテート無水物）、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、４，４’－カルボニルジフタル酸二無水物等が挙げられる。なかでも、溶解性、耐熱性、及び、入手性に優れることから、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物、３，４’－オキシジフタル酸二無水物、４，４’－オキシジフタル酸二無水物、４，４’－カルボニルジフタル酸二無水物が好ましい。 As said acid dianhydride, the compound represented by following formula (3) is used suitably.
Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3′-oxydiphthalic dianhydride, 3,4′-oxydiphthalic dianhydride, and 4,4′-oxydiphthalic acid. Dianhydrides, 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 4,4'-bis (3,4-dicarboxylphenoxy) diphenyl ether, p-phenylenebis (trimellitate anhydride) ), 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-carbonyldiphthalic dianhydride Etc. Among these, 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic anhydride, 3,4′-oxydiphthalic dianhydride, because of its excellent solubility, heat resistance, and availability, 4,4′-oxydiphthalic dianhydride and 4,4′-carbonyldiphthalic dianhydride are preferred.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
式（３）中、Ａは、下記式（４－１）又は下記式（４－２）で表される４価の基である。 In the formula (3), A is a tetravalent group represented by the following formula (4-1) or the following formula (4-2).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
式（４－１）及び式（４－２）中、＊は、結合位置であり、式（４－１）中、Ｚは、結合手、酸素原子、カルボニル基、又は、置換されていてもよく、結合位置に酸素原子を有していてもよい２価の炭化水素基である。式（４－１）及び式（４－２）中における芳香環の水素原子は置換されていてもよい。 In formula (4-1) and formula (4-2), * represents a bonding position, and in formula (4-1), Z represents a bond, an oxygen atom, a carbonyl group, or may be substituted. It is a divalent hydrocarbon group that may have an oxygen atom at the bonding position. The hydrogen atom of the aromatic ring in formula (4-1) and formula (4-2) may be substituted.
上記ジアミンとしては、下記式（５）で表される化合物が好適に用いられる。
上記ジアミンとしては、具体的には例えば、例えば、３，３’－ジアミノジフェニルメタン、３，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルメタン、３，３’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルエーテル、１，２－フェニレンジアミン、１，３－フェニレンジアミン、１，４－フェニレンジアミン、３，３’－ジアミノジフェニルスルフォン、４，４’－ジアミノジフェニルスルフォン、ビス（４－（３－アミノフェノキシ）フェニル）スルフォン、ビス（４－（４－アミノフェノキシ）フェニル）スルフォン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、ビス（４－（４－アミノフェノキシ）フェニル）メタン、２，２－ビス（４－（４－アミノフェノキシ）フェニル）プロパン、１，３－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼン、１，４－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼン、３，３’－ジアミノ－４，４’－ジヒドロキシジフェニルメタン、４，４’－ジアミノ－３，３’－ジヒドロキシジフェニルメタン、３，３’－ジアミノ－４，４’－ジヒドロキシジフェニルエーテル、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）プロパン、ビスアミノフェニルフルオレン、ビストルイジンフルオレン、４，４’－ビス（４－アミノフェノキシ）ビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシジフェニルエーテル、３，３’－ジアミノ－４，４’－ジヒドロキシビフェニル、４，４’－ジアミノ－２，２’－ジヒドロキシビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシビフェニル、４，４’－ビス（４－アミノベンザミド）－３，３’－ジヒドロキシビフェニル、４，４’－ビス（３－アミノベンザミド）－３，３’－ジヒドロキシビフェニル等が挙げられる。なかでも、溶解性、耐熱性、及び、入手性に優れることから、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルエーテル、１，２－フェニレンジアミン、１，３－フェニレンジアミン、１，４－フェニレンジアミン、ビス（４－（３－アミノフェノキシ）フェニル）スルフォン、ビス（４－（４－アミノフェノキシ）フェニル）スルフォン、１，３－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼン、１，４－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼンが好ましい。 As said diamine, the compound represented by following formula (5) is used suitably.
Specific examples of the diamine include, for example, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenyl ether, 3,4′- Diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, Bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino) Phenoxy) benzene, 1,4-bis (4-aminophenoxy) Zen, bis (4- (4-aminophenoxy) phenyl) methane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (2- (4-aminophenyl) -2 -Propyl) benzene, 1,4-bis (2- (4-aminophenyl) -2-propyl) benzene, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 4,4'-diamino-3, 3'-dihydroxydiphenylmethane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-hydroxy-4- Aminophenyl) propane, bisaminophenylfluorene, bistoluidinefluorene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diamy -3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-3,3 ' -Dihydroxybiphenyl, 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl, 4,4'-bis (3-aminobenzamide) -3,3'-dihydroxybiphenyl, etc. It is done. Among these, since it has excellent solubility, heat resistance, and availability, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,2-phenylenediamine, 1,3-phenylenediamine, 1, 4-phenylenediamine, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 1,3-bis (2- (4-aminophenyl) -2- Propyl) benzene and 1,4-bis (2- (4-aminophenyl) -2-propyl) benzene are preferred.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
式（５）中、Ｂは、下記式（６－１）又は下記式（６－２）で表される２価の基であり、Ｒ５～Ｒ８は、それぞれ独立に、水素原子又は１価の炭化水素基である。 In the formula (5), B is a divalent group represented by the following formula (6-1) or the following formula (6-2), and R 5 to R 8 are each independently a hydrogen atom or 1 Valent hydrocarbon group.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
式（６－１）及び式（６－２）中、＊は、結合位置であり、式（６－１）中、Ｙは、結合手、酸素原子、又は、置換されていてもよい２価の炭化水素基である。式（６－１）及び式（６－２）中のフェニレン基は、一部又は全部の水素原子が水酸基で置換されていてもよい。 In Formula (6-1) and Formula (6-2), * is a bond position, and in Formula (6-1), Y is a bond, an oxygen atom, or an optionally substituted divalent group. It is a hydrocarbon group. In the phenylene groups in the formulas (6-1) and (6-2), some or all of the hydrogen atoms may be substituted with hydroxyl groups.
本発明のイミドオリゴマーのイミド化率の好ましい下限は７０％である。上記イミド化率が７０％以上であることにより、硬化剤として用いた場合に高温での機械的強度及び長期耐熱性により優れる硬化物を得ることができる。上記イミド化率のより好ましい下限は７５％、更に好ましい下限は８０％である。また、本発明のイミドオリゴマーのイミド化率の好ましい上限は特にないが、実質的な上限は９８％である。
なお、上記「イミド化率」は、フーリエ変換赤外分光法（ＦＴ－ＩＲ）により求めることができる。具体的には、フーリエ変換赤外分光光度計（例えば、Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製、「ＵＭＡ６００」等）を用いて全反射測定法（ＡＴＲ法）にて測定を行い、アミック酸のカルボニル基に由来する１６６０ｃｍ－１付近のピーク吸光度面積から下記式にて導出することができる。なお、下記式中における「アミック酸オリゴマーのピーク吸光度面積」は、酸無水物基を有する化合物とフェノール性水酸基を有するモノアミンとを反応させた後、イミド化工程を行わずに溶媒をエバポレーションにより除去することで得られるアミック酸オリゴマーの吸光度面積である。
イミド化率（％）＝１００×（１－（イミド化後のピーク吸光度面積）／（アミック酸オリゴマーのピーク吸光度面積）） A preferable lower limit of the imidization ratio of the imide oligomer of the present invention is 70%. When the imidation ratio is 70% or more, a cured product excellent in mechanical strength at high temperature and long-term heat resistance can be obtained when used as a curing agent. A more preferable lower limit of the imidization ratio is 75%, and a more preferable lower limit is 80%. Further, there is no particular upper limit for the imidation ratio of the imide oligomer of the present invention, but the substantial upper limit is 98%.
The “imidation ratio” can be determined by Fourier transform infrared spectroscopy (FT-IR). Specifically, measurement is performed by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (for example, “UMA600” manufactured by Agilent Technologies), and is derived from a carbonyl group of an amic acid. It can be derived from the peak absorbance area around 1660 cm −1 by the following equation. The “peak absorbance area of the amic acid oligomer” in the following formula is obtained by reacting a compound having an acid anhydride group with a monoamine having a phenolic hydroxyl group, and then evaporating the solvent without performing an imidization step. It is the absorbance area of the amic acid oligomer obtained by removing.
Imidation ratio (%) = 100 × (1- (peak absorbance area after imidization) / (peak absorbance area of amic acid oligomer))
上述したように、本発明のイミドオリゴマーは、硬化剤として用いた場合に長期耐熱性に優れる硬化物を得ることができる。本発明のイミドオリゴマーからなる硬化剤もまた、本発明の１つである。また、硬化性樹脂と本発明の硬化剤とを含有する接着剤もまた、本発明の１つである。 As described above, the imide oligomer of the present invention can provide a cured product having excellent long-term heat resistance when used as a curing agent. The curing agent comprising the imide oligomer of the present invention is also one aspect of the present invention. Moreover, the adhesive agent containing curable resin and the hardening | curing agent of this invention is also one of this invention.
本発明の接着剤における本発明の硬化剤の含有量は、硬化性樹脂１００重量部に対して、好ましい下限が５０重量部、好ましい上限が５００重量部である。本発明の硬化剤の含有量がこの範囲であることにより、得られる接着剤の硬化物が長期耐熱性により優れるものとなる。本発明の硬化剤の含有量のより好ましい下限は７０重量部、より好ましい上限は４００重量部である。 The content of the curing agent of the present invention in the adhesive of the present invention is preferably 50 parts by weight with a preferred lower limit and 500 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the curing agent of the present invention is within this range, a cured product of the obtained adhesive is superior in long-term heat resistance. The minimum with more preferable content of the hardening | curing agent of this invention is 70 weight part, and a more preferable upper limit is 400 weight part.
本発明の接着剤は、未硬化状態での加工性を向上させる等のために、本発明の目的を阻害しない範囲において、本発明の硬化剤に加えて他の硬化剤を含有してもよい。
上記他の硬化剤としては、例えば、フェノール系硬化剤、チオール系硬化剤、アミン系硬化剤、酸無水物系硬化剤、シアネート系硬化剤、活性エステル系硬化剤等が挙げられる。なかでも、フェノール系硬化剤、酸無水物系硬化剤、シアネート系硬化剤、活性エステル系硬化剤が好ましい。 The adhesive of the present invention may contain other curing agents in addition to the curing agent of the present invention as long as the object of the present invention is not impaired, for example, in order to improve processability in an uncured state. .
Examples of the other curing agents include phenolic curing agents, thiol curing agents, amine curing agents, acid anhydride curing agents, cyanate curing agents, and active ester curing agents. Of these, phenolic curing agents, acid anhydride curing agents, cyanate curing agents, and active ester curing agents are preferred.
本発明の接着剤が上記他の硬化剤を含有する場合、硬化剤全体中における上記他の硬化剤の含有割合の好ましい上限は７０重量％、より好ましい上限は５０重量％、更に好ましい上限は３０重量％である。 When the adhesive of the present invention contains the other curing agent, the preferable upper limit of the content of the other curing agent in the entire curing agent is 70% by weight, the more preferable upper limit is 50% by weight, and the more preferable upper limit is 30. % By weight.
本発明の接着剤は、硬化性樹脂を含有する。
上記硬化性樹脂は、得られる接着剤の流動性及び加工性の観点から、２５℃で液状であることが好ましい。 The adhesive of the present invention contains a curable resin.
The curable resin is preferably liquid at 25 ° C. from the viewpoint of fluidity and workability of the resulting adhesive.
上記硬化性樹脂としては、エポキシ樹脂が好適に用いられる。
上記エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、２，２’－ジアリルビスフェノールＡ型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スルフィド型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンフェノールノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アルキルポリオール型エポキシ樹脂、ゴム変性型エポキシ樹脂、グリシジルエステル化合物等が挙げられる。なかでも、粘度が低く、得られる接着剤の室温における加工性を調整しやすいことから、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、レゾルシノール型エポキシ樹脂が好ましい。 An epoxy resin is preferably used as the curable resin.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, and hydrogenated bisphenol type epoxy resin. , Propylene oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, naphthylene ether Type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolak type epoxy resin, biffe Examples thereof include nil novolac type epoxy resins, naphthalene phenol novolac type epoxy resins, glycidyl amine type epoxy resins, alkyl polyol type epoxy resins, rubber-modified epoxy resins, and glycidyl ester compounds. Of these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and resorcinol type epoxy resin are preferred because of low viscosity and easy adjustment of the processability of the resulting adhesive at room temperature.
本発明の接着剤は、硬化促進剤を含有してもよい。上記硬化促進剤を含有することにより、硬化時間を短縮させて生産性を向上させることができる。 The adhesive of the present invention may contain a curing accelerator. By containing the said hardening accelerator, hardening time can be shortened and productivity can be improved.
上記硬化促進剤としては、例えば、イミダゾール系硬化促進剤、３級アミン系硬化促進剤、ホスフィン系硬化促進剤、光塩基発生剤、スルホニウム塩系硬化促進剤等が挙げられる。なかでも、イミダゾール系硬化促進剤が好ましい。 Examples of the curing accelerator include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, photobase generators, sulfonium salt-based curing accelerators, and the like. Of these, imidazole curing accelerators are preferable.
上記硬化促進剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．０１重量部、好ましい上限が１０重量部である。上記硬化促進剤の含有量がこの範囲であることにより、優れた接着性等を維持したまま、硬化時間を短縮させる効果により優れるものとなる。上記硬化促進剤の含有量のより好ましい下限は０．０５重量部、より好ましい上限は５重量部である。 The content of the curing accelerator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the curing accelerator is within this range, the effect of shortening the curing time is maintained while maintaining excellent adhesiveness and the like. The minimum with more preferable content of the said hardening accelerator is 0.05 weight part, and a more preferable upper limit is 5 weight part.
本発明の接着剤は、応力緩和、靭性付与、難燃性付与等を目的として有機充填剤を含有してもよい。
上記有機充填剤としては、例えば、シリコーンゴム粒子、アクリルゴム粒子、ウレタンゴム粒子、ポリアミド粒子、ポリアミドイミド粒子、ポリイミド粒子、ベンゾグアナミン粒子、及び、これらのコアシェル粒子等が挙げられる。なかでも、ポリアミド粒子、ポリアミドイミド粒子、ポリイミド粒子が好ましい。 The adhesive of the present invention may contain an organic filler for the purpose of stress relaxation, toughness imparting, flame retardancy imparting and the like.
Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core-shell particles thereof. Of these, polyamide particles, polyamideimide particles, and polyimide particles are preferable.
上記有機充填剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が１０重量部、好ましい上限が５００重量部である。上記有機充填剤の含有量がこの範囲であることにより、優れた接着性等を維持したまま、得られる硬化物が靭性等により優れるものとなる。上記有機充填剤の含有量のより好ましい下限は３０重量部、より好ましい上限は４００重量部である。 The content of the organic filler is preferably 10 parts by weight and preferably 500 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the organic filler is within this range, the obtained cured product is excellent in toughness and the like while maintaining excellent adhesiveness and the like. The minimum with more preferable content of the said organic filler is 30 weight part, and a more preferable upper limit is 400 weight part.
本発明の接着剤は、硬化後の線膨張率を低下させてそりを低減させたり、難燃性を付与したり、接着信頼性を向上させたりする等を目的として無機充填剤を含有してもよい。 The adhesive of the present invention contains an inorganic filler for the purpose of reducing warpage by reducing the linear expansion coefficient after curing, imparting flame retardancy, improving adhesion reliability, and the like. Also good.
上記無機充填剤としては、例えば、コロイダルシリカ等のシリカ、アルミナ、窒化アルミニウム、窒化ホウ素、窒化ケイ素、水酸化アルミミニウム、水酸化マグネシウム、ガラスパウダー、ガラスフリット、ガラス繊維、カーボンファイバー、無機イオン交換体等が挙げられる。 Examples of the inorganic filler include silica such as colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, aluminum hydroxide, magnesium hydroxide, glass powder, glass frit, glass fiber, carbon fiber, and inorganic ion exchange. Examples include the body.
上記無機充填剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が１０重量部、好ましい上限が１０００重量部である。上記無機充填剤の含有量がこの範囲であることにより、優れた加工性等を維持したまま、接着信頼性を向上させる等の効果により優れるものとなる。上記無機充填剤の含有量のより好ましい下限は２０重量部、より好ましい上限は９００重量部である。 The content of the inorganic filler is such that the preferred lower limit is 10 parts by weight and the preferred upper limit is 1000 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the inorganic filler is within this range, the adhesive reliability is improved while maintaining excellent processability and the like. The minimum with more preferable content of the said inorganic filler is 20 weight part, and a more preferable upper limit is 900 weight part.
また、無機充填剤は、被着体への短時間での塗れ性と形状保持性とを向上させる等の目的で流動調整剤として用いることもできる。 The inorganic filler can also be used as a flow regulator for the purpose of improving the paintability and shape retention in a short time on the adherend.
流動調整剤として用いられる無機充填剤は、例えば、ヒュームドシリカや層状ケイ酸塩等が挙げられる。 Examples of the inorganic filler used as the flow regulator include fumed silica and layered silicate.
上記流動調整剤として用いる無機充填剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が５０重量部である。上記流動調整剤として用いる無機充填剤の含有量がこの範囲であることにより、被着体への短時間での塗れ性と形状保持性とを向上させる等の効果により優れるものとなる。上記流動調整剤として用いる無機充填剤の含有量のより好ましい下限は０．５重量部、より好ましい上限は３０重量部である。 The content of the inorganic filler used as the flow regulator is preferably 0.1 parts by weight and preferably 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the inorganic filler used as the flow regulator is within this range, the effect of improving the wettability and shape retention on the adherend in a short time becomes excellent. The minimum with more preferable content of the inorganic filler used as the said flow regulator is 0.5 weight part, and a more preferable upper limit is 30 weight part.
本発明の接着剤は、本発明の目的を阻害しない範囲で高分子化合物を含有してもよい。上記高分子化合物は、造膜成分としての役割を果たす。 The adhesive of the present invention may contain a polymer compound as long as the object of the present invention is not impaired. The polymer compound serves as a film forming component.
上記高分子化合物は、反応性官能基を有していてもよい。
上記反応性官能基としては、例えば、アミノ基、ウレタン基、イミド基、水酸基、カルボキシル基、エポキシ基等が挙げられる。 The polymer compound may have a reactive functional group.
Examples of the reactive functional group include an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, and an epoxy group.
また、上記高分子化合物は、硬化物中で相分離構造を形成してもよいし、相分離構造を形成しなくてもよい。上記高分子化合物が硬化物中で相分離構造を形成しない場合、上記高分子化合物としては、高温での機械的強度、長期耐熱性、及び、耐湿性により優れることから、上記反応性官能基としてエポキシ基を有する高分子化合物が好ましい。 In addition, the polymer compound may form a phase separation structure in the cured product or may not form a phase separation structure. When the polymer compound does not form a phase separation structure in the cured product, the polymer compound is superior in mechanical strength at high temperatures, long-term heat resistance, and moisture resistance. A polymer compound having an epoxy group is preferred.
本発明の接着剤は、本発明の目的を阻害しない範囲で反応性希釈剤を含有してもよい。
上記反応性希釈剤としては、接着信頼性の観点から、１分子中に２つ以上の反応性官能基を有する反応性希釈剤が好ましい。
上記反応性希釈剤の有する反応性官能基としては、上述した高分子化合物が有する反応性官能基と同様のものが挙げられる。 The adhesive of the present invention may contain a reactive diluent as long as the object of the present invention is not impaired.
As the reactive diluent, a reactive diluent having two or more reactive functional groups in one molecule is preferable from the viewpoint of adhesion reliability.
As a reactive functional group which the said reactive diluent has, the thing similar to the reactive functional group which the high molecular compound mentioned above has is mentioned.
本発明の接着剤は、更に、溶剤、カップリング剤、分散剤、貯蔵安定化剤、ブリード防止剤、フラックス剤、液状難燃剤等の添加剤を含有してもよい。 The adhesive of the present invention may further contain additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, a bleed inhibitor, a flux agent, and a liquid flame retardant.
本発明の接着剤を製造する方法としては、例えば、ホモディスパー、万能ミキサー、バンバリーミキサー、ニーダー等の混合機を用いて、硬化性樹脂と、本発明の硬化剤と、必要に応じて添加する他の硬化剤や硬化促進剤等とを混合する方法等が挙げられる。
また、本発明の接着剤を離型フィルム上に塗工し、乾燥させることにより、本発明の接着剤からなる接着フィルムを得ることができる。 As a method for producing the adhesive of the present invention, for example, using a mixer such as a homodisper, a universal mixer, a Banbury mixer, a kneader, etc., a curable resin, the curing agent of the present invention and, if necessary, are added. Examples thereof include a method of mixing with other curing agents and curing accelerators.
Moreover, the adhesive film which consists of an adhesive agent of this invention can be obtained by apply | coating the adhesive agent of this invention on a release film, and making it dry.
本発明の接着剤は、広い用途に用いることができるが、特に高い耐熱性が求められている電子材料用途に好適に用いることができる。例えば、航空、車載用電気制御ユニット（ＥＣＵ）用途や、ＳｉＣ、ＧａＮを用いたパワーデバイス用途におけるダイアタッチ剤等に用いることができる。また、例えば、パワーオーバーレイパッケージ用接着剤、プリント配線基板用接着剤、フレキシブルプリント回路基板のカバーレイ用接着剤、半導体接合用接着剤、構造材料用接着剤等にも用いることができる。更に、接着剤用途以外にも、硬化性組成物として、例えば、封止剤、銅張積層板、半導体接合用接着剤、層間絶縁膜、プリプレグ等に用いることができる。 The adhesive of the present invention can be used for a wide range of applications, but can be suitably used for electronic materials that require particularly high heat resistance. For example, it can be used for die attach agents in aviation, in-vehicle electric control unit (ECU) applications, power device applications using SiC, and GaN. Also, for example, it can be used as an adhesive for power overlay packages, an adhesive for printed wiring boards, an adhesive for coverlays of flexible printed circuit boards, an adhesive for semiconductor bonding, an adhesive for structural materials, and the like. Furthermore, besides the adhesive application, the curable composition can be used, for example, as a sealant, a copper clad laminate, a semiconductor bonding adhesive, an interlayer insulating film, a prepreg, and the like.
本発明によれば、長期耐熱性に優れる硬化物に用いることができるイミドオリゴマーを提供することができる。また、本発明によれば、該イミドオリゴマーからなる硬化剤、及び、該硬化剤を用いてなる接着剤を提供することができる。更に、本発明によれば、該イミドオリゴマーの製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the imide oligomer which can be used for the hardened | cured material excellent in long-term heat resistance can be provided. Further, according to the present invention, a curing agent comprising the imide oligomer and an adhesive using the curing agent can be provided. Furthermore, according to this invention, the manufacturing method of this imide oligomer can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（合成例１（イミドオリゴマーＡの作製））
３－アミノフェノール（東京化成工業社製）３２．７４重量部（反応させる３，４’－オキシジフタル酸二無水物の酸無水物基に対して１．５当量）をＮ，Ｎ－ジメチルホルムアミド２００ｍＬに溶解させた。得られた溶液に３，４’－オキシジフタル酸二無水物（東京化成工業社製）３１．０重量部を添加し、２５℃で２時間撹拌して反応させてアミック酸オリゴマー溶液を得た。得られたアミック酸オリゴマー溶液を１ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物をＮ，Ｎ－ジメチルホルムアミド１００ｍＬに溶解させ、得られた溶液を０．５ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物をＮ，Ｎ－ジメチルホルムアミド１００ｍＬに溶解させ、得られた溶液を０．１ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物について、１８０℃で２時間加熱した後、３００℃で２時間加熱するイミド化条件で反応させることにより、フェノール性水酸基を有するイミドオリゴマーＡ（イミド化率９４％）を得た。
なお、イミドオリゴマーＡは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－１）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＡは、エステル結合を有するイミドオリゴマーの含有割合が５．５％であることを確認した。更に、イミドオリゴマーＡの数平均分子量は５０６であった。 (Synthesis example 1 (production of imide oligomer A))
3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 32.74 parts by weight (1.5 equivalents relative to the acid anhydride group of 3,4'-oxydiphthalic dianhydride to be reacted) in 200 mL of N, N-dimethylformamide Dissolved in. 31.0 parts by weight of 3,4'-oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the resulting solution and stirred for 2 hours at 25 ° C. to obtain an amic acid oligomer solution. The obtained amic acid oligomer solution was added to 2 L of 1 mol / L hydrochloric acid to collect precipitates. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid to collect the precipitate. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid to collect the precipitate. The obtained precipitate was heated at 180 ° C. for 2 hours and then reacted under imidization conditions of heating at 300 ° C. for 2 hours to obtain an imide oligomer A having a phenolic hydroxyl group (imidation rate of 94%). .
The imide oligomer A was confirmed to contain the imide oligomer represented by the above formula (1-1) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer having an ester bond in the imide oligomer A was 5.5%. Furthermore, the number average molecular weight of the imide oligomer A was 506.
（合成例２（イミドオリゴマーＢの作製））
析出物のイミド化条件を、真空乾燥オーブンを用いて、２００℃、５ｍｍＨｇで３時間加熱することに変更したこと以外は合成例１と同様にして、フェノール性水酸基を有するイミドオリゴマーＢ（イミド化率４６％）を得た。
イミドオリゴマーＢは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－１）で表されるイミドオリゴマーを含むことを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＢは、エステル結合を有するイミドオリゴマーの含有割合が５．５％であることを確認した。更に、イミドオリゴマーＢの数平均分子量は５１０であった。 (Synthesis Example 2 (Production of Imide Oligomer B))
Imide oligomer B having a phenolic hydroxyl group (imidization) was carried out in the same manner as in Synthesis Example 1 except that the imidization condition of the precipitate was changed to heating at 200 ° C. and 5 mmHg for 3 hours using a vacuum drying oven. 46%).
The imide oligomer B was confirmed to contain the imide oligomer represented by the above formula (1-1) by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer B having an ester bond in the imide oligomer B was 5.5%. Furthermore, the number average molecular weight of the imide oligomer B was 510.
（合成例３（イミドオリゴマーＣの作製））
３－アミノフェノールの使用量を６５．４８重量部（反応させる３，４’－オキシジフタル酸二無水物の酸無水物基に対して３当量）に変更したこと以外は合成例１と同様にして、フェノール性水酸基を有するイミドオリゴマーＣ（イミド化率９４％）を得た。
なお、イミドオリゴマーＣは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－１）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＣは、エステル結合を有するイミドオリゴマーの含有割合が４．７％であることを確認した。更に、イミドオリゴマーＣの数平均分子量は５０６であった。 (Synthesis Example 3 (Production of Imide Oligomer C))
The same procedure as in Synthesis Example 1 except that the amount of 3-aminophenol used was changed to 65.48 parts by weight (3 equivalents relative to the acid anhydride group of 3,4'-oxydiphthalic dianhydride to be reacted). An imide oligomer C having a phenolic hydroxyl group (imidation rate: 94%) was obtained.
The imide oligomer C was confirmed to contain the imide oligomer represented by the above formula (1-1) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC fractionation and FT-IR analysis that the content ratio of the imide oligomer C having an ester bond in the imide oligomer C was 4.7%. Furthermore, the number average molecular weight of the imide oligomer C was 506.
（合成例４（イミドオリゴマーＤの作製））
３－アミノフェノール３２．７４重量部を、５－アミノ－ｏ－クレゾール（東京化成工業社製）３６．９５重量部（反応させる３，４’－オキシジフタル酸二無水物の酸無水物基に対して１．５当量）に変更したこと以外は合成例１と同様にして、フェノール性水酸基を有するイミドオリゴマーＤ（イミド化率９４％）を得た。
なお、イミドオリゴマーＤは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－１）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＤは、エステル結合を有するイミドオリゴマーの含有割合が５．３％であることを確認した。更に、イミドオリゴマーＤの数平均分子量は５３１であった。 (Synthesis example 4 (production of imide oligomer D))
3-aminophenol 32.74 parts by weight 5-amino-o-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) 36.95 parts by weight (based on the acid anhydride group of 3,4'-oxydiphthalic dianhydride to be reacted) In the same manner as in Synthesis Example 1 except that it was changed to 1.5 equivalents), an imide oligomer D having a phenolic hydroxyl group (imidization rate of 94%) was obtained.
The imide oligomer D was confirmed to contain the imide oligomer represented by the above formula (1-1) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer D having an ester bond in the imide oligomer D was 5.3%. Furthermore, the number average molecular weight of the imide oligomer D was 531.
（合成例５（イミドオリゴマーＥの作製））
３，４’－オキシジフタル酸二無水物３１．０重量部に代えて、４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物（東京化成工業社製）５２．０重量部を添加したこと以外は合成例１と同様にして、フェノール性水酸基を有するイミドオリゴマーＥ（イミド化率９３％）を得た。３－アミノフェノールの使用量は、反応させる４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物の酸無水物基に対して１．５当量である。
なお、イミドオリゴマーＥは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－１）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＥは、エステル結合を有するイミドオリゴマーの含有割合が５．４％であることを確認した。更に、イミドオリゴマーＥの数平均分子量は７１２であった。 (Synthesis Example 5 (production of imide oligomer E))
Instead of 31.0 parts by weight of 3,4′-oxydiphthalic dianhydride, 42.0 ′ of 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) Except having added a part, it carried out similarly to the synthesis example 1, and obtained the imide oligomer E (imidation rate 93%) which has a phenolic hydroxyl group. The amount of 3-aminophenol used is 1.5 equivalents relative to the acid anhydride group of 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic anhydride to be reacted.
The imide oligomer E was confirmed to contain the imide oligomer represented by the above formula (1-1) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer E having an ester bond was 5.4%. Furthermore, the number average molecular weight of the imide oligomer E was 712.
（合成例６（イミドオリゴマーＦの作製））
１，３－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼン（三井化学ファイン社製、「ビスアニリンＭ」）３４．４５重量部をＮ，Ｎ－ジメチルホルムアミド２００ｍＬに溶解させた。得られた溶液に４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物（東京化成工業社製）１０４．１重量部を添加し、２５℃で２時間撹拌して反応させて両末端に酸無水物基を有するアミック酸オリゴマー（Ａ）の溶液を得た。得られたアミック酸オリゴマー（Ａ）の溶液に３－アミノフェノール（東京化成工業社製）３２．７４重量部（反応させるアミック酸オリゴマー（Ａ）の酸無水物基に対して１．５当量）を添加し、２５℃で２時間撹拌して反応させてアミック酸オリゴマー（Ｂ）の溶液を得た。得られたアミック酸オリゴマー（Ｂ）の溶液を１ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物をＮ，Ｎ－ジメチルホルムアミド１００ｍＬに溶解させ、得られた溶液を０．５ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物をＮ，Ｎ－ジメチルホルムアミド１００ｍＬに溶解させ、得られた溶液を０．１ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物について、１８０℃で２時間加熱した後、３００℃で２時間加熱するイミド化条件で反応させることにより、フェノール性水酸基を有するイミドオリゴマーＦ（イミド化率９２％）を得た。
なお、イミドオリゴマーＦは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－２）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＦは、エステル結合を有するイミドオリゴマーの含有割合が５．５％であることを確認した。更に、イミドオリゴマーＦの数平均分子量は１５４８であった。 (Synthesis Example 6 (production of imide oligomer F))
34.45 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene (“Bisaniline M” manufactured by Mitsui Chemical Fine Co., Ltd.) was dissolved in 200 mL of N, N-dimethylformamide. To the obtained solution, 104.1 parts by weight of 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 25 ° C. for 2 hours to react. Thus, a solution of an amic acid oligomer (A) having acid anhydride groups at both ends was obtained. 32.74 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.5 equivalents relative to the acid anhydride group of the amic acid oligomer (A) to be reacted) was added to the solution of the obtained amic acid oligomer (A). Was stirred and reacted at 25 ° C. for 2 hours to obtain a solution of the amic acid oligomer (B). The solution of the obtained amic acid oligomer (B) was added to 2 L of 1 mol / L hydrochloric acid to collect the precipitate. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid to collect the precipitate. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid to collect the precipitate. About the obtained deposit, after heating at 180 degreeC for 2 hours, it was made to react on the imidation conditions heated at 300 degreeC for 2 hours, and the imide oligomer F (imidation rate 92%) which has a phenolic hydroxyl group was obtained. .
The imide oligomer F was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer F having an ester bond in the imide oligomer F was 5.5%. Furthermore, the number average molecular weight of the imide oligomer F was 1548.
（合成例７（イミドオリゴマーＧの作製））
１，３－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼンの使用量を１７．２３重量部に変更し、かつ、３－アミノフェノールの使用量を４９．１１重量部に変更したこと以外は合成例６と同様にして、フェノール性水酸基を有するイミドオリゴマーＧ（イミド化率９３％）を得た。３－アミノフェノールの使用量は、反応させるアミック酸オリゴマー（Ａ）の酸無水物基に対して１．５当量である。
なお、イミドオリゴマーＧは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－２）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＧは、エステル結合を有するイミドオリゴマーの含有割合が５．４％であることを確認した。更に、イミドオリゴマーＧの数平均分子量は１１２６であった。 (Synthesis Example 7 (production of imide oligomer G))
The amount of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene used was changed to 17.23 parts by weight, and the amount of 3-aminophenol used was changed to 49.11 parts by weight. Except that, an imide oligomer G having a phenolic hydroxyl group (imidization ratio of 93%) was obtained in the same manner as in Synthesis Example 6. The amount of 3-aminophenol used is 1.5 equivalents relative to the acid anhydride group of the amic acid oligomer (A) to be reacted.
The imide oligomer G was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC fractionation and FT-IR analysis that the imide oligomer G had a content of imide oligomer having an ester bond of 5.4%. Furthermore, the number average molecular weight of the imide oligomer G was 1126.
（合成例８（イミドオリゴマーＨの作製））
１，３－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼン（三井化学ファイン社製、「ビスアニリンＭ」）３４．５重量部をＮ－メチルピロリドン（和光純薬工業社製、「ＮＭＰ」）２００ｍＬに溶解させた。得られた溶液に４，４’－（４，４’－イソプロピリデンジフェノキシ）ジフタル酸無水物（東京化成工業社製）１０４．１重量部を添加し、２５℃で２時間撹拌して反応させてアミック酸オリゴマー溶液（Ａ）を得た。得られたアミック酸オリゴマー溶液（Ａ）に対し、更に３－アミノフェノール（東京化成工業社製）３２．７４重量部（反応させるアミック酸オリゴマー（Ａ）の酸無水物基に対して１．５当量）を添加し２５℃で２時間撹拌して反応させてアミック酸オリゴマー溶液（Ｂ）を得た。得られたアミック酸オリゴマー（Ｂ）の溶液を１ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物をＮ，Ｎ－ジメチルホルムアミド１００ｍＬに溶解させ、得られた溶液を０．５ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物をＮ，Ｎ－ジメチルホルムアミド１００ｍＬに溶解させ、得られた溶液を０．１ｍｏｌ／Ｌの塩酸２Ｌに加えて析出物を回収した。得られた析出物について、１８０℃で２時間加熱した後、３００℃で２時間加熱するイミド化条件で反応させることにより、フェノール性水酸基を有するイミドオリゴマーＨ（イミド化率９２％）を得た。
なお、イミドオリゴマーＨは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－２）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＨは、エステル結合を有するイミドオリゴマーの含有割合が５．５％であることを確認した。更に、イミドオリゴマーＨの数平均分子量は２７２０であった。 (Synthesis Example 8 (Production of Imide Oligomer H))
34.5 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene (Mitsui Chemical Fine Co., Ltd., “Bisaniline M”) was added to N-methylpyrrolidone (Wako Pure Chemical Industries, “NMP”) was dissolved in 200 mL. To the obtained solution, 104.1 parts by weight of 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 25 ° C. for 2 hours to react. To obtain an amic acid oligomer solution (A). With respect to the obtained amic acid oligomer solution (A), 32.74 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.5% with respect to the acid anhydride group of the amic acid oligomer (A) to be reacted) Equivalent) was added and stirred at 25 ° C. for 2 hours for reaction to obtain an amic acid oligomer solution (B). The solution of the obtained amic acid oligomer (B) was added to 2 L of 1 mol / L hydrochloric acid to collect the precipitate. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid to collect the precipitate. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid to collect the precipitate. About the obtained deposit, after heating at 180 degreeC for 2 hours, it was made to react on the imidation conditions heated at 300 degreeC for 2 hours, and the imide oligomer H (imidation rate 92%) which has a phenolic hydroxyl group was obtained. .
The imide oligomer H was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content of the imide oligomer having an ester bond in the imide oligomer H was 5.5%. Furthermore, the number average molecular weight of the imide oligomer H was 2720.
（合成例９（イミドオリゴマーＩの作製））
１，３－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼン３４．４５重量部を、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン２５．８３重量部に変更したこと以外は合成例６と同様にして、フェノール性水酸基を有するイミドオリゴマーＩ（イミド化率９３％）を得た。
なお、イミドオリゴマーＩは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－２）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＩは、エステル結合を有するイミドオリゴマーの含有割合が５．４％であることを確認した。更に、イミドオリゴマーＩの数平均分子量は１４９０であった。 (Synthesis Example 9 (Production of Imide Oligomer I))
34.45 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene was changed to 25.83 parts by weight of 2,2-bis (3-amino-4-hydroxyphenyl) propane Except for this, in the same manner as in Synthesis Example 6, an imide oligomer I having a phenolic hydroxyl group (imidization rate of 93%) was obtained.
The imide oligomer I was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer I having an ester bond in the imide oligomer I was 5.4%. Furthermore, the number average molecular weight of the imide oligomer I was 1490.
（合成例１０（イミドオリゴマーＪの作製））
３－アミノフェノールの使用量を２１．８３重量部（反応させる３，４’－オキシジフタル酸二無水物の酸無水物基に対して１当量）に変更したこと以外は合成例１と同様にして、フェノール性水酸基を有するイミドオリゴマーＪ（イミド化率９３％）を得た。
なお、イミドオリゴマーＪは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－１）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＪは、エステル結合を有するイミドオリゴマーの含有割合が８．２％であることを確認した。更に、イミドオリゴマーＪの数平均分子量は５４３であった。 (Synthesis Example 10 (Production of Imide Oligomer J))
The same procedure as in Synthesis Example 1 except that the amount of 3-aminophenol used was changed to 21.83 parts by weight (1 equivalent to the acid anhydride group of 3,4'-oxydiphthalic dianhydride to be reacted). Thus, an imide oligomer J having a phenolic hydroxyl group (imidation ratio: 93%) was obtained.
The imide oligomer J was confirmed to contain the imide oligomer represented by the above formula (1-1) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer having an ester bond in the imide oligomer J was 8.2%. Furthermore, the number average molecular weight of the imide oligomer J was 543.
（合成例１１（イミドオリゴマーＫの作製））
析出物のイミド化条件を、真空乾燥オーブンを用いて、２００℃、５ｍｍＨｇで３時間加熱することに変更したこと以外は合成例１０と同様にして、イミドオリゴマーＫ（イミド化率４４％）を得た。
イミドオリゴマーＫは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－１）で表されるイミドオリゴマーを含むことを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＫは、エステル結合を有するイミドオリゴマーの含有割合が８．２％であることを確認した。更に、イミドオリゴマーＫの数平均分子量は５５６であった。 (Synthesis Example 11 (Production of Imide Oligomer K))
Imide oligomer K (imidation ratio: 44%) was obtained in the same manner as in Synthesis Example 10 except that the imidization conditions of the precipitate were changed to heating at 200 ° C. and 5 mmHg for 3 hours using a vacuum drying oven. Obtained.
The imide oligomer K was confirmed to contain the imide oligomer represented by the above formula (1-1) by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC fractionation and FT-IR analysis that the content ratio of the imide oligomer having an ester bond in the imide oligomer K was 8.2%. Furthermore, the number average molecular weight of the imide oligomer K was 556.
（合成例１２（イミドオリゴマーＬの作製））
３－アミノフェノールの使用量を２１．８３重量部に変更したこと以外は合成例６と同様にして、フェノール性水酸基を有するイミドオリゴマーＬ（イミド化率９２％）を得た。３－アミノフェノールの使用量は、反応させるアミック酸オリゴマー（Ａ）の酸無水物基に対して１当量である。
なお、イミドオリゴマーＬは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－２）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＬは、エステル結合を有するイミドオリゴマーの含有割合が８．０％であることを確認した。更に、イミドオリゴマーＬの数平均分子量は１７１０であった。 (Synthesis Example 12 (Production of Imide Oligomer L))
Except that the amount of 3-aminophenol used was changed to 21.83 parts by weight, an imide oligomer L having a phenolic hydroxyl group (imidization rate of 92%) was obtained in the same manner as in Synthesis Example 6. The amount of 3-aminophenol used is 1 equivalent to the acid anhydride group of the amic acid oligomer (A) to be reacted.
The imide oligomer L was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC fractionation and FT-IR analysis that the content ratio of the imide oligomer L having an ester bond in the imide oligomer L was 8.0%. Furthermore, the number average molecular weight of the imide oligomer L was 1710.
（合成例１３（イミドオリゴマーＭの作製））
１，３－ビス（２－（４－アミノフェニル）－２－プロピル）ベンゼンの使用量を１７．２３重量部に変更したこと以外は合成例６と同様にして、フェノール性水酸基を有するイミドオリゴマーＭ（イミド化率９２％）を得た。３－アミノフェノールの使用量は、反応させるアミック酸オリゴマー（Ａ）の酸無水物基に対して１当量である。
なお、イミドオリゴマーＭは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－２）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＭは、エステル結合を有するイミドオリゴマーの含有割合が８．１％であることを確認した。更に、イミドオリゴマーＭの数平均分子量は１２４１であった。 (Synthesis Example 13 (production of imide oligomer M))
An imide oligomer having a phenolic hydroxyl group in the same manner as in Synthesis Example 6 except that the amount of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene used was changed to 17.23 parts by weight. M (imidization rate 92%) was obtained. The amount of 3-aminophenol used is 1 equivalent to the acid anhydride group of the amic acid oligomer (A) to be reacted.
The imide oligomer M was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC fractionation and FT-IR analysis that the content ratio of the imide oligomer M having an ester bond in the imide oligomer M was 8.1%. Furthermore, the number average molecular weight of the imide oligomer M was 1241.
（合成例１４（イミドオリゴマーＮの作製））
３－アミノフェノールの使用量を２１．８３重量部（反応させるアミック酸オリゴマー（Ａ）の酸無水物基に対して１当量）に変更したこと以外は合成例９と同様にして、フェノール性水酸基を有するイミドオリゴマーＮ（イミド化率９４％）を得た。
なお、イミドオリゴマーＮは、１Ｈ－ＮＭＲ、ＧＰＣ、及び、ＦＴ－ＩＲ分析により、上記式（１－２）で表されるイミドオリゴマーを主成分とすることを確認した。また、ＧＰＣ分取、ＦＴ－ＩＲ分析により、イミドオリゴマーＮは、エステル結合を有するイミドオリゴマーの含有割合が８．４％であることを確認した。更に、イミドオリゴマーＮの数平均分子量は１５７１であった。 (Synthesis Example 14 (Production of Imide Oligomer N))
A phenolic hydroxyl group was prepared in the same manner as in Synthesis Example 9 except that the amount of 3-aminophenol used was changed to 21.83 parts by weight (1 equivalent to the acid anhydride group of the amic acid oligomer (A) to be reacted). An imide oligomer N (imidation rate: 94%) was obtained.
The imide oligomer N was confirmed to contain the imide oligomer represented by the above formula (1-2) as a main component by 1 H-NMR, GPC, and FT-IR analysis. Further, it was confirmed by GPC preparative analysis and FT-IR analysis that the content ratio of the imide oligomer N having an ester bond in the imide oligomer N was 8.4%. Furthermore, the number average molecular weight of the imide oligomer N was 1571.
（実施例１～９、比較例１～５）
表１、２に記載された配合比に従い、各材料を撹拌混合し、実施例１～９、比較例１～５の各接着剤を作製した。 (Examples 1 to 9, Comparative Examples 1 to 5)
According to the blending ratios described in Tables 1 and 2, the materials were stirred and mixed to prepare adhesives of Examples 1 to 9 and Comparative Examples 1 to 5.
＜評価＞
実施例及び比較例で得られた各接着剤について以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluation was performed about each adhesive agent obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
（５％重量減少温度）
実施例及び比較例で得られた各接着剤を離型フィルム上に塗工し、乾燥させることにより、２５μｍ厚の接着フィルムを得た。
得られた接着フィルムを１９０℃で１時間加熱することにより硬化させた接着フィルムについて、熱重量測定装置（エスアイアイ・ナノテクノロジー社製、「ＥＸＴＥＡＲ　ＴＧ／ＤＴＡ６２００」）を用いて、４０℃～４５０℃の温度範囲、１０℃／ｍｉｎの昇温条件で５％重量減少温度を測定した。 (5% weight loss temperature)
Each adhesive obtained in Examples and Comparative Examples was coated on a release film and dried to obtain a 25 μm thick adhesive film.
About the adhesive film cured by heating the obtained adhesive film at 190 ° C. for 1 hour, using a thermogravimetric measuring device (“EXTEAR TG / DTA6200”, manufactured by SII Nanotechnology Inc.), 40 ° C. to 450 ° C. A 5% weight loss temperature was measured under a temperature range of 10 ° C. and a temperature increase condition of 10 ° C./min.
（長期耐熱性（接着力））
実施例及び比較例で得られた各接着剤の両面に５０μｍ厚のカプトン（登録商標）を積層し、１９０℃で１時間加熱することにより硬化、接着させた後、１ｃｍ幅の短冊状に切り出して試験片を得た。得られた試験片について、１７５℃で１０００時間熱処理を行った。熱処理後の試験片について、引張試験機（ＯＲＩＥＮＴＥＣ社製、「ＵＣＴ－５００」）を用いて、剥離速度２０ｍｍ／ｍｉｎの条件で接着力を測定した。
接着力が３．４Ｎ／ｃｍ以上であった場合を「○」、３．４Ｎ／ｃｍ未満２．４Ｎ／ｃｍ以上であった場合を「△」、２．４Ｎ／ｃｍ未満であった場合を「×」として長期耐熱性を評価した。 (Long-term heat resistance (adhesive strength))
50 μm thick Kapton (registered trademark) was laminated on both sides of each adhesive obtained in the examples and comparative examples, and cured and adhered by heating at 190 ° C. for 1 hour, and then cut into 1 cm wide strips. A test piece was obtained. The obtained test piece was heat-treated at 175 ° C. for 1000 hours. About the test piece after heat processing, the adhesive force was measured on conditions with a peeling speed of 20 mm / min using the tensile tester (the product made by ORIENTEC, "UCT-500").
The case where the adhesive strength is 3.4 N / cm or more is “◯”, the case where it is less than 3.4 N / cm, the case where it is 2.4 N / cm or more is “Δ”, and the case where it is less than 2.4 N / cm. Long-term heat resistance was evaluated as “×”.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
本発明によれば、長期耐熱性に優れる硬化物に用いることができるイミドオリゴマーを提供することができる。また、本発明によれば、該イミドオリゴマーからなる硬化剤、及び、該硬化剤を用いてなる接着剤を提供することができる。更に、本発明によれば、該イミドオリゴマーの製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the imide oligomer which can be used for the hardened | cured material excellent in long-term heat resistance can be provided. Further, according to the present invention, a curing agent comprising the imide oligomer and an adhesive using the curing agent can be provided. Furthermore, according to this invention, the manufacturing method of this imide oligomer can be provided.

Claims (6)

  1. フェノール性水酸基を有するイミドオリゴマーであって、
    エステル結合を有するイミドオリゴマーの含有割合が７％以下である
    ことを特徴とするイミドオリゴマー。     An imide oligomer having a phenolic hydroxyl group,
    An imide oligomer having a content ratio of an imide oligomer having an ester bond of 7% or less.
  2. 数平均分子量が４００以上４２００以下であることを特徴とする請求項１記載のイミドオリゴマー。 2. The imide oligomer according to claim 1, having a number average molecular weight of 400 or more and 4200 or less.
  3. イミド化率が７０％以上である請求項１又は２記載のイミドオリゴマー。 The imide oligomer according to claim 1 or 2, wherein the imidization ratio is 70% or more.
  4. 請求項１、２又は３記載のイミドオリゴマーからなることを特徴とする硬化剤。 A curing agent comprising the imide oligomer according to claim 1, 2 or 3.
  5. 硬化性樹脂と請求項４記載の硬化剤とを含有することを特徴とする接着剤。 An adhesive comprising a curable resin and the curing agent according to claim 4.
  6. 酸無水物基を有する化合物とフェノール性水酸基を有するモノアミンとを反応させる工程を有し、
    前記フェノール性水酸基を有するモノアミンの使用量が前記酸無水物基を有する化合物の酸無水物基に対して１．５当量以上であることを特徴とするイミドオリゴマーの製造方法。     Having a step of reacting a compound having an acid anhydride group with a monoamine having a phenolic hydroxyl group,
    The manufacturing method of the imide oligomer characterized by the usage-amount of the monoamine which has the said phenolic hydroxyl group being 1.5 equivalent or more with respect to the acid anhydride group of the compound which has the said acid anhydride group.
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