WO2022215743A1 - 硬化用組成物及び硬化物 - Google Patents

硬化用組成物及び硬化物 Download PDF

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WO2022215743A1
WO2022215743A1 PCT/JP2022/017330 JP2022017330W WO2022215743A1 WO 2022215743 A1 WO2022215743 A1 WO 2022215743A1 JP 2022017330 W JP2022017330 W JP 2022017330W WO 2022215743 A1 WO2022215743 A1 WO 2022215743A1
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polyimide precursor
curable composition
oxazoline
absorption peak
polyimide
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PCT/JP2022/017330
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English (en)
French (fr)
Japanese (ja)
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慎治 宇都宮
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住友ファーマフード＆ケミカル株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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

Definitions

  • the present invention relates to, for example, a curable composition that becomes a cured product by curing treatment, and a cured product obtained by curing the curable composition.
  • a curable composition that is cured by a curing treatment for example, a curable composition containing at least a polyimide precursor obtained by partially hydrolyzing the imide bonds of a polyimide resin is known.
  • the polyimide precursor has in its molecule a plurality of cyclic imide structures and a plurality of amic acid structures (carboxy groups and amide groups) capable of forming cyclic imide structures by imidization reaction.
  • the amic acid structure in the polyimide precursor is imidized (dehydration condensation reaction) to form an imide bond, thereby producing a cured product. Since the resulting cured product has heat resistance, electrical insulation, etc., this type of curable composition is used to form a cured product such as an insulating coating material by a curing treatment.
  • Examples of the curable composition as described above include an imide group-containing compound (polyimide precursor) obtained by partially hydrolyzing a polyimide molded article, an epoxy compound, and a blocked isocyanate compound.
  • Patent Document 1 The curable composition described in Patent Document 1 can be cured by a relatively low-temperature curing treatment, can improve the adhesion (adhesion) of the cured product to the adherend, and can improve the heat resistance of the cured product. .
  • an imide group-containing compound obtained by partially hydrolyzing a polyimide molded article, an aqueous solvent, and an amine compound having a boiling point of 85 to 145 ° C.
  • the imide group-containing compound has an absorption peak at a wave number of 1500 cm -1 derived from the benzene ring and an absorption peak at a wave number of 1375 cm -1 derived from the imide group in the infrared spectroscopy chart.
  • Patent Document 2 When the height of the absorption peak at a wave number of 1500 cm ⁇ 1 derived from a benzene ring is S1 and the height of an absorption peak at a wave number of 1375 cm ⁇ 1 derived from an imide group is S2, the ratio of S1/S2 A curable composition having a ratio in the range of 2 to 10 is known (Patent Document 2).
  • the curable composition described in Patent Document 2 has good stability while containing an aqueous solvent such as water, and can be cured by a relatively low-temperature curing treatment.
  • An object of the present invention is to provide a curable composition capable of producing a cured product having uniformity, flexibility, and adhesion to an adherend. .
  • the curable composition according to the present invention is a polyimide precursor in which a part of the imide bond of the polyimide resin is hydrolyzed, and an oxazoline compound having an oxazoline ring in the molecule,
  • the amount of the oxazoline ring of the oxazoline compound is 0.20 mol or more and 1.60 mol or less per 1 mol of the repeating structural unit of the polyimide precursor.
  • the oxazoline compound may be a polymer compound.
  • the curable composition according to the present invention may further contain an aqueous solvent.
  • the polyimide precursor has a benzene ring in the molecule, and the infrared spectroscopic spectrum obtained by infrared spectroscopic analysis of the polyimide precursor has an absorption peak at a wave number of 1500 cm -1 due to the benzene ring.
  • the cured product according to the present invention is obtained by curing the above curable composition.
  • FIG. 2 is a diagram showing a schematic molecular structural formula of each example of polyimide resin before hydrolysis.
  • FIG. 3 is an IR chart of an example polyimide resin before hydrolysis.
  • the curable composition of the present embodiment includes a polyimide precursor in which a portion of the imide bond of the polyimide resin is hydrolyzed, and an oxazoline compound having an oxazoline ring in the molecule,
  • the amount of the oxazoline ring of the oxazoline compound is 0.20 mol or more and 1.60 mol or less per 1 mol of the repeating structural unit of the polyimide precursor. According to the curable composition of the present embodiment, a cured product having uniformity, flexibility, and adhesion to an adherend can be produced.
  • the polyimide precursor has multiple cyclic imide structures and multiple amic acid structures in the molecule.
  • Each amic acid structure contains a carboxy group and an amide group.
  • a carboxy group and an amide group in each amic acid structure can be imidized (dehydration condensation reaction) by curing treatment such as heating to form an imide bond (imide group).
  • imidization creates a new cyclic imide structure.
  • the amic acid structure is a structure obtained by hydrolyzing the imide bond that constitutes the cyclic imide structure
  • the cyclic imide structure is a structure obtained by imidization (dehydration condensation reaction) of the carboxy group and the amide group in the amic acid structure.
  • the polyimide precursor described above is a hydrolyzate of a polyimide resin, it may have a carboxy group at the molecular chain end.
  • a commercially available product can be used as the polyimide resin before hydrolysis.
  • polyimide resin products include the product name “Kapton” series (manufactured by Toray DuPont), the product name “Upilex” series (manufactured by Ube Industries, Ltd.), and the product name “Aurum” (manufactured by Mitsui Chemicals, Inc.). be able to. Specific examples of the molecular structures of these polyimide resins will be described in detail later (see FIG. 1).
  • As the polyimide resin before hydrolysis it is preferable to use a polyimide precursor obtained by hydrolyzing a polyimide resin film or the like, which has conventionally been discarded, from the viewpoint of protecting the global environment. As a result, the polyimide resin can be recycled more actively, and a cured product having uniformity, flexibility, and adhesion to the adherend can be produced.
  • the above polyimide precursor has, for example, a molecular structure represented by the following general formula (1).
  • Ar may include at least one of an aromatic structure, a cyclic saturated hydrocarbon structure, a linear or branched saturated hydrocarbon structure, an ether group, and the like.
  • Ar' may contain at least one of, for example, an aromatic structure, a cyclic saturated hydrocarbon structure, a branched saturated hydrocarbon structure, an ether group, and the like.
  • the repeating structural unit in the above polyimide precursor corresponds to the repeating structural unit in the polyimide resin before hydrolysis.
  • the polyimide resin before hydrolysis has a structure in which structural units of a reaction product of a diamine monomer and a tetracarboxylic acid (dianhydride) monomer are repeated in the molecule.
  • the above polyimide precursor also has similar repeating structural units in its molecule.
  • part of the cyclic imide structure is hydrolyzed to an amic acid structure, so the part in parentheses on the left side of general formula (1) is also represented by general formula (1)
  • the parts in parentheses on the right side of are also repeating structural units.
  • the number of moles of the repeating structural unit can be calculated as follows.
  • the repeating structural unit of the polyimide resin before hydrolysis is, for example, the portion in parentheses on the right side of the general formula (1).
  • the number of moles of the repeating structural unit can be calculated by dividing (dividing) the mass of the polyimide resin by the molecular weight of the portion inside the right parenthesis.
  • the number of nitrogen atoms in the repeating structural unit is two. Therefore, the amount of the oxazoline ring of the oxazoline compound with respect to 1 mol of the repeating structural unit of the polyimide precursor can also be expressed as the amount per 2 mol of nitrogen atoms in the polyimide precursor.
  • the above polyimide precursor is a hydrolyzate obtained by partially hydrolyzing a plurality of imide bonds in the polyimide resin, so the above polyimide precursor is represented on the left side of general formula (1)
  • the molecule has both the amic acid structure (portion indicated by ⁇ ) shown on the right side and the cyclic polyimide structure (portion indicated by ⁇ ) shown on the right side.
  • the above polyimide precursor preferably has an aromatic structure (particularly a benzene ring structure) in its molecule.
  • an aromatic structure particularly a benzene ring structure
  • the cured product can exhibit higher heat resistance.
  • the molar ratio of the number of nitrogen atoms to one benzene ring may be 0.2 or more and 1.0 or less, or 0.4 or more and 0.8 or less.
  • Such a molar ratio can be analyzed by infrared spectroscopic analysis, NMR measurement, or the like, which will be described later.
  • Ar may be Ar-1 (structure having one benzene ring) or Ar-2 (structure having two benzene rings), as shown below.
  • Ar' may be Ar'-1 (structure having two benzene rings) or Ar'-2 (structure having one benzene ring).
  • Ar may be Ar-1 (having one benzene ring) and Ar' may be Ar'-1 (having two benzene rings).
  • the polyimide precursor of this embodiment is a hydrolysis reaction product of polyimide resin.
  • the method for producing the above polyimide precursor will be described in detail later.
  • the average molecular weight (mass average molecular weight) of the polyimide precursor may be, for example, 1,000 or more and 100,000 or less.
  • the average molecular weight (weight average molecular weight) of the polyimide precursor is preferably 3,000 or more, more preferably 5,000 or more.
  • the average molecular weight (weight average molecular weight) is preferably 60,000 or less, more preferably 30,000 or less. When the weight average molecular weight of the polyimide precursor is within the above range, the solubility in the solvent described later becomes better.
  • the mass average molecular weight of the polyimide precursor is determined by gel permeation chromatography (GPC) measurement. Details of the GPC measurement conditions are as follows. Device name: Tosoh product name “HLC-8320GPC” Detector: Differential refractive index (RI) detector Column: Styrenedivinylbenzene (average particle size: 3 ⁇ m, average pore size: 2 nm) Column temperature: 40°C Standard substance for creating a calibration curve: polyethylene glycol Data processing software: software attached to the above equipment Eluent: N,N-dimethylacetamide (DMAc) [Number average molecular weight (Mn), mass average molecular weight (Mw), molecular weight distribution (Mw/Mn)]
  • DMAc N,N-dimethylacetamide
  • the Mw/Mn of the polyimide precursor determined by the GPC measurement is preferably 1.0 or more, more preferably 1.5 or more. Such Mw/Mn is preferably 3.0 or less, more preferably 2.5 or less. When the Mw/Mn of the polyimide precursor is 1.0 or more and 3.0 or less, there is an advantage that the physical properties of the cured product are made more uniform and stabilized. In the hydrolysis reaction product of the polyimide resin, that is, in the above-described polyimide precursor produced by hydrolysis of the polyimide resin, the Mw/Mn can fall within the above range.
  • each wavenumber shown below is a numerical value for defining the absorption peak in the vicinity of the wavenumber, as is commonly judged in the technical field of infrared spectroscopic analysis. In other words, each wavenumber shown below does not represent only an absorption peak having a peak apex at that wavenumber.
  • the infrared spectroscopic analysis of the polyimide precursor is carried out under the following measurement conditions. Infrared spectroscopic analysis can be performed using a commercially available measuring instrument under the following measurement conditions.
  • Device name Fourier transform infrared spectrophotometer (“FT/IR-4600” manufactured by JASCO Corporation) Analysis method: Attenuated Total Reflection (ATR) Measurement wavenumber range: 4000 cm -1 to 400 cm -1
  • the polyimide precursor of the present embodiment exhibits an absorption peak P1 due to a benzene ring at (near) 1500 cm -1 wavenumber in the infrared spectrum when analyzed by infrared spectroscopy, as shown in FIG. 5, for example.
  • the polyimide precursor in the present embodiment exhibits an absorption peak P2 due to the imide group at (near) 1375 cm -1 wavenumber in the infrared spectroscopic spectrum when analyzed by infrared spectroscopy, as shown in FIG. 5, for example. Since the polyimide precursor has an imide group in its molecule, a cured product produced by a curing treatment such as heating has good heat resistance.
  • the polyimide precursor in the present embodiment exhibits an absorption peak P3 due to an amide group (-NHCO-) at (near) 1600 cm -1 wavenumber, as shown in Fig. 5, for example. Since the polyimide precursor has an amide group in its molecule, it can be cured at a relatively low temperature.
  • the polyimide precursor in the present embodiment exhibits an absorption peak P4 due to a carboxy group (—COOH) at (near) 1413 cm ⁇ 1 wavenumber, as shown in FIG. 5, for example. Since the polyimide precursor has a carboxyl group in the molecule, it has good solubility in the solvent described later, and the cured product after curing treatment can have good adhesion.
  • the polyimide precursor in this embodiment exhibits an absorption peak P5 due to a carbonyl group (—CO—) at (near) 1710 cm ⁇ 1 wavenumber, as shown in FIG. 5, for example.
  • the polyimide precursor has a carbonyl group in its molecule, and thus has good solubility in the solvent described below.
  • the imide group amount (absorption peak height), the amide group amount (absorption peak height), and the carboxy group amount in the polyimide precursor can be an index indicating the degree of hydrolysis of the polyimide resin.
  • the degree of hydrolysis can be confirmed by determining the height of the absorption peak of each functional group with respect to the height of the absorption peak of the benzene ring whose chemical structure does not change even by hydrolysis.
  • the height of the absorption peak P2 due to the imide group, the height of the absorption peak P3 due to the amide group, and the absorption due to the carboxy group can be an index indicating the degree of hydrolysis of the polyimide resin.
  • the above height ratios P1/P2, P1/P3, P1/P4 can be employed.
  • each ratio of the heights of the absorption peaks described above is calculated as follows.
  • the horizontal axis is the wavenumber [cm -1 ]
  • the vertical axis is the transmittance [%] (upper side is 100% transmittance) Infrared spectrum spectrum (IR chart).
  • IR chart Infrared spectrum spectrum
  • the baseline height [%] is 90 [%]
  • the height of the absorption peak P1 is 70 [%]
  • the height of the absorption peak P2 is 80 [%]
  • ) 2.0
  • the ratio of the height of the absorption peak P1 due to the benzene ring to the height of the absorption peak P2 due to the imide group P1/P2
  • the ratio of the height of the absorption peak P1 at a wave number of 1500 cm -1 due to the benzene ring to the height of the absorption peak P2 at a wave number of 1375 cm -1 due to the imide group is preferably 2 or more, and may be 3 or more.
  • the ratio (P1/P2) is preferably 10 or less, more preferably 9 or less, and more preferably 5 or less.
  • the polyimide precursor can be cured at a lower temperature because the height ratio (P1/P2) is within the above range. Moreover, it can have better solubility in the solvent described later. In addition, the cured product that has undergone the curing treatment can have better adhesion, uniformity and flexibility.
  • the ratio of the height of the absorption peak P1 due to the benzene ring to the height of the absorption peak P3 due to the amide group is preferably 2 or more, more preferably 3 or more. Also, the ratio (P1/P3) is preferably 20 or less, more preferably 12 or less, even more preferably 10 or less.
  • the polyimide precursor can have better solubility in the solvent described below.
  • the cured product that has undergone the curing treatment can have better adhesion, uniformity and flexibility.
  • the ratio of the height of the absorption peak P1 at a wave number of 1500 cm -1 due to the benzene ring to the height of the absorption peak P4 at a wave number of 1413 cm -1 due to the carboxy group is preferably 2 or more, more preferably 3 or more. Also, the ratio (P1/P4) is preferably 20 or less, more preferably 12 or less, and even more preferably 11 or less. When the height ratio (P1/P4) is within the above range, the polyimide precursor can have better solubility in the solvent described below. In addition, the cured product that has undergone the curing treatment can have better adhesion, uniformity and flexibility.
  • the benzene ring in the above polyimide precursor may be an unsubstituted benzene ring, or a substituted benzene ring in which hydrogen atoms respectively bonded to a plurality of carbon atoms constituting the benzene ring are substituted with substituents.
  • the substituent of the substituted benzene ring is, for example, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkoxysilyl group having 1 to 3 carbon atoms, or a trifluoromethyl group. There may be.
  • the benzene ring in the polyimide precursor is an unsubstituted benzene ring, a benzene ring substituted with an alkoxysilyl group having 1 to 3 carbon atoms, or a benzene ring substituted with a trifluoromethyl group. More preferably, the benzene ring in the polyimide precursor is an unsubstituted benzene ring.
  • a monovalent substituent such as a halogen atom
  • the monovalent group bonded to the carbon atoms constituting the benzene ring is preferably a hydrogen atom (--H).
  • polyimide precursor for example, a polyimide precursor represented by formula (3) described later can be used.
  • a partial hydrolyzate obtained by partially hydrolyzing the product name "Kapton H" manufactured by DuPont-Toray Co., Ltd.
  • the polyimide precursor in the present embodiment can be obtained by subjecting a discarded polyimide resin film to hydrolysis treatment.
  • the oxazoline compound contained in the curable composition of this embodiment is a compound containing one or more oxazoline rings in the molecule.
  • Oxazoline compounds include low-molecular-weight compounds and high-molecular-weight compounds.
  • the oxazoline compound may be a low-molecular-weight oxazoline compound with a molecular weight of less than 1,000, or a high-molecular-weight oxazoline compound with a molecular weight of 1,000 or more.
  • Examples of low-molecular-weight oxazoline compounds include compounds in which two oxazoline rings are directly bonded to each other, compounds in which two oxazoline rings are bonded via an organic group, or compounds having three oxazoline rings. be done.
  • Examples of compounds in which two oxazoline rings are directly bonded to each other include 2,2'-bis(2-oxazoline) and 2,2'-bis-4-benzyl-2-oxazoline.
  • Compounds in which two oxazoline rings are bonded via an organic group include 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydro-2- oxazolyl)benzene, 2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine, 2,2'-methylenebis(4-tert-butyl-2-oxazoline), 2,2'-methylenebis(4-phenyl -2-oxazoline) and the like.
  • Compounds having three oxazoline rings include 1,2,4-tris-(2-oxazoline-2-yl)benzene and the like.
  • the polymer oxazoline compound includes, for example, an oxazoline ring-containing acrylic polymer having an oxazoline ring at the end of a side chain and polymerized with at least an acrylic acid ester.
  • the oxazoline ring-containing acrylic polymer is a polymer compound obtained by polymerizing an acrylic acid ester monomer having an oxazoline ring as at least one of the monomers.
  • Such oxazoline ring-containing acrylic polymers may be homopolymers or copolymers.
  • oxazoline ring-containing acrylic polymer for example, the product name "Epocross WS” series (manufactured by Nippon Shokubai Co., Ltd.), “Epocross K-2000” series (manufactured by Nippon Shokubai Co., Ltd.), and the like can be used.
  • the monovalent group bonded to the carbon atoms constituting the oxazoline ring is preferably only a hydrogen atom (--H) as shown in formula (2) below.
  • oxazoline compound a high molecular weight oxazoline compound is preferable in terms of better reactivity with the polyimide precursor and better storage stability of the cured product after the curing treatment.
  • An oxazoline ring-containing acrylic polymer having an oxazoline ring at the end of is more preferable.
  • the oxazoline group content (oxazoline ring content) of the oxazoline compound is preferably 1 [mmol/g] or more and 10 [mmol/g] or less, more preferably 3 [mmol/g] or more.
  • the amount of oxazoline groups in the high-molecular-weight oxazoline compound can be calculated based on the quantitative ratio between the monomer unit having an oxazoline group and other monomer units constituting the high-molecular-weight oxazoline compound. Such a ratio can be determined, for example, based on the peak intensity derived from the oxazoline group and the peak intensity derived from other monomers in the 1 H-NMR analysis results by a nuclear magnetic resonance spectrometer (NMR). can.
  • oxazoline compound one type may be employed alone, or two or more types may be employed in combination.
  • the amount of the oxazoline ring of the oxazoline compound is 0.20 mol or more and 1.60 mol or less per 1 mol of the repeating structural unit of the polyimide precursor.
  • the amount of the oxazoline ring may be 0.30 mol or more, 0.35 mol or more, or 0.39 mol or more.
  • the amount of the oxazoline ring may be 1.50 mol or less, or may be 1.20 mol or less.
  • the polyimide precursor is preferably a partial hydrolyzate of a polyimide resin
  • the oxazoline compound is a polymeric oxazoline compound (for example, a oxazoline ring-containing acrylic polymer).
  • Partially hydrolyzed polyimide precursors have a higher amount of low-molecular-weight compounds than polyimide precursors composed of monomers, and therefore may be hard and brittle when cured.
  • the curable composition of the present embodiment further contains a high-molecular-weight oxazoline compound, the physical properties of being hard and brittle can be suppressed. Therefore, the adhesion of the cured product to the adherend can be improved.
  • the curable composition of the present embodiment preferably contains 5 parts by mass or more and 95 parts by mass or less of the oxazoline compound with respect to 100 parts by mass of the polyimide precursor.
  • the curable composition of the present embodiment may contain 8 parts by mass or more, or 10 parts by mass or more of the oxazoline compound based on 100 parts by mass of the polyimide precursor.
  • the curable composition of the present embodiment may contain 90 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less of the oxazoline compound with respect to 100 parts by mass of the polyimide precursor.
  • the curable composition of this embodiment may contain a solvent.
  • Solvents include non-polar solvents and polar solvents. Examples of non-polar solvents include hydrocarbon solvents containing only carbon atoms and hydrogen atoms in the molecule, chlorine solvents such as carbon tetrachloride, and the like.
  • the curable composition of the present embodiment preferably contains a polar solvent for dissolving both the polyimide precursor and the oxazoline compound.
  • a polar solvent is a compound that also contains atoms other than carbon atoms and hydrogen atoms (eg, oxygen atoms, nitrogen atoms) in the molecule.
  • both the polyimide precursor and the oxazoline compound are dissolved in a polar solvent.
  • Polar solvents include amine solvents, amide solvents, ketone solvents, ether solvents, pyrrolidone solvents, glycol ether solvents, ester solvents, alcohol solvents, polyhydric alcohol solvents, halogen solvents, water, etc. is mentioned.
  • amine-based solvents examples include ammonia (water), diethylamine, ethylethanolamine, diethanolamine, triethanolamine, monoethanolamine, monopropanolamine, isopropanolamine, triethylamine, tributylamine, dimethylaminoethanol, diethylaminoethanol, and methylethanol.
  • amide solvents examples include N,N-dimethylformamide and N,N-dimethylacetamide.
  • Ketone solvents include, for example, methyl ethyl ketone, methyl isobutyl ketone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone and the like.
  • ether solvents include tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, methylphenyl ether and the like.
  • pyrrolidone-based solvents include N-methyl-2-pyrrolidone and the like.
  • Glycol ether solvents include, for example, methyldiglyme, ethyldiglyme, methyltriglyme, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, 1-methoxy-2-propanol, ethylene glycol monoethyl ether, etc. Or those acetates etc. are mentioned.
  • ester solvents include ethyl acetate, butyl acetate, isopropyl acetate and the like.
  • alcohol solvents examples include methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol and the like.
  • polyhydric alcohol solvents examples include glycerin.
  • halogen-based solvents include chloroform and dichloromethane.
  • Aqueous solvents are preferred as polar solvents.
  • Aqueous solvents are water or hydrophilic organic solvents that are soluble in water in any ratio relative to water.
  • the curable composition of the present embodiment more preferably contains an aqueous solvent among polar solvents, and more preferably contains at least water as an aqueous solvent.
  • hydrophilic organic solvents examples include amine solvents such as dimethylaminoethanol and diethanolamine, amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, Alcohol solvents such as methyl alcohol, ethyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether , 1-methoxy-2-propanol and propylene glycol monomethyl ether, and polyhydric alcohol solvents such as glycerin.
  • amine solvents such as dimethylaminoethanol and diethanolamine
  • amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide
  • pyrrolidone solvents such as N-methyl-2-pyr
  • Amine-based solvents have a high affinity for polyimide precursors and cured products of such polyimide precursors. Therefore, for the purpose of improving the solubility of the polyimide precursor in the curable composition, or for the purpose of forming a nearly uniform cured product, it is preferable that the curable composition contains an amine solvent.
  • dimethylaminoethanol and diethanolamine as amine-based solvents have relatively high boiling points, so they gradually volatilize when the curable composition is subjected to curing treatment by heating. As a result, the cured product in which curing has progressed can form a more uniform cured film.
  • a plurality of types of the above polar solvents may be used in combination.
  • the above aqueous solvents may also be used in combination of multiple types.
  • the curable composition of the present embodiment may contain 60% by mass or more of a polar solvent (particularly an aqueous solvent). Moreover, a polar solvent (especially an aqueous solvent) may be included in an amount of 99% by mass or less.
  • the total weight ratio of the polyimide precursor and the oxazoline compound may be 1% by weight or more. Moreover, such a ratio may be 40% by mass or less.
  • the above curing composition includes an imidization reaction catalyst, a surfactant, an antioxidant, a leveling agent, an antistatic agent, a dye or pigment, a viscosity modifier, an antifoaming agent, a stabilizer,
  • a resin other than the polyimide resin or a coupling agent may be further included.
  • the other resins include acrylic resins, fluorine resins, epoxy resins, phenol resins, silicone resins, olefin resins, polyester resins, polyamide resins, and hydrocarbon resins. These components can be blended for the purpose of improving good workability during application of the curable composition, or improving various properties of the cured product that has undergone curing treatment.
  • the properties of the curable composition of the present embodiment are not particularly limited, but are liquid, for example.
  • the curable composition of the present embodiment may be solid.
  • the curable composition of the present embodiment can be produced, for example, by mixing the above polyimide precursor, the oxazoline compound, and, if necessary, the above polar solvent.
  • a polyimide precursor can be obtained by partially hydrolyzing a polyimide resin.
  • a method for producing such a curable composition includes, for example, A hydrolysis step of preparing a polyimide precursor by hydrolyzing a polyimide resin in the presence of water and an alkaline compound; A curable composition is prepared by mixing the polyimide precursor and the oxazoline compound so that the amount of the oxazoline ring of the oxazoline compound is 0.20 mol or more and 1.60 mol or less per 1 mol of the repeating structural unit of the polyimide precursor. and a mixing step.
  • the polyimide resin before hydrolysis is not particularly limited as long as it produces the polyimide precursor represented by the above general formula (1), for example.
  • Specific examples of the molecular structure of the polyimide resin are shown in formulas (A) to (J) in FIG.
  • polyimide resin partially hydrolyzed in the hydrolysis step for example, discarded polyimide resin can be used.
  • polyimide resin molded articles, more specifically polyimide resin film waste, and the like can be used.
  • the polyimide resin can be hydrolyzed under temperature conditions of, for example, 50° C. or higher and 100° C. or lower.
  • the duration of the hydrolysis treatment is, for example, 1 hour or more and 24 hours or less.
  • sodium hydroxide or potassium hydroxide is used as an alkaline compound.
  • the hydrolysis treatment may be continued until the molecular weight of the polyimide precursor reaches the above-mentioned predetermined range. Further, for example, the hydrolysis treatment may be continued until the ratio of the heights of the absorption peaks in the infrared spectroscopy spectrum obtained by infrared absorption analysis of the polyimide precursor falls within the above-described predetermined range.
  • the hydrolysis treatment can be performed until the weight average molecular weight of the polyimide precursor reaches 1,000 or more and 100,000 or less. Further, in the hydrolysis step, for example, the hydrolysis treatment can be performed until the Mw/Mn of the polyimide precursor obtained by the GPC measurement described above becomes 1 or more and 4 or less.
  • the hydrolysis treatment in the infrared spectrum of the polyimide precursor, the ratio of the height of the absorption peak P1 at a wave number of 1500 cm due to the benzene ring to the height of the absorption peak P2 due to the imide group at a wave number of 1375 cm -1 ( The hydrolysis treatment can be carried out until P1/P2) becomes 2 or more and 10 or less.
  • the hydrolysis step in the infrared spectrum of the polyimide precursor, the ratio of the height of the absorption peak P1 at a wave number of 1500 cm -1 due to the benzene ring to the height of the absorption peak P3 at a wave number of 1600 cm -1 due to the amide group ( The hydrolysis treatment can be carried out until P1/P3) becomes 2 or more and 20 or less.
  • the hydrolysis treatment in the infrared spectroscopic spectrum of the polyimide precursor, the ratio of the height of the absorption peak P1 at a wave number of 1500 cm -1 due to the benzene ring to the height of the absorption peak P4 at a wave number of 1413 cm -1 due to the carboxy group ( The hydrolysis treatment can be carried out until P1/P4) becomes 2 or more and 20 or less.
  • the next mixing step may be performed with the polyimide precursor dissolved.
  • the solvent used in the hydrolysis treatment may be volatilized by drying treatment or the like.
  • the polyimide precursor obtained by the hydrolysis treatment as described above is represented, for example, by the following formula (3).
  • the polyimide precursor represented by formula (3) has a structural unit a and a structural unit b in its molecule.
  • Structural unit a has a portion where the imide group is hydrolyzed (a portion where the cyclic imide structure becomes an amic acid structure).
  • Structural unit b has a portion in which the imide group is not hydrolyzed and remains.
  • structural unit a (left portion) and structural unit b (right portion) correspond to the repeating structural units described above.
  • the polyimide precursor may have two carboxy groups at the terminal of the molecular chain. These carboxy groups can be generated by complete hydrolysis of the cyclic imide structure by hydrolysis treatment.
  • the hydrolysis step by increasing the temperature or increasing the pH of the reaction solution (making the reaction solution more alkaline), the weight average molecular weight of the polyimide precursor can be reduced, and the amic acid in the polyimide precursor The proportion of structure can be increased.
  • the aforementioned Mw/Mn can be reduced by lengthening the hydrolysis reaction time in the hydrolysis step.
  • the mixing step for example, the powdery polyimide precursor prepared as described above, the oxazoline compound, and the solvent are mixed.
  • a common device can be used for mixing. If necessary, they may be mixed and stirred while being heated.
  • the polyimide precursor and the oxazoline compound are mixed so that the oxazoline compound has a specific amount ratio as described above with respect to 100 parts by mass of the polyimide precursor.
  • the curable composition may be produced by mixing the powdery polyimide precursor and an aqueous solution in which the oxazoline compound is dissolved. It is preferable to dissolve the polyimide precursor and the oxazoline compound in the solvent in the mixing step to prepare a curable composition in the form of a solution, and more preferably to prepare the curable composition in the form of an aqueous solution. Due to the fact that the curable composition is in the form of a solution (particularly in the form of an aqueous solution), the curable composition can be applied in various ways. Therefore, there is an advantage that the application range of the curable composition is widened. In addition, since the curable composition is an aqueous solution, it is not flammable, so there is an advantage that safety is enhanced.
  • the curable composition described above is used by being applied to an adherend such as an electric wire, film, flexible circuit board, or semiconductor.
  • the applied curable composition is subjected to a curing treatment such as heating to form a cured product (specifically, a cured resin or the like).
  • the above-mentioned curing composition is, for example, a curing composition for fiber coating, a curing composition for resin film coating, a curing composition for resin molding coating, or a curing composition for metal coating may be either
  • the above-mentioned curable composition that becomes a cured product e.g., cured resin molded article
  • is used for example, as a film, as a paint, as an electrical insulating material, as a heat-resistant component, as a heat-resistant container, as a fiber, etc. may be used in
  • the method of using the curable composition is not particularly limited.
  • the above-described curing composition is applied onto an object to be coated (an adherend such as a substrate), or impregnated into the object and then cured to obtain a cured product. (such as a cured coating film) can be formed.
  • an adherend such as a substrate
  • a cured coating film can be formed.
  • general application methods such as spray coating, dip coating, spin coating, die coating, and gravure coating can be used.
  • the solvent contained in the curable composition can be volatilized by subjecting the curable composition applied to the substrate and the substrate to heat treatment.
  • the heat treatment is not particularly limited, and general methods such as hot air heat treatment and infrared heat treatment can be employed.
  • the heating conditions for the heat treatment are, for example, 60° C. to 100° C. for 30 minutes.
  • a heat treatment can then be performed at a higher temperature to further promote thermosetting.
  • Such a heat treatment at a higher temperature is not particularly limited, either, and can be carried out by a general method.
  • the temperature condition for the heat treatment at high temperature may be 200°C or higher, preferably 300°C to 400°C.
  • the heating time may be 10 minutes to 5 hours, preferably 10 to 60 minutes.
  • the heat treatment can be performed under an inert gas atmosphere or under reduced pressure conditions.
  • curable composition and cured product of the present invention are as exemplified above, but the present invention is not limited to the above-exemplified embodiments. Moreover, in the present invention, various forms employed in general curable compositions and the like can be employed as long as the effects of the present invention are not impaired.
  • Matters disclosed by this specification include the following. (1) A polyimide precursor in which a part of the imide bond of the polyimide resin is hydrolyzed, and an oxazoline compound having an oxazoline ring in the molecule, A curable composition, wherein the amount of the oxazoline ring of the oxazoline compound is 0.20 mol or more and 1.60 mol or less per 1 mol of the repeating structural unit of the polyimide precursor. (2) The curable composition according to (1) above, wherein the oxazoline compound is either a low-molecular-weight oxazoline compound having a molecular weight of less than 1,000 or a high-molecular-weight oxazoline compound having a molecular weight of 1,000 or more.
  • the polyimide precursor has a benzene ring in the molecule
  • An infrared spectroscopic spectrum obtained by infrared spectroscopic analysis of the polyimide precursor shows an absorption peak P1 at a wave number of 1500 cm ⁇ 1 due to a benzene ring and an absorption peak P2 at a wave number of 1375 cm ⁇ 1 due to an imide group
  • the curable composition according to any one of (1) to (6) above, wherein the ratio (P1/P2) of the height of the absorption peak P1 to the height of the absorption peak P2 is 2 or more and 10 or less.
  • the polyimide precursor has a benzene ring in the molecule
  • An infrared spectroscopic spectrum obtained by infrared spectroscopic analysis of the polyimide precursor shows an absorption peak P1 at a wave number of 1500 cm ⁇ 1 due to a benzene ring and an absorption peak P3 at a wave number of 1600 cm ⁇ 1 due to an amide group
  • the curable composition according to any one of (1) to (7) above, wherein the ratio (P1/P3) of the height of the absorption peak P1 to the height of the absorption peak P3 is 2 or more and 20 or less.
  • the polyimide precursor has a benzene ring in the molecule
  • An infrared spectroscopic spectrum obtained by infrared spectroscopic analysis of the polyimide precursor shows an absorption peak P1 at a wave number of 1500 cm ⁇ 1 due to a benzene ring and an absorption peak P4 at a wave number of 1413 cm ⁇ 1 due to a carboxy group
  • the curable composition according to any one of (1) to (8) above, wherein the ratio (P1/P4) of the height of the absorption peak P1 to the height of the absorption peak P4 is 2 or more and 20 or less.
  • the above (1) which is any one of a curing composition for fiber coating, a curing composition for resin film coating, a curing composition for resin molding coating, or a curing composition for metal coating.
  • the curable composition according to any one of (9).
  • (11) A cured product obtained by curing the curable composition according to any one of (1) to (10) above.
  • (12) The cured product according to (11) above, which is used for film applications, paint applications, electrical insulating material applications, heat-resistant parts applications, heat-resistant container applications, or fiber applications.
  • (13) A curable composition for forming a cured product by applying the curable composition described in any one of the above (1) to (10) onto an object to be coated or impregnating the object and then curing the composition. how to use things.
  • an alkaline aqueous solution was prepared by dissolving 40 g of potassium hydroxide in 600 g of deionized water in a 1000 mL vessel equipped with a stirrer. 100 g of pulverized polyimide resin was added to this alkaline aqueous solution, and hydrolysis treatment was carried out at 80 to 90° C. for 3 hours to obtain a crude polyimide precursor solution. Subsequently, the crude polyimide precursor solution was neutralized to obtain a deposit. The precipitate was filtered and washed with deionized water. Furthermore, after removing neutralized salt compounds and excess acidic compounds, drying treatment was performed. In addition, pulverization treatment was performed so as to form a powder.
  • FIG. 2 shows a GPC chart when the polyimide precursor (A-1), which is a hydrolyzate of the polyimide resin, was measured under the above-described gel permeation chromatography (GPC) measurement conditions.
  • GPC gel permeation chromatography
  • FIG. 3 shows an infrared spectroscopic spectrum (IR chart) when the polyimide resin before hydrolysis of the polyimide precursor (A-1) was subjected to infrared spectroscopic analysis under the analysis conditions and analysis method described above.
  • FIG. 4 shows an infrared spectrum (IR chart) obtained by similarly analyzing the polyimide resin before hydrolysis of the polyimide precursor (A-3).
  • FIG. 5 shows an infrared spectroscopic spectrum (IR chart) when the polyimide precursor (A-1), which is a hydrolyzate of the polyimide resin, was subjected to infrared spectroscopic analysis under the analysis conditions and analysis method described above.
  • FIG. 6 shows an infrared spectroscopic spectrum (IR chart) when the polyimide precursor (A-2), which is a hydrolyzate of the polyimide resin, was similarly analyzed.
  • FIG. 7 shows an infrared spectroscopic spectrum (IR chart) when the polyimide precursor (A-3), which is a hydrolyzate of the polyimide resin, was similarly analyzed.
  • Example 1 (Examples 1 to 9, Comparative Examples 1 to 13)
  • the above raw materials were mixed in the amounts shown in the following tables, and (A-1) was dissolved to prepare the curable compositions of Examples and Comparative Examples.
  • Table 1 shows the composition of each curing composition.
  • Each curable composition was produced such that the total amount (solid content) of (A) and (B) was about 20% by mass. Specifically, 68.1 g of ion-exchanged water and 11.6 g of diethanolamine were placed in a container equipped with a stirrer and heated to 60°C. Next, 20 g of the polyimide precursor (A) was added and stirred for 60 minutes.
  • ⁇ Uniformity of cured coating> The curable composition of each example and each comparative example was applied onto an aluminum foil (manufactured by UACJ Foil Corporation) using a bar coater. After coating, the composition was pre-dried at 60° C. for 30 minutes, and then cured by heating at 300° C. for 30 minutes to prepare a cured coating film (cured product) having a thickness of 20 ⁇ m. The uniformity of the cured coating was determined by visual observation. Good ( ⁇ ): Brown transparent film Somewhat good ( ⁇ ): Slightly cloudy Poor ( ⁇ ): Cloudy
  • Adhesion of cured coating The adhesiveness of the cured coating film of each example and each comparative example was measured by making cuts in a grid pattern with a cutter knife and performing a peeling operation with the adhesive tape. The measurement was carried out according to JIS K5600-5-6:1999 General Test Methods for Paints, Part 5: Mechanical properties of coating film, Section 6: Adhesion (cross-cut method, so-called cross-cut test). A polyimide film and SUS were used as adherends. Adhesion was evaluated according to the following criteria. Good ( ⁇ ): Remaining number is 90 to 100/100 Somewhat good ( ⁇ ): The number of remaining is 50 to 90/100 Defective (x): Remaining number is 0 to 50/100
  • Table 2 shows the results of evaluating each of the above performances for each curing composition. It was confirmed that the uniformity of the cured coating films of Comparative Examples 4 to 7 was not good, so other evaluations (flexibility and adhesion) were not performed.
  • the reason why the cured product (cured coating film) of the curable composition of the example can exhibit good performance is considered as follows.
  • a curing treatment such as heating, at least part of the plurality of amic acid structures in the polyimide precursor is imidized.
  • a new cyclic polyimide structure is formed.
  • the carboxy group in the amic acid structure of a portion of the polyimide precursor and the carboxy group at the molecular chain end of the polyimide precursor can form an amide ester bond with the oxazoline ring of the oxazoline compound.
  • the polyimide precursor and a relatively large amount of the oxazoline compound can be bonded.
  • the cured product (cured resin, cured coating film, etc.) obtained by curing the curable composition is , can exhibit good adhesion to the adherend. Moreover, cracking of the cured product can be suppressed, and the cured product can have flexibility. In addition, the cured product is also excellent in terms of uniformity.
  • the cured coating films obtained by curing the curable compositions of Examples have good uniformity and good adhesion to adherends. , and was also good in terms of bendability (that is, flexibility). That is, the cured coating film obtained by curing the curable composition of the example had uniformity, flexibility, and adhesion to the adherend at the same time.
  • a curable composition that does not contain an oxazoline compound or a curable composition that contains less than a specific amount of an oxazoline compound the internal stress of the cured coating film cured by the curing treatment cannot be relaxed, and the adhesion of the cured coating film is reduced. This is thought to be due to the lower flexibility and flexibility.
  • each curing composition containing the above-mentioned polyimide precursors (A-2) and (A-3) shown as a reference can also form a good cured coating film.
  • the curable composition of the present invention is applied to, for example, metals, resin moldings, fibers, and films in order to produce cured products having properties such as heat resistance, electrical insulation, and chemical resistance. be.

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