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WO2010107045A1 - Résine de polyimide, composition de résine durcissable et objet durci à partir de celle-ci - Google Patents

Résine de polyimide, composition de résine durcissable et objet durci à partir de celle-ci Download PDF

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Publication number
WO2010107045A1
WO2010107045A1 PCT/JP2010/054499 JP2010054499W WO2010107045A1 WO 2010107045 A1 WO2010107045 A1 WO 2010107045A1 JP 2010054499 W JP2010054499 W JP 2010054499W WO 2010107045 A1 WO2010107045 A1 WO 2010107045A1
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Prior art keywords
polyimide resin
resin
epoxy
acid anhydride
tricarboxylic acid
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Ceased
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PCT/JP2010/054499
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English (en)
Japanese (ja)
Inventor
誠一 宇野
栄寿 一ノ瀬
聡子 伊東
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DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2011504856A priority Critical patent/JPWO2010107045A1/ja
Publication of WO2010107045A1 publication Critical patent/WO2010107045A1/fr
Anticipated expiration legal-status Critical
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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
    • C08G73/14—Polyamide-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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
    • C08G18/345—Polycarboxylic acids having at least three carboxylic acid groups having three carboxylic acid groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • 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
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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 a polyimide resin, a curable resin composition containing the polyimide resin, and a cured product thereof.
  • the present invention is a field that requires transparency in addition to heat resistance, for example, a field for optical materials, a solder resist material for printed wiring boards, a protective material and insulation for household appliances such as refrigerators and rice cookers.
  • the present invention relates to a polyimide resin that can be suitably used in the field of display devices such as liquid crystal alignment films and protective films for color filters, a curable resin composition containing the polyimide resin, and a cured product thereof.
  • Polyimide resin is excellent in heat resistance and mechanical properties, and has been used in various fields mainly in the electrical and electronic industries. In recent years, it has been used as a general-purpose solvent such as EDGA (diethylene glycol monoethyl ether acetate) for the purpose of reducing the burden on the environment. The ability to dissolve has been sought.
  • polyimide resins are expected to be used in fields where transparency of cured products such as liquid crystal displays is required in view of heat resistance and mechanical properties. In these fields, for example, light transmittance from the visible to the ultraviolet region (around 300 nm) is required.
  • a polyimide resin that dissolves in a general-purpose solvent for example, a polyimide resin obtained by reacting an isocyanurate-type polyisocyanate (a1) of an isocyanate having an aliphatic structure with trimellitic anhydride is disclosed (for example, Patent Documents). 1).
  • the cured product obtained by using the polyimide resin disclosed in Patent Document 1 has transparency such as insufficient light transmittance particularly in the ultraviolet region (around 300 nm) in light transmittance measurement. Is not enough.
  • An object of the present invention is a curable resin composition that is soluble in a general-purpose solvent and that can provide a cured product (cured coating film) that has high light transmittance from the visible region to the ultraviolet region near 300 nm, and is preferable for this preparation.
  • the object is to provide a polyimide resin that can be used.
  • the present inventors have obtained a polyimide resin obtained by using a tricarboxylic acid anhydride having an aliphatic structure in place of the tricarboxylic acid anhydride having an aromatic structure such as trimellitic anhydride in Patent Document 1.
  • a curable resin composition capable of obtaining a cured coating film that is soluble in a general-purpose solvent and excellent in heat resistance and light transmittance was obtained, and the present invention was completed.
  • the present invention provides a polyimide resin obtained by reacting an isocyanurate type polyisocyanate (a1) synthesized from an isocyanate having an aliphatic structure and a tricarboxylic acid anhydride (a2) having an aliphatic structure. It is.
  • this invention provides the curable resin composition characterized by containing a polyimide resin (A) and an epoxy resin (B) which has a 2 or more epoxy group in a molecule
  • the present invention provides a cured product obtained by curing the curable resin composition.
  • the curable resin composition obtained by using the polyimide resin of the present invention is soluble in a general-purpose solvent and provides a cured coating film having excellent heat resistance and light transmittance. It can be suitably used in fields where transparency of the cured product is required. In addition, in fields where transparency of cured products is not required, such as various heat-resistant coating materials and electrical insulating materials, such as interlayer insulating materials for printed wiring boards, build-up materials, semiconductor passivation films, gate insulating films, protection It can also be suitably used in the fields of membranes and insulating materials, batteries such as lithium ion batteries, conductive films, and heat-resistant adhesives.
  • the polyimide resin of the present invention is obtained by reacting an isocyanurate type polyisocyanate (a1) synthesized from an isocyanate having an aliphatic structure with a tricarboxylic acid anhydride (a2) having an aliphatic structure.
  • Examples of the isocyanurate type polyisocyanate (a1) synthesized from an isocyanate having an aliphatic structure include an isocyanurate type polyisocyanate synthesized from an isocyanate having a linear aliphatic structure and an isocyanate having a cyclic aliphatic structure. Examples include synthesized isocyanurate type polyisocyanates.
  • Examples of the isocyanurate type polyisocyanate synthesized from an isocyanate having a linear aliphatic structure include HDI3N (isocyanurate type triisocyanate synthesized from hexamethylene diisocyanate (including polymers such as pentamers)), HTMDI3N, and the like. (Isocyanurate-type triisocyanate synthesized from trimethylhexamethylene diisocyanate (including polymers such as pentamers)) and the like. These may be used in combination or alone.
  • Examples of the isocyanurate type polyisocyanate synthesized from an isocyanate having a cycloaliphatic structure include IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate (including polymers such as pentamers)), HTDI3N ( Isocyanurate type triisocyanate (including polymer such as pentamer) synthesized from hydrogenated tolylene diisocyanate, HXDI3N (Isocyanurate type triisocyanate synthesized from hydrogenated xylene diisocyanate (polymer such as pentamer) ), NBDI3N (isocyanurate-type triisocyanate synthesized from norbornane diisocyanate (including polymers such as pentamers)), HMDI3N (isocyanur synthesized from hydrogenated diphenylmethane diisocyanate) Chromatography (including 5-mers, etc. of the polymer)
  • the isocyanurate type polyisocyanate (a1) synthesized from an isocyanate having an aliphatic structure used in the present invention has a cycloaliphatic structure because a cured coating film having a particularly high Tg and excellent thermal properties can be obtained.
  • Isocyanurate type polyisocyanate synthesized from isocyanate is preferable, and isocyanurate type triisocyanate synthesized from isophorone diisocyanate is particularly preferable.
  • the isocyanurate type triisocyanate synthesized from isophorone diisocyanate may contain a polymer such as a pentamer.
  • the isocyanurate type polyisocyanate synthesized from an isocyanate having a cyclic aliphatic structure in the isocyanurate type polyisocyanate (a1) synthesized from an isocyanate having an aliphatic structure is based on the weight of the compound (a1). 50 to 80% by weight is preferable because a cured coating film having a high Tg and excellent thermal properties can be obtained, more preferably 80 to 100% by weight, and most preferably 100% by weight.
  • an adduct obtained by urethanization reaction of the isocyanate compound and various polyols can be used as long as the solvent solubility of the polyimide resin of the present invention is not impaired.
  • the carboxy group-containing imide resin (A) used in the present invention has a problem in stability and the like by directly forming an imide bond from the above-described isocyanate compound (a1) and the tricarboxylic acid anhydride (a2) having an aliphatic structure. Without passing through a certain polyamic acid intermediate, a polyimide resin having good reproducibility, good solubility and excellent transparency can be synthesized.
  • the transparency of the polyimide resin obtained by using a tricarboxylic acid anhydride (a2) having an aliphatic structure as a raw material for polyimide is improved.
  • the tricarboxylic acid anhydride having an aliphatic structure include a tricarboxylic acid anhydride having a linear aliphatic structure, a tricarboxylic acid anhydride having a cyclic aliphatic structure, and the like.
  • Examples of the tricarboxylic acid anhydride having a linear aliphatic structure include propane tricarboxylic acid anhydride.
  • Examples of the tricarboxylic acid anhydride having a cycloaliphatic structure include cyclohexanetricarboxylic acid anhydride, methylcyclohexanetricarboxylic acid anhydride, cyclohexentricarboxylic acid anhydride, methylcyclohexentricarboxylic acid anhydride, and the like.
  • tricarboxylic acid anhydrides (a2) having an aliphatic structure used in the present invention in addition to transparency, a cured coating film having a high Tg and excellent thermal properties can be obtained, so that a tricarboxylic acid anhydride having a cyclic aliphatic structure is obtained. Things are preferred.
  • the tricarboxylic acid anhydride having a cycloaliphatic structure include cyclohexane tricarboxylic acid anhydride. One or more of these can be used.
  • bifunctional dicarboxylic acid compounds such as adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid and acid anhydrides thereof may be used in combination.
  • cyclohexanetricarboxylic acid anhydride examples include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1 2,3-tricarboxylic acid-2,3-anhydride and the like.
  • cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is obtained because it becomes a polyimide resin having excellent solvent solubility in addition to transparency, and a cured coating film having a high Tg and excellent thermal properties can be obtained. preferable.
  • cyclohexanetricarboxylic acid anhydride is represented by the structure of the following general formula (1), and cyclohexane-1,2,3-tricarboxylic acid, cyclohexane-1,3,4, which is used as a production raw material.
  • impurities such as tricarboxylic acid do not impair the curing of the present invention, for example, 10% by weight or less, preferably 5% by weight or less, they may be mixed.
  • the carboxylic acid component of the tricarboxylic acid anhydride (a2) reacts with the isocyanate component in the polyisocyanate (a1), an imide and an amide are formed, and the polyimide resin of the present invention becomes an imidoamide resin.
  • the polyisocyanate (a1) is reacted with the tricarboxylic acid anhydride (a2) having an aliphatic structure, the tricarboxylic acid anhydride (a2) is left in such a ratio as to leave the carboxylic acid component of the tricarboxylic acid anhydride (a2).
  • polyisocyanate (a1) are reacted, the resulting polyimide resin has a carboxy group.
  • This carboxy group reacts with the epoxy group of the epoxy resin contained in the curable resin composition of the present invention described later to form a crosslinked structure of the cured product. Since the reaction rate is fast imidization, even in the reaction of tricarboxylic acid and triisocyanate, tricarboxylic acid selectively forms an imide at the acid anhydride.
  • the isocyanurate type polyisocyanate (a1) synthesized from the isocyanate having an aliphatic structure is reacted with the tricarboxylic acid anhydride (a2) having an aliphatic structure to obtain the polyimide resin (A) of the present invention.
  • the reaction is preferably carried out in a polar solvent that does not contain any nitrogen atom or sulfur atom.
  • a polar solvent containing nitrogen or sulfur atoms In the presence of a polar solvent containing nitrogen or sulfur atoms, environmental problems are likely to occur, and in the reaction of isocyanurate type polyisocyanate (a1) with tricarboxylic acid anhydride (a2), molecular growth occurs. Is likely to be disturbed. When such a molecule is cut, the physical properties of the composition are likely to deteriorate, and film defects such as “repellency” tend to occur.
  • the polar solvent containing neither a nitrogen atom nor a sulfur atom is more preferably an aprotic solvent.
  • a cresol solvent is a phenolic solvent having protons, but is somewhat unfavorable in terms of the environment, and easily reacts with an isocyanate compound to hinder molecular growth.
  • the cresol solvent easily reacts with an isocyanate group to easily become a blocking agent. Therefore, it is difficult to obtain good physical properties by reacting with other curing components (for example, epoxy resin) during curing. Furthermore, if the blocking agent is removed, it is likely to cause contamination of the equipment used and other materials.
  • alcohol solvents are not preferred because they react with isocyanates or acid anhydrides.
  • the aprotic solvent include ether-based, ester-based, and ketone-based solvents having no hydroxyl group, and among these, ether-based solvents having no hydroxyl group are particularly preferable.
  • the polar solvent containing neither a nitrogen atom nor a sulfur atom is more preferably an ether solvent.
  • the ether solvent has a weak polarity and has an excellent reaction field in the reaction of the above-mentioned isocyanate isocyanurate type polyisocyanate (a1) having an aliphatic structure and the tricarboxylic acid anhydride (a2) having an aliphatic structure. provide.
  • ether solvents known and commonly used solvents can be used.
  • ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Polyethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether and triethylene glycol dibutyl ether; ethylene glycol monomers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate Alkyl ether acetates; polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoeth
  • the isocyanurate type polyisocyanate (a1) synthesized from an isocyanate having an aliphatic structure and the tricarboxylic acid anhydride (a2) having an aliphatic structure are an isocyanurate type polyisocyanate synthesized from an isocyanate having an aliphatic structure.
  • the reaction is carried out so that the ratio [(M1) + (M2)) / (N)] is 1.1 to 3, because the polarity in the reaction system becomes high and the reaction proceeds to lubrication.
  • the remaining polyimide resin has good stability, the residual amount of tricarboxylic acid anhydride (a2) is small, and separation problems such as recrystallization hardly occur. It preferred by reason of an equal. Among these, 1.2 to 2 is more preferable.
  • the acid anhydride group refers to a —CO—O—CO— group obtained by intramolecular dehydration condensation of two molecules of carboxylic acid.
  • the imidization reaction is performed in a solvent or in the absence of a solvent by mixing one or more isocyanate compounds (a1) and one or more tricarboxylic acid anhydrides (a2) and raising the temperature while stirring.
  • the reaction temperature is preferably 50 ° C. to 250 ° C., particularly preferably 70 ° C. to 180 ° C. By setting such a reaction temperature, the reaction rate is increased, and the side reaction and decomposition are less likely to occur.
  • the reaction is accompanied by decarboxylation, the acid anhydride group and the isocyanate group form an imide group.
  • the progress of the reaction can be followed by an analytical means such as an infrared vector, acid value, or isocyanate group quantification.
  • the infrared spectrum, 2270 cm -1 which is the characteristic absorption of an isocyanate group was reduced as the reaction further acid anhydride group is reduced with a characteristic absorption at 1860 cm -1 and 850 cm -1.
  • the absorption of imide groups increases at 1780 cm ⁇ 1 and 1720 cm ⁇ 1 .
  • the reaction may be terminated by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the reaction until the isocyanate group disappears from the standpoint of stability over time.
  • a catalyst, an antioxidant, a surfactant, other solvents, and the like may be added as long as the physical properties of the synthesized resin are not impaired.
  • the acid value of the polyimide resin of the present invention is preferably 70 to 210 KOH mg / g, and particularly preferably 90 to 190 KOH mg / g. When it is 70 to 210 KOHmg / g, it exhibits excellent performance as a cured material.
  • the polyimide resin of the present invention is preferably a polyimide resin that dissolves in a polar solvent that does not contain any of the nitrogen and sulfur atoms. Examples of such a polyimide resin include a branched polyimide resin having a branched structure and an acid value of the resin of 60 KOHmg / g or more.
  • the number average molecular weight of the polyimide resin of the present invention is preferably from 1,000 to 20,000, more preferably from 2,000 to 8,000, from the viewpoints of good solubility in a solvent and a cured product having excellent mechanical strength.
  • the molecular weight can be measured by gel permeation chromatography (GPC) or quantitative analysis of the terminal functional group amount.
  • GPC gel permeation chromatography
  • the number average molecular weight was determined using GPC under the following conditions.
  • Measuring device Tosoh Corporation HLC-8120GPC, UV8020 Column: TFKguardcolumnHXL-L, TFKgel (G1000HXL, G2000HXL, G3000HXL, G4000HXL) manufactured by Tosoh Corporation Detector: RI (differential refractometer) and UV (254 nm) Measurement conditions: Column temperature 40 ° C Solvent THF Flux 1.0ml / min Standard: Calibration curve prepared with polystyrene standard sample: 0.1% by weight THF solution in terms of resin solid content filtered through microfilter (injection amount: 200 ⁇ l)
  • Examples of the carboxy group-containing imide resin (A) used in the present invention include imide resins represented by the following (formula 2).
  • N is a repeating unit of 0-30.
  • Rb is, for example, a structural unit represented by the following structural formula (Formula 3) or (Formula 4).
  • R 2 is, for example, an aliphatic tricarboxylic acid residue that may have a substituent having 6 to 20 carbon atoms.
  • Rc is, for example, a structural unit represented by the following structural formula (formula 5) is there.
  • Rd is, for example, a trivalent organic group represented by the following (formula 6):
  • Ra represents, for example, a residue of a divalent aliphatic diisocyanate.
  • the curable resin composition of the present invention comprises the polyimide resin of the present invention (hereinafter referred to as polyimide resin (A)). And a curable resin (B).
  • the thermosetting resin composition which contains the epoxy compound (B1) component which has a 2 or more epoxy group in a molecule
  • numerator is mention
  • the component (B1) known and commonly used epoxy resins can be used, and two or more kinds may be mixed and used.
  • Other examples include melamine resins, isocyanate compounds, silicates and alkoxysilane compounds, (meth) acrylic resins, etc., which are excellent in heat resistance, dimensional stability and mechanical properties (toughness, flexibility).
  • an epoxy resin is preferable in that a cured product such as a cured coating film is obtained.
  • cured material property described in this invention does not react with the polyimide resin of this invention alone or the polyimide resin of this invention other than the hardened
  • a curing agent that reacts by heating or light and / or does not react with the polyimide resin of the present invention, but is cured by heat, light, etc., as an additive component itself.
  • the physical properties are also included in the meaning.
  • epoxy resins examples include bisphenol A type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and dicyclopentadiene reacted with various phenols.
  • Epoxidized products of various dicyclopentadiene-modified phenolic resins epoxidized products of 2,2 ′, 6,6′-tetramethylbiphenol, epoxidized products of 4,4′-methylenebis (2,6-dimethylphenol), naphthol and binaphthol
  • an epoxy derived from a naphthalene skeleton such as a novolak modification of naphthol or binaphthol
  • an aromatic epoxy resin such as an epoxy resin obtained by epoxidizing a phenol resin of a fluorene skeleton, and the like can be given.
  • aliphatic epoxy resins such as neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, 3,4-epoxycyclohexylmethyl- 3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxybicyclohexyl) adipate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol
  • a cycloaliphatic epoxy resin such as an adduct, an epoxy resin containing a polyalkylene glycol chain in the main chain, such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and triglycidyl isocyanurate Heterocycle-containing epoxy resins can be used.
  • an epoxy group-containing polymerization resin obtained by polymerizing an unsaturated group of an epoxy compound having a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and other monomers having a polymerizable unsaturated bond Copolymers with can also be used.
  • Examples of the compound having both (meth) acryloyl group and epoxy group include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxydibutyl (meth) acrylate glycidyl ether.
  • 6-hydroxyhexyl (meth) acrylate glycidyl ether 5-hydroxy-3-methylpentyl (meth) acrylate glycidyl ether, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone modified (meth) acrylic acid-3, 4-epoxycyclohexyl, vinylcyclohexene oxide and the like.
  • the epoxy resin (B) component having two or more epoxy groups in the molecule in the present invention is particularly preferably a cycloaliphatic epoxy resin. If it is a cycloaliphatic epoxy resin, a cured coating film having a high Tg and excellent thermal properties can be obtained, and a cured product having a high light transmittance in the ultraviolet region (around 300 nm) can be obtained.
  • cycloaliphatic epoxy resins hydrogenated bisphenol A type epoxy resin, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like are preferable. .
  • Such cycloaliphatic epoxy resins can be obtained on the market, and examples thereof include Denacol EX-252 (manufactured by Nagase ChemteX Corporation), EHPE3150, EHPE3150CE (manufactured by Daicel Chemical Industries, Ltd.), and the like.
  • the amount of the epoxy resin (B) having two or more epoxy groups in the molecule is 6 to 1100 parts by weight with respect to 100 parts by weight of the polyimide resin (A) to obtain a cured product having excellent heat resistance and transparency. Therefore, the amount is preferably 15 to 300 parts by weight.
  • the polyimide resin (A) and the epoxy resin (B) having two or more epoxy groups in the molecule can be freely blended according to various desired physical properties, but thermal such as Tg.
  • An epoxy resin having a carboxy group-containing imide resin (A) having a mole number n (COOH) of the carboxy group-containing imide resin (A) and two or more epoxy groups in the molecule in terms of the balance between physical properties, mechanical properties, etc. and transparency of the cured coating film.
  • the curable resin composition of the present invention may be mixed with an epoxy-carboxylic acid-based curing catalyst or the like.
  • epoxy-carboxylic acid curing catalysts include primary to tertiary amines for promoting the reaction, quaternary ammonium salts, nitrogen compounds such as dicyandiamide and imidazole compounds, TPP (triphenylphosphine). ),
  • TPP triphenylphosphine
  • Known epoxy curing accelerators such as phosphine compounds such as alkyl-substituted trialkyl phonylphosphine and derivatives thereof, phosphophonium salts thereof, dialkylureas, carboxylic acids, phenols, or methylol group-containing compounds. Etc., and a small amount of these can be used in combination.
  • the curable resin composition of the present invention can be cured by heating after coating, casting or the like on the object. Thereby, the articles
  • the curing temperature is preferably 80 ° C. to 300 ° C., particularly preferably 120 ° C. to 250 ° C. Further, step curing at various temperatures may be performed. Alternatively, a sheet-like or film-like composition semi-cured at a temperature of about 50 ° C. to 170 ° C. may be stored and treated at the above-described curing temperature when necessary.
  • the curing reaction between the carboxy group-containing imide resin (A) component and the epoxy resin (B) component having two or more epoxy groups in the molecule is basically a reaction between the carboxy group and the epoxy group. It is possible to obtain a curable resin composition having excellent physical properties and the like by selecting the type, blending ratio, curing conditions, etc. of (A) and an epoxy resin (B) having two or more epoxy groups in the molecule. it can.
  • Various additives such as other solvents, various leveling agents, antifoaming agents, antioxidants, anti-aging agents, ultraviolet absorbers, anti-settling agents, rheology control agents and the like are added to the curable resin composition of the present invention as necessary.
  • additives such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, silica, colloidal silica, glass, various metal powders, fibrous fillers such as glass fiber, carbon fiber, Kevlar fiber, etc.
  • blend well-known and usual coloring pigments such as phthalocyanine blue, phthalocyanine green, a titanium oxide, carbon black, a silica, and other adhesive provision agents.
  • blend polymers such as an acrylic resin, a cellulose resin, a polyvinyl resin, polyphenylene ether, and polyether sulfone, as needed.
  • EDGA diethylene glycol monoethyl ether acetate
  • 2070 g 3 mol
  • PGMAc propylene glycol monomethyl ether acetate
  • Example 1 The curable resin composition 1 of the present invention was prepared according to the formulation shown in Table 1.
  • Table 1 The appearance of the cured coating film of the thermosetting resin composition 1 and the Tg and light transmittance of the film of the thermosetting resin composition 1 were evaluated according to the following methods.
  • Table 2 shows the appearance of the cured coating film and Tg of the film, and
  • Table 3 shows the evaluation result of the light transmittance.
  • thermosetting resin composition 1 was coated on a glass substrate so that the film thickness after curing was 25 to 35 microns. Next, the coated plate was dried with a dryer at 50 ° C. for 30 minutes, then dried at 100 ° C. for 30 minutes, and finally cured at 170 ° C. for 1 hour, and the appearance of the cured coating film was evaluated according to the following criteria. A: Uniform and no foreign matter is seen. X: Repelling, irregularities, foreign matter and cracks can be confirmed.
  • Example 2 and Comparative Examples 1 and 2 Thermosetting resin composition 2 and comparative thermosetting resin compositions 1 and 2 were prepared according to the formulation shown in Table 1. Evaluation was performed in the same manner as in Example 1, and the results are shown in Tables 2 and 3.
  • EHPE3150 Cyclic aliphatic epoxy resin (1,2-epoxy-4- (2-oxiranyl) of 2,2-bis (hydroxymethyl) -1-butanol) manufactured by Daicel Chemical Industries, Ltd. Cyclohexane adduct). Epoxy equivalent is 177. The resin content is 100% by weight.
  • Epicron N-680 Cresol novolac type epoxy resin manufactured by DIC Corporation. The epoxy equivalent is 211. The resin content is 100% by weight.
  • Denacol EX-252 Cyclic aliphatic epoxy resin (hydrogenated bisphenol A type epoxy resin) manufactured by Nagase ChemteX Corporation. Epoxy equivalent is 212. The resin content is 100% by weight.
  • ⁇ TPP Triphenylphosphine

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention porte sur une composition de résine thermodurcissable qui est soluble dans les solvants généraux et peut donner un objet durci (film de revêtement durci) qui transmet de façon élevée de la lumière allant de la lumière visible à la région des ultraviolets autour de 300 nm ; et sur une résine de polyimide appropriée pour être utilisée dans la préparation de la composition. La résine de polyimide est obtenue par réaction d'un polyisocyanate de type isocyanurate (a1) synthétisé à partir d'un isocyanate ayant une structure aliphatique avec un anhydride d'acide tricarboxylique (a2) ayant une structure aliphatique. La composition de résine durcissable contient la résine de polyimide. L'invention porte également sur un objet durci obtenu à partir de la composition.
PCT/JP2010/054499 2009-03-18 2010-03-17 Résine de polyimide, composition de résine durcissable et objet durci à partir de celle-ci Ceased WO2010107045A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013040253A (ja) * 2011-08-12 2013-02-28 Dic Corp 熱硬化性樹脂組成物、白色プリプレグ、白色積層板及びプリント配線基板
JP2013071969A (ja) * 2011-09-27 2013-04-22 Dic Corp 熱硬化性樹脂組成物、その硬化物、プリント配線板用層間接着フィルム、白色プリプレグ、白色積層板及びプリント配線基板。
US20140162071A1 (en) * 2011-05-31 2014-06-12 Mitsubishi Gas Chemical Company, Inc. Resin composition, and prepreg and metal foil-clad laminate using the same
WO2015008744A1 (fr) * 2013-07-18 2015-01-22 Dic株式会社 Résine polyamide-imide, composition de résine durcissable et produit durci correspondant
US20150056454A1 (en) * 2012-03-13 2015-02-26 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, and metal foil-clad laminate
JP2016199678A (ja) * 2015-04-10 2016-12-01 日本化薬株式会社 ポリアミド樹脂及びポリイミド樹脂
JP2017226737A (ja) * 2016-06-21 2017-12-28 Dic株式会社 ポリアミドイミド樹脂およびその製造方法
KR20190020295A (ko) 2016-06-21 2019-02-28 디아이씨 가부시끼가이샤 알코올 변성 폴리아미드이미드 수지 및 그 제조 방법
KR20190114608A (ko) * 2018-03-30 2019-10-10 동우 화인켐 주식회사 필름 터치 센서용 구조체 및 그 제조방법
KR20220061086A (ko) * 2019-09-06 2022-05-12 다이요 잉키 세이조 가부시키가이샤 경화성 수지 조성물, 그의 드라이 필름 및 경화물, 그리고 그 경화물을 포함하는 전자 부품

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI876067B (zh) * 2020-06-29 2025-03-11 日商日本化藥股份有限公司 異氰酸酯改質聚醯亞胺樹脂、樹脂組成物及其硬化物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001316469A (ja) * 2000-05-01 2001-11-13 Dainippon Ink & Chem Inc カルボキシル基含有アミドイミド樹脂及び／又はカルボキシル基含有イミド樹脂
WO2005049597A1 (fr) * 2003-11-20 2005-06-02 Mitsubishi Gas Chemical Company, Inc. Anhydride liquide d'acide cyclohexane-tricarboxylique
JP2008133442A (ja) * 2006-10-31 2008-06-12 Nippon Shokubai Co Ltd 樹脂組成物、光学材料、及び、該光学材料の制御方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001316469A (ja) * 2000-05-01 2001-11-13 Dainippon Ink & Chem Inc カルボキシル基含有アミドイミド樹脂及び／又はカルボキシル基含有イミド樹脂
WO2005049597A1 (fr) * 2003-11-20 2005-06-02 Mitsubishi Gas Chemical Company, Inc. Anhydride liquide d'acide cyclohexane-tricarboxylique
JP2008133442A (ja) * 2006-10-31 2008-06-12 Nippon Shokubai Co Ltd 樹脂組成物、光学材料、及び、該光学材料の制御方法

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US20140162071A1 (en) * 2011-05-31 2014-06-12 Mitsubishi Gas Chemical Company, Inc. Resin composition, and prepreg and metal foil-clad laminate using the same
JP2013040253A (ja) * 2011-08-12 2013-02-28 Dic Corp 熱硬化性樹脂組成物、白色プリプレグ、白色積層板及びプリント配線基板
JP2013071969A (ja) * 2011-09-27 2013-04-22 Dic Corp 熱硬化性樹脂組成物、その硬化物、プリント配線板用層間接着フィルム、白色プリプレグ、白色積層板及びプリント配線基板。
US20150056454A1 (en) * 2012-03-13 2015-02-26 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, and metal foil-clad laminate
US10202493B2 (en) 2013-07-18 2019-02-12 Dic Corporation Polyamide-imide resin, and curable resin composition and cured product of same
WO2015008744A1 (fr) * 2013-07-18 2015-01-22 Dic株式会社 Résine polyamide-imide, composition de résine durcissable et produit durci correspondant
JP5839149B2 (ja) * 2013-07-18 2016-01-06 Dic株式会社 ポリアミドイミド樹脂、硬化性樹脂組成物及びその硬化物
CN105408394A (zh) * 2013-07-18 2016-03-16 Dic株式会社 聚酰胺酰亚胺树脂、固化性树脂组合物及其固化物
KR20160034252A (ko) 2013-07-18 2016-03-29 디아이씨 가부시끼가이샤 폴리아미드이미드 수지, 경화성 수지 조성물 및 그 경화물
EP3023449A4 (fr) * 2013-07-18 2017-03-22 DIC Corporation Résine polyamide-imide, composition de résine durcissable et produit durci correspondant
KR102051442B1 (ko) * 2013-07-18 2019-12-03 디아이씨 가부시끼가이샤 폴리아미드이미드 수지, 경화성 수지 조성물 및 그 경화물
JP2016199678A (ja) * 2015-04-10 2016-12-01 日本化薬株式会社 ポリアミド樹脂及びポリイミド樹脂
KR20190020295A (ko) 2016-06-21 2019-02-28 디아이씨 가부시끼가이샤 알코올 변성 폴리아미드이미드 수지 및 그 제조 방법
JP2017226737A (ja) * 2016-06-21 2017-12-28 Dic株式会社 ポリアミドイミド樹脂およびその製造方法
KR20190114608A (ko) * 2018-03-30 2019-10-10 동우 화인켐 주식회사 필름 터치 센서용 구조체 및 그 제조방법
KR102381831B1 (ko) * 2018-03-30 2022-03-31 동우 화인켐 주식회사 필름 터치 센서용 구조체 및 그 제조방법
KR20220061086A (ko) * 2019-09-06 2022-05-12 다이요 잉키 세이조 가부시키가이샤 경화성 수지 조성물, 그의 드라이 필름 및 경화물, 그리고 그 경화물을 포함하는 전자 부품
US12351686B2 (en) 2019-09-06 2025-07-08 Taiyo Holdings Co., Ltd. Curable resin composition, dry film and cured product of same, and electronic component containing said cured product
KR102877942B1 (ko) 2019-09-06 2025-10-30 다이요 홀딩스 가부시키가이샤 경화성 수지 조성물, 그의 드라이 필름 및 경화물, 그리고 그 경화물을 포함하는 전자 부품

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