Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
• • 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
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
• • 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
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08G73/1003—Preparatory processes
  • C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
• • 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
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
• • 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
  • C08G73/16—Polyester-imides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
  • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to an imide group-containing resin composition that has excellent solvent solubility, flexibility, and adhesion, and is suitable for use in adhesives and coatings.
• Imide group-containing resins such as polyimide
• they due to their rigid molecular structure, they have poor solvent solubility. For this reason, they must be dissolved in a solvent in the form of amic acid, which is the precursor of the imide group, and then coated.
• the amic acid In addition to drying the solvent, the amic acid must undergo a dehydration ring-closing reaction to form the imide group.
• heating to above 200°C, and preferably 300°C is required, which limits the applications in which they can be used.
• imide group-containing resins are to be used in applications such as adhesives and paints while retaining their characteristic heat resistance and mechanical strength, they must be easily soluble in solvents, have excellent adhesion to substrates, and be flexible.
• Methods being considered for improving solvent solubility for use in adhesives and paints include copolymerizing monomers with bulky structures to improve solvent solubility, copolymerizing monomers with flexible long-chain structures, and introducing amide groups to improve solvent solubility.
• Patent Document 1 proposes that by using a bulky monomer with a special structure, it is possible to obtain a polyimide resin with excellent solvent solubility.
• Patent Document 2 proposes using modified polyamideimide, a polyimide resin in which a long-chain siloxane having an amine, which is flexible and has a reactive functional group, is introduced to the molecular chain end, as the main component of the adhesive.
• Patent Document 1 the bulky monomers in Patent Document 1 are very expensive due to their special structure, making them less economical, and it is difficult to impart the flexibility and adhesion required for applications such as adhesives and paints.
• the use of a monomer having a long-chain siloxane structure as in Patent Document 2 makes it possible to impart flexibility, but there is a risk that the inherent heat resistance of the resin will decrease.
• conventional technologies have not been able to obtain resins and resin compositions that are excellent in solvent solubility, flexibility, and adhesion and are suitable for adhesive and paint applications.
• the present invention was made to solve the problems of the conventional technology described above, and its purpose is to provide an imide group-containing resin that retains the excellent heat resistance of imide group-containing resins while simultaneously satisfying the solvent solubility, flexibility, and adhesion properties suitable for adhesive and coating applications, and an adhesive composition and coating composition containing the same.
• the inventors discovered that by introducing an acid dianhydride compound having an ester group or ether group and a long-chain aliphatic dicarboxylic acid into an imide group-containing resin, and further using a component having an aromatic ring in the amine or isocyanate component, the resulting imide group-containing resin can simultaneously satisfy solvent solubility, flexibility, and adhesion, thereby solving the above-mentioned problems, and thus completing the present invention.
• the present invention comprises the following configurations [1] to [11].
• An imide group-containing resin having, as structural units, an acid dianhydride compound (A) having an ester group or an ether group, and a long-chain aliphatic dicarboxylic acid (B).
• the imide group-containing resin according to [1] wherein the acid dianhydride compound (A) is 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride or oxydiphthalic dianhydride.
• the imide group-containing resin according to [1] characterized in that, when the total amount of amine components or the total amount of isocyanate components constituting the imide group-containing resin is taken as 100 mol %, a copolymerization amount of a component having an aromatic ring among amine components and isocyanate components is 30 mol % or more.
• An adhesive composition comprising the imide group-containing resin according to any one of [1] to [6].
• a coating composition comprising the imide group-containing resin according to any one of [1] to [6].
• a resin composition comprising the imide group-containing resin according to any one of [1] to [6] and a curing agent (C).
• An adhesive composition comprising the resin composition according to [9].
• a coating composition comprising the resin composition according to [9].
• the imide group-containing resin of the present invention can simultaneously exhibit excellent solvent solubility, flexibility, and adhesion. For this reason, the imide group-containing resin of the present invention can be suitably used as a raw material for adhesive compositions and coating compositions.
• the imide group-containing resin of the present invention is characterized by having an acid dianhydride compound (A) having an ester group or an ether group (hereinafter also referred to as the acid dianhydride compound (A) or simply as the (A) component) and a long-chain aliphatic dicarboxylic acid (B) (hereinafter also referred to as the (B) component) as constituent units.
• A acid dianhydride compound having an ester group or an ether group
• B long-chain aliphatic dicarboxylic acid
• the imide group-containing resin is a resin having imide groups as a repeating unit, and refers to a so-called polyimide resin.
• the resin may also have bonds of other groups, such as amide groups, urethane groups, ester groups, and ether groups, as repeating units.
• the acid dianhydride compound (A) having an ester group or an ether group has the effect of enhancing the interaction between the adhesive and the surface of the adherend by the polarity of the ester group or the ether group when the resulting imide group-containing resin is used as an adhesive composition, thereby enabling the adhesive to exhibit stronger adhesive strength.
• the presence of the ester group or the ether group increases the distance between the acid anhydride groups in the monomer. As a result, the amount of imide groups in the resulting polyimide resin is reduced, which is expected to improve the solvent solubility.
• Examples of the acid dianhydride compound (A) having an ester group include alkylene glycol bisanhydrotrimellitates such as ethylene glycol bisanhydrotrimellitate, propylene glycol bisanhydrotrimellitate, 1,4-butanediol bisanhydrotrimellitate, hexamethylene glycol bisanhydrotrimellitate, polyethylene glycol bisanhydrotrimellitate, and polypropylene glycol bisanhydrotrimellitate.
• Examples of the acid dianhydride compound (A) having an ether group include 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic dianhydride and oxydiphthalic dianhydride.
• the copolymerization amount of the (A) component is preferably 1 to 80 mol%, more preferably 10 to 60 mol%, and even more preferably 15 to 50 mol%, when the total amount of polycarboxylic acid components constituting the imide group-containing resin is taken as 100 mol%. If the amount of copolymerization of the components is less than the lower limit, the solvent solubility and adhesiveness may be poor, and if it is more than the upper limit, the amount of long-chain aliphatic carboxylic acid described below will be relatively small, resulting in insufficient flexibility and high raw material costs, which may be industrially disadvantageous.
• the long-chain aliphatic dicarboxylic acid (B) refers to a compound containing a structure having an alkyl chain with 10 or more carbon atoms and two carboxylic acids. A part of the alkyl chain may have a branched or cyclic structure or a double bond.
• dimer acid and the like having carboxylic acids at both ends of the molecular chain of each alkane, such as dodecanedioic acid may be mentioned. These may be used alone or in combination. Among these, dimer acid is preferred. When dimer acid is used, the resulting resin composition is likely to exhibit flexibility and solvent solubility when used for adhesives or paints. Dimer acid is a dicarboxylic acid with 36 carbon atoms produced by dimerization of unsaturated fatty acids with 18 carbon atoms. As the dimer acid, one in which the unsaturated bonds are hydrogenated may also be used.
• Imide group-containing resins are generally poor in solvent solubility because they are mainly aromatic.
• the imide group-containing resin of the present invention has a long-chain aliphatic structure introduced into it, which makes the resin skeleton flexible and improves solvent solubility.
• imide group-containing resins generally have poor fluidity and flexibility during the adhesive lamination process and during deformation of the substrate after coating and drying, and as a result, it is difficult to obtain sufficient adhesive strength to the substrate.
• the imide group-containing resin of the present invention is copolymerized with long-chain aliphatic dicarboxylic acid (B) as a constituent unit, and the aliphatic chain imparts fluidity and flexibility to the resin, allowing it to fill in the unevenness of the adherend surface during thermocompression bonding, thereby improving adhesion.
• the flexibility imparted to the resin allows it to deform in response to deformation of the substrate after coating and drying.
• the copolymerization amount of long-chain aliphatic dicarboxylic acid (B) is preferably 1 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 30 to 60 mol%, when the total amount of polycarboxylic acid components constituting the imide group-containing resin is taken as 100 mol%. If the copolymerization amount of the long-chain aliphatic dicarboxylic acid (B) is less than the lower limit, the solvent solubility, adhesiveness, and flexibility may be poor, and if it exceeds the upper limit, the imide group-containing resin may not have good heat resistance.
• the imide group-containing resin may have a polycarboxylic acid component other than the components (A) and (B).
• a polycarboxylic acid component it is preferable to use a polycarboxylic acid component having an aromatic ring from the viewpoint of improving the heat resistance of the resulting imide group-containing resin and adhesive or coating composition.
• polycarboxylic acid components having an aromatic ring examples include trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, (hexafluoroisopropylidene) diphthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid. These may be used alone or in combination.
• the copolymerization amount of the polycarboxylic acid component having an aromatic ring is preferably 20 to 90 mol%, more preferably 30 to 80 mol%, and even more preferably 40 to 70 mol%, when the total amount of polycarboxylic acid components constituting the imide group-containing resin is taken as 100 mol%. Note that if component (A) has an aromatic ring, it is included in this calculation.
• the polycarboxylic acid components may be long-chain aliphatic or alicyclic polycarboxylic acids or monoanhydrides or dianhydrides of polycarboxylic acids already described, to the extent that the effects of the present invention are not impaired.
• any of the polycarboxylic acid components having an aromatic ring described above may be hydrogenated, meso-butane-1,2,3,4-tetracarboxylic acid dianhydride, pentane-1,2,4,5-tetracarboxylic acid dianhydride, cyclobutane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic acid dianhydride, cyclohexane dicarboxylic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid, octanedioic acid, azelaic acid, sebacic acid, 2-methylsuccinic acid, etc. These may be used alone or in combination.
• the imide group-containing resin can be obtained by polymerizing a polycarboxylic acid component and an amine component or an isocyanate component as the main raw materials.
• the amine component can be a compound with an amino group having two or more functionalities
• the isocyanate component can be a compound with an isocyanate group having two or more functionalities.
• the isocyanate component constituting the imide group-containing resin a component having an aromatic ring is preferable from the viewpoint of improving the heat resistance of the adhesive composition, and examples thereof include diphenylmethane-4,4'-diisocyanate and its structural isomers, as well as dimethyldiphenylmethane diisocyanate, diethyldiphenylmethane diisocyanate, dimethoxydiphenylmethane diisocyanate, diphenylether diisocyanate, benzophenone diisocyanate, diphenylsulfone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4'-[2,2-bis(4-phenoxyphenyl)propane]diisocyanate, dimethylbiphenyl diisocyanate, diethylbiphenyl diisocyanate, dimethoxybiphenyl di
• examples of the amine component include those in which the isocyanate group of the isocyanate component is replaced with an amino group. These may be used alone or in combination.
• the copolymerization amount of the aromatic ring-containing component among these amine components and isocyanate components is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more, when the total amount of amine components or the total amount of isocyanate components constituting the imide group-containing resin is taken as 100 mol%, in terms of the balance between heat resistance, flexibility, and adhesive strength.
• the upper limit is not particularly limited, but is generally 100 mol%.
• an aliphatic or alicyclic isocyanate component or amine component can be used as the isocyanate component or amine component to the extent that the effect of the present invention is not impaired.
• any of the isocyanate components or amine components having an aromatic ring described above that have been hydrogenated isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, ethylene diisocyanate, propylene diisocyanate, hexamethylene diisocyanate, etc.
• the amine component can be any of these isocyanate components in which the isocyanate group has been replaced with an amino group. These may be used alone or in combination. From the viewpoint of the heat resistance of the resulting resin composition using the imide group-containing resin, the copolymerization amount of these components is preferably 50 mol% or less, and more preferably 20 mol% or less, when the total amount of isocyanate components and amine components is taken as 100 mol%.
• imide group-containing resins can be copolymerized with compounds having three or more functional groups.
• examples include polyfunctional carboxylic acids such as trimesic acid, dicarboxylic acids having hydroxyl groups such as 5-hydroxyisophthalic acid, dicarboxylic acids having amino groups such as 5-aminoisophthalic acid, compounds having three or more hydroxyl groups such as glycerin and polyglycerin, and compounds having three or more amino groups such as tris(2-aminoethyl)amine.
• the amount of copolymerization is preferably 20 mol% or less when the total amount of all polycarboxylic acid components, or the total amount of all isocyanate components and amine components is taken as 100 mol%. If it exceeds 20 mol%, there is a risk of gelation or the generation of insoluble matter during resin polymerization.
• the imide group-containing resin can be copolymerized with polyesters, polyethers, polycarbonates, polysiloxanes, etc., as components that impart flexibility to the resulting resin, to an extent that does not impair the effects of the present invention.
• the amount of these components copolymerized in the imide group-containing resin is large, there is a risk that the heat resistance and economic efficiency will be impaired, so it is preferable that the amount of these components copolymerized is 10 mol % or less when the total amount of all polycarboxylic acid components, or the total amount of all isocyanate components and amine components is taken as 100 mol %.
• the imide group-containing resin can be produced by known methods such as a method of reacting a polycarboxylic acid component with an isocyanate component (isocyanate method), a method of reacting a polycarboxylic acid component with an amine component to form an amic acid and then ring-closing the amic acid (direct method), or a method of reacting a compound having a carboxylic acid anhydride and a carboxylic acid chloride with an amine component (acid chloride method).
• isocyanate method is advantageous in that the by-product carbon dioxide is removed from the system as a gas.
• imide group-containing resins typically using the isocyanate method
• imide group-containing resins can also be produced using the direct method and acid chloride method by using compounds that contain the corresponding amine components or carboxylic acid chlorides.
• the polymerization reaction of the imide group-containing resin can be carried out by stirring the polycarboxylic acid component and the isocyanate component in a solvent while heating them to 60°C to 200°C.
• the molar ratio of the polycarboxylic acid component/isocyanate component is preferably in the range of 90/100 to 100/90.
• the content (copolymerization amount) of the polycarboxylic acid component and the isocyanate component in the imide group-containing resin is the same as the ratio of each component during polymerization.
• catalysts such as alkali metals such as sodium fluoride, potassium fluoride, and sodium methoxide, amines such as triethylenediamine, triethylamine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonene, and dibutyltin dilaurate can be used.
• the amount of these catalysts is too small, the desired catalytic effect will not be fully achieved, and if the amount is too large, side reactions may occur, so it is preferable to use 0.01 to 5 mol%, and more preferably 0.1 to 3 mol%, of the polycarboxylic acid component or the isocyanate component, whichever is larger, taken as 100 mol%.
• Solvents that can be used in the polymerization reaction of imide group-containing resins include, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, ⁇ -butyrolactone, dimethylimidazolidinone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, cyclohexanone, and cyclopentanone.
• N-methyl-2-pyrrolidone or dimethylacetamide is preferred because of the solubility of the resulting imide group-containing resin and the efficiency of the polymerization reaction.
• the non-volatile content and solution viscosity can be adjusted by diluting with the solvent used in the polymerization reaction or with another low-boiling point solvent. These may be used alone or in combination.
• Low boiling point solvents for dilution include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane, and octane, alcohol solvents such as methanol, ethanol, propanol, butanol, and isopropanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, ether solvents such as diethyl ether and tetrahydrofuran, and ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate.
• aromatic solvents such as toluene and xylene
• aliphatic solvents such as hexane, heptane, and octane
• alcohol solvents such as methanol, ethanol, propanol,
• the imide group-containing resin of the present invention can be used alone or, if necessary, in combination with a curing agent (C) to form a resin composition for adhesives or coatings.
• a curing agent C
• the imide group-containing resin which has excellent heat resistance, can be made to adhere well to a substrate and then strengthened by reaction with the curing agent, providing excellent adhesion and making the resin suitable for use as an adhesive or coating material.
• the curing agent (C) used in combination with the imide group-containing resin is not particularly limited, but examples thereof include epoxy resins, isocyanate-based curing agents, polycarbodiimides, etc. Among these, epoxy resins are preferred in terms of the suitable reaction temperature and reaction time with the imide group-containing resin, the heat resistance of the resulting reaction product, and the stability after mixing the imide group-containing resin and the curing agent.
• the epoxy resin may be modified with silicone, urethane, polyimide, polyamide, etc., and may contain sulfur atoms, nitrogen atoms, etc. in the molecular skeleton.
• epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin, novolac type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin, alicyclic epoxy resins such as hexahydrophthalic acid glycidyl ester, hydrogenated products of the bisphenol type epoxy resins, and hydrogenated products of the novolac type epoxy resins, linear aliphatic epoxy resins such as dimer acid glycidyl ester, epoxidized polybutadiene, and epoxidized soybean oil.
• the epoxy equivalent of the epoxy resin is preferably 100 to 300 g/eq, and more preferably 150 to 200 g/eq.
• the type of epoxy resin is preferably one having an aromatic ring, and bisphenol type epoxy resin and novolac type epoxy resin are more preferred.
• epoxy resins include, for example, bisphenol A type epoxy resins such as jER828 and 1001 manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A type epoxy resins such as ST-2004 and 2007 manufactured by Nippon Steel Chemical & Material Co., Ltd., bisphenol F type epoxy resins such as EXA-9726 manufactured by DIC Corporation and YDF-170 and 2004 manufactured by Nippon Steel Chemical & Material Co., Ltd., phenol novolacs such as jER152 and 154 manufactured by Mitsubishi Chemical Corporation and DEN-438 manufactured by The Dow Chemical Company.
• cresol novolac type epoxy resins such as YDCN-700 series manufactured by Nippon Steel Chemical & Material Co., Ltd., and EOCN-125S, 103S, and 104S manufactured by Nippon Kayaku Co., Ltd., flexible epoxy resins such as YD-171 manufactured by Nippon Steel Chemical & Material Co., Ltd., Epon 1031S manufactured by Mitsubishi Chemical Co., Ltd., Araldite 0163 manufactured by BASF Japan Ltd., and Nagase Chemtex Co., Ltd.
• Polyfunctional epoxy resins such as DENACOL EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, and EX-321 manufactured by Mitsubishi Chemical Corporation; heterocycle-containing epoxy resins such as EPICOAT 604 manufactured by Mitsubishi Chemical Corporation, YH-434 manufactured by Nippon Steel Chemical & Material Co., Ltd., and Araldite PT810 manufactured by BASF Japan Ltd.; alicyclic epoxy resins such as CELLOXIDE 2021 and EHPE3150 manufactured by Daicel Chemical Industries, Ltd., and ERL4234 manufactured by UCC Corporation; Examples of such epoxy resins include bisphenol S type epoxy resins such as Epiclon EXA-1514 (trade name) manufactured by Nissan Chemical Industries, Ltd., triglycidyl isocyanurates such as TEPIC (trade name) manufactured by Nissan Chemical Industries, Ltd., bixylenol type epoxy resins such as YX-4000 (trade name) manufactured by Mitsubishi Chemical Corporation, bisphenol
• the content of the imide group-containing resin in the resin composition of the present invention is preferably 30 to 99% by mass, more preferably 60 to 95% by mass, when the entire non-volatile content of the resin composition is taken as 100% by mass. If the content of the imide group-containing resin is too low, the resin composition may become brittle and difficult to handle due to the small amount of high molecular weight components in the resin composition. On the other hand, if the content of the imide group-containing resin is too high, the ratio of the curing agent is low, and curing may be insufficient, resulting in a decrease in heat resistance.
• the content of the curing agent (C) in the resin composition of the present invention is preferably 1 to 70% by mass, more preferably 5 to 40% by mass, when the entire non-volatile content of the resin composition is taken as 100% by mass. If the content of the curing agent is too low, sufficient thermosetting properties may not be obtained, and as a result, the heat resistance of the adhesive composition may be poor. If the content of the curing agent is too high, the flexibility of the resin composition may be impaired, and the adhesive strength may be reduced.
• a further curing agent for curing the epoxy resin and a curing catalyst for promoting the reaction between the epoxy resin and the imide group-containing resin can be added within a range that does not impair the properties.
• a curing agent is not particularly limited as long as it is a compound that reacts with the epoxy resin, and examples thereof include amine-based curing agents, compounds having a phenolic hydroxyl group, compounds having a carboxylic acid, and compounds having an acid anhydride. These curing agents are used to adjust the functional group equivalent of the epoxy resin and the imide group-containing resin.
• the curing catalyst is not particularly limited as long as it promotes the reaction between the epoxy resin, the imide group-containing resin, and the curing agent.
• the curing catalyst include imidazole derivatives such as 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, and 2P4BHZ manufactured by Shikoku Chemical Industry Co., Ltd.; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, and m-xylenediamine.
• tertiary amines such as azabicyclo[5,4,0]-7-undecene (DBN) and DBN (1,5-diazabicyclo[4,3,0]-5-nonene), organic acid salts thereof and/or tetraphenylborate, polyvinylphenol, polyvinylphenol bromide, organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine, quaternary phosphonium salts such as tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide, hexadecyltributylphosphonium chloride and tetraphenylphosphonium tetraphenylborate, benzyltrimethylammonium chloride, phenyltributyl
• the curing agent include quaternary ammonium salts such as ammonium chloride, the polycar
• a silane coupling agent can be added to the resin composition of the present invention in order to improve adhesion to the substrate.
• Specific examples include aminosilane, mercaptosilane, vinylsilane, epoxysilane, methacrylsilane, isocyanatesilane, ketiminesilane, or mixtures or reactants thereof, or compounds obtained by reacting these with polyisocyanates.
• silane coupling agents include aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane; mercapto
• silane coupling agent examples include methacrylsilanes such as epoxy silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; isocyanate silanes such as isocyanatepropyltriethoxysilane and isocyanatepropyltrimethoxysilane; and ketimine silanes such as ketimine propyltrimethoxysilane and ketimine propyltriethoxysilane. These may be used alone or in combination of two or more.
• methacrylsilanes such as epoxy silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltrieth
• epoxy silane has a reactive epoxy group and can react with an imide group-containing resin, so it is preferable in terms of improving heat resistance and moist heat resistance.
• the amount of the silane coupling agent is preferably 0 to 3 mass%, and more preferably 0 to 2 mass%, when the entire non-volatile content of the resin composition is 100 mass%. If the amount exceeds the above range, the heat resistance tends to decrease.
• an organic filler or an inorganic filler can be added for the purpose of improving heat resistance, within a range that does not impair the effects of the present invention.
• the organic filler include powders of heat-resistant resins such as polyimide and polyamideimide.
• the inorganic filler examples include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO.TiO 2 ), barium carbonate (BaCO 3 ), lead titanate (PbO.TiO 2 ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga 2 O 3 ), spinel (MgO.Al 2 O 3 ), mullite (3Al 2 O 3.2SiO 2 ), cordierite (2MgO.2Al 2 O 3.5SiO 2 ), talc (3MgO.4SiO 2.H 2 O), aluminum titanate (TiO 2 -Al 2 O 3 ), yttria-containing zirconia (Y 2
• silica is preferred because of its ease of dispersion and heat resistance improvement effect. These may be used alone or in combination of two or more.
• the amount of these organic fillers and inorganic fillers added is preferably 1 to 30 mass % relative to the non-volatile components of the resin composition, and more preferably 3 to 15 mass %. If the amount of organic filler or inorganic filler added is too large, the coating film may become embrittled, and if the amount added is too small, the effect of improving heat resistance may not be sufficient.
• various contents can be used as coating resin compositions for the purpose of coloring.
• a flame retardant can be added to the resin composition of the present invention for the purpose of imparting flame retardancy, as long as the effect of the present invention is not impaired.
• flame retardants there are no particular limitations on the flame retardants that can be used, and general filler-based flame retardants and solvent-soluble flame retardants can be used, and they can be used alone or in combination of two or more types.
• the imide group-containing resin of the present invention and the resin composition of the present invention are suitable for use as an adhesive composition containing them, since they have excellent adhesion to substrates and flexibility.
• the adhesive when used as an adhesive, but they are particularly suitable for bonding metals to each other, heat-resistant films to each other, or metals to heat-resistant films, since they have excellent adhesion to metals and heat-resistant films. Since the heat resistance and insulating properties of polyimide resins are also maintained, more specifically, they are suitable for use in the construction of parts of electrical and electronic products. They can also be used as adhesives for bonding metals to each other or metals to engineering plastics, as structural or interior adhesives for automobiles, or as building adhesives.
• the imide group-containing resin of the present invention and the resin composition of the present invention are excellent in adhesion to substrates and flexibility, and therefore are suitable for use as coating compositions containing them.
• the solution of the resin composition was applied to a polyimide film (Apical 12.5NPI, manufactured by Kaneka) so that the thickness after drying was 20 ⁇ m, and dried in a hot air dryer at 140 ° C for 3 minutes to obtain a sample in a B-stage state.
• the resin composition-coated surface of this B-stage sample was overlapped with the glossy surface of a copper foil (BHY, manufactured by JX Nippon Oil & Gas Exploration Co., Ltd., thickness 18 ⁇ m), and placed in an oven heated to 150 ° C. for 4 hours to be thermally cured.
• Adhesive strength is 0.5 N/mm or more
• Adhesive strength is less than 0.5 N/mm
• Propylene glycol bisanhydrotrimellitate TMA Fujifilm Wako Pure Chemical Industries, Ltd. Trimellitic anhydride PMDA: Tokyo Chemical Industry Co., Ltd. Pyromellitic anhydride MDI: Fujifilm Wako Pure Chemical Industries, Ltd. Diphenylmethane diisocyanate TDI: Tokyo Chemical Industry Co., Ltd. Tolylene diisocyanate ToDI: Nippon Soda Co., Ltd. o-Tolidine diisocyanate NMP: Fujifilm Wako Pure Chemical Industries, Ltd. N-Methyl-2-pyrrolidone DMAc: N,N-dimethylacetamide manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• Example 1 A resin composition was prepared by mixing 85 parts by mass of the imide group-containing resin (1) solution as solid content and 15 parts by mass of jER828 (epoxy resin (C) as a curing agent) as solid content. Note that a dimethylacetamide solution of jER828 with a solid content of 30% by mass was prepared in advance and used. The adhesive composition obtained was evaluated for its adhesiveness as an adhesive, its adhesion as a coating, and its processability. The results are shown in Table 2.
• Examples 2 to 11 and Comparative Examples 1 to 3 Resin compositions were prepared in the same manner as in Example 1, except that the type and amount of imide group-containing resin and curing agent were changed to obtain the adhesive composition formulation shown in Table 2. Note that a dimethylacetamide solution with a solid content of 30 mass% was prepared in advance and used as the curing agent. The adhesive properties as an adhesive, adhesion as a coating, and processability of the obtained adhesive compositions were evaluated. The results are shown in Table 2.
• jER828 Mitsubishi Chemical epoxy resin (bisphenol type epoxy resin, epoxy equivalent: 189 g/eq)
• jER152 Epoxy resin manufactured by Mitsubishi Chemical (phenol novolac type epoxy resin, epoxy equivalent: 177 g/eq)
• jER1001 Mitsubishi Chemical epoxy resin (bisphenol type epoxy resin, epoxy equivalent: 475 g/eq)
• the resin compositions of Examples 1 to 11 that satisfy the requirements of the present invention were able to simultaneously exhibit excellent solvent solubility, flexibility, and adhesion, and were suitable for adhesive and paint applications.
• Comparative Example 1 since the imide group-containing resin does not have a long-chain aliphatic dicarboxylic acid (B) as a constituent unit, it showed adhesion to the substrate as a paint, but in the evaluation of adhesive adhesion and paint processability, which involved large deformation of the resin composition during testing, it was not flexible enough to obtain good results.
• Comparative Example 2 since the imide group-containing resin did not have an acid dianhydride compound (A) having an ester group or an ether group as a constituent unit, it showed poor adhesion to the substrate, and as a result, the adhesive adhesion, paint adhesion, and paint processability were poor.
• Comparative Example 3 since the imide group-containing resin did not have either an acid dianhydride compound (A) having an ester group or an ether group or a long-chain aliphatic dicarboxylic acid (B) as a constituent unit, it showed extremely poor solvent solubility, and the resin became insoluble during polymerization of the imide group-containing resin. Therefore, a resin composition could not be obtained, and it could not be evaluated as an adhesive or paint.
• the resin composition using the imide group-containing resin of the present invention has excellent solvent solubility, flexibility, and adhesion, making it suitable for use as an adhesive or paint. Therefore, the present invention is extremely useful in this industry.

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• 2023
  • 2023-09-22 JP JP2024561200A patent/JPWO2024116572A1/ja active Pending
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