JP6580980B2 - Amidoimide resin and amidoimide resin composition - Google Patents

Description

  The present invention relates to an amideimide resin and an amideimide resin composition.

  Due to its excellent strength, heat resistance, and electrical insulation, the demand for polyimide resins has increased rapidly in recent years in applications such as films, paints, and electrical / electronic devices.

  However, conventionally developed and used polyimide resins have restrictions on solvents used such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, cresol and the like from the viewpoint of solubility (see Patent Documents 1 and 2). There was room for improvement in terms of environmental burden of these solvents.

Japanese Patent Laid-Open No. 9-12879 JP 58-174441 A

  Accordingly, an object of the present invention is to provide an amide imide resin and an amide imide resin composition that are easy to handle, have excellent heat resistance, and do not exhibit brittleness.

  As a result of intensive studies, the present inventors have found that a specific amideimide resin exhibits excellent heat resistance and flexibility while having good handleability.

That is, the object of the present invention is achieved by the following (1) to ( 7 ).
(1) an aliphatic dicarboxylic acid compound (a), amide-imide containing a constitutional unit derived from the isocyanate compound (c) having two or more isocyanate groups compound having a carboxylic acid anhydride structure (b), and in a molecule An amidoimide resin that is a resin and each component satisfies the following relationships (i) and (ii):

(I) the molar ratio of the isocyanate compound (c) (aliphatic dicarboxylic acid compound (a) + carboxylic acid compound having an anhydride structure (b)) ((c) / ((a) + (b))) Is 0.45 to 0.75.

(Ii) an aliphatic dicarboxylic acid compound (a) with a compound having a carboxylic anhydride structure molar ratio of (b) ((a) / (b)) is 0.01 to 0.5.

Preferably, the aliphatic dicarboxylic acid compound (a), a compound having a carboxylic acid anhydride structure (b), and an isocyanate compound having two or more isocyanate groups in one molecule mixture containing, as essential component (c) It is an amide imide resin obtained by making it react, Comprising: Each component is an amide imide resin which satisfy | fills said relationship (i) and (ii).
(2) The aliphatic dicarboxylic acid compound (a) was selected from the group consisting of succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid The amidoimide resin according to (1), which is at least one compound.
( 3 ) An amideimide resin composition comprising the amideimide resin according to (1) or (2) and an organic solvent.
( 4 ) The amideimide resin composition according to ( 3 ), wherein the organic solvent is a polar solvent containing neither a nitrogen atom nor a sulfur atom.
( 5 ) A cured product obtained by curing the amideimide resin according to (1) or (2) or the amideimide resin composition according to ( 3 ) or ( 4 ).
(6) aliphatic dicarboxylic acid compound (a), a compound having a carboxylic acid anhydride structure (b), and the components the following relationship isocyanate compound (c) having two or more isocyanate groups in one molecule A method for producing an amide-imide resin, comprising mixing and reacting so as to satisfy (i) and (ii).
(7) The aliphatic dicarboxylic acid compound (a) is selected from the group consisting of succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid The method for producing an amideimide resin according to (6), which is at least one compound.

(I) the molar ratio of the isocyanate compound (c) (aliphatic dicarboxylic acid compound (a) + carboxylic acid compound having an anhydride structure (b)) ((c) / ((a) + (b))) Is 0.45 to 0.75.

(Ii) an aliphatic dicarboxylic acid compound (a) with a compound having a carboxylic acid anhydride structure molar ratio of (b) ((a) / (b)) is 0.01 to 0.5.

  The amidoimide resin composition of the present invention has good handleability, and the resulting cured product has excellent heat resistance but does not exhibit brittleness.

  The amidoimide resin of the present invention comprises a polyvalent carboxylic acid compound (a) having two or more carboxyl groups in one molecule, a compound (b) having a carboxylic anhydride structure, and two or more isocyanate groups in one molecule. It is obtained by reacting a mixture containing an isocyanate compound (c) having an essential component at a specific molar ratio. That is, it includes the structural unit derived from the above (a), (b) and (c).

  Preferably, it is obtained by the following production method.

  Polyvalent carboxylic acid compound (a) having two or more carboxyl groups in one molecule, compound (b) having a carboxylic anhydride structure, and isocyanate compound (c) having two or more isocyanate groups in one molecule ) Is mixed and reacted so as to satisfy the following relationships (i) and (ii):

  (I) The molar ratio ((c) / ((a) + (b))) of the isocyanate compound (c) and (polyvalent carboxylic acid compound (a) + compound (b) having a carboxylic anhydride structure) 0.45 to 0.75.

  (Ii) The molar ratio ((a) / (b)) of the polyvalent carboxylic acid compound (a) having two or more carboxyl groups in one molecule to the compound (b) having a carboxylic anhydride structure is 0. 01-0.5.

Examples of the polyvalent carboxylic acid compound (a) having two or more carboxyl groups in one molecule include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, Aliphatic dicarboxylic acids such as dodecanedioic acid, phthalic acid compounds such as isophthalic acid, terephthalic acid, orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7- Naphthalenedicarboxylic acid such as naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, etc. Is, it can be used either alone or in combination.
Can be used, and one or more can be mixed and used. Among these, aliphatic dicarboxylic acids are preferable, and adipic acid is particularly preferable.

  The compound (b) having a carboxylic acid anhydride structure preferably has one or more carboxylic acid anhydride structures in one molecule, and preferably contains a tricarboxylic acid anhydride as an essential component.

  Examples of the tricarboxylic acid anhydride include trimellitic anhydride, naphthalene-1,2,4-tricarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid anhydride, and the like. Two or more kinds can be used.

  Tetracarboxylic acid anhydrides may be used in combination. Examples of tetracarboxylic acid anhydrides include pyromellitic dianhydride and benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride. , Diphenyl ether-3,4,3 ′, 4′-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,4,3 ′, 4′- Tetracarboxylic dianhydride, biphenyl-2,3,2 ′, 3′-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4 , 5-tetracarboxylic dianhydride, naphthalene-1,8,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 4,8- Dimethyl-1,2,3 , 6,7-Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, berylene-3,4,9,10 -Tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxy) Phenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, and the like. It can be used either alone or in combination.

  In the present invention, a compound having two or more carboxyl groups and a carboxylic acid anhydride structure per molecule belongs to the polyvalent carboxylic acid compound (a).

  As the isocyanate compound (c) having two or more isocyanate groups in one molecule, compounds having two or more isocyanate groups in the molecule can be used. For example, o-tolylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4 Aromatic isocyanates such as' -diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, naphthalene diisocyanate, and isophorone di Aliphatic and alicyclic isocyanates such as socyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornylene diisocyanate, lysine diisocyanate and the like, and one kind of these isocyanate compounds Polyisocyanate materials such as the above burettes or nurates can also be used. These can use 1 type (s) or 2 or more types.

  Among these, from the viewpoint of solubility of the obtained amideimide resin in a solvent, it is preferable to have 2 to 4 isocyanate groups in one molecule, more preferably a compound having an alicyclic structure. Of these, isophorone diisocyanate is preferred.

  Polyvalent carboxylic acid compound (a) having two or more carboxyl groups in one molecule, compound (b) having a carboxylic anhydride structure, isocyanate compound (c) having two or more isocyanate groups in one molecule In the reaction of the mixture containing as an essential component, the isocyanate compound (c) is 0.75 mol or less with respect to 1 mol of the (polycarboxylic acid compound (a) + the compound (b) having a carboxylic anhydride structure). It is preferable to do. More preferably, it is 0.73 mol or less, More preferably, it is 0.71 mol or less. By using below these, since the molecular weight of an amide imide resin can be controlled to an appropriate range, the solubility to a solvent becomes more favorable. Moreover, it is preferable that an isocyanate compound (c) shall be 0.45 mol or more with respect to 1 mol of (polyhydric carboxylic acid compound (a) + compound (b) which has a carboxylic anhydride structure). More preferably, it is 0.5 mol or more, More preferably, it is 0.55 mol or more. Since the remaining polyvalent carboxylic acid compound (a) or compound (b) having a carboxylic anhydride structure can be reduced by using more than these, it does not cause a decrease in heat resistance due to low molecular weight substances.

  Moreover, it is preferable to make 0.5 mol or less of polyvalent carboxylic acid compound (a) which has a 2 or more carboxyl group in 1 molecule with respect to 1 mol of compounds (b) which have a carboxylic anhydride structure. More preferably, it is 0.4 mol or less, More preferably, it is 0.3 mol or less. Moreover, it is preferable that polyhydric carboxylic acid compound (a) which has a 2 or more carboxyl group in 1 molecule shall be 0.01 mol or more with respect to 1 mol of compounds (b) which have a carboxylic anhydride structure. More preferably, it is 0.02 mol or more, More preferably, it is 0.03 mol or more. By using in these ranges, the amount of imide bond (generated by reaction of acid anhydride group and isocyanate group) and amide bond (generated by reaction of carboxyl group and isocyanate group) can be controlled within an appropriate range. Both solubility in solvents and heat resistance are improved.

  As a preferable production method of the amide-imide resin, in the organic solvent described later, the polyvalent carboxylic acid compound (a), the compound (b) having a carboxylic anhydride structure, and an isocyanate having two or more isocyanate groups in one molecule The compound (c) may be reacted at a temperature of 50 to 250 ° C., preferably 130 to 180 ° C. for 1 to 30 hours.

  In the present invention, a high molecular weight amidimide resin can be obtained by reacting the amideimide resin obtained above with a compound having two or more functional groups capable of reacting with a carboxyl group in one molecule.

  Specifically, the polyvalent carboxylic acid compound (a) having two or more carboxyl groups in one molecule, the compound (b) having a carboxylic anhydride structure, an isocyanate compound having two or more isocyanate groups in one molecule. (C) is reacted, and a compound having two or more functional groups capable of reacting with a carboxyl group in one molecule is reacted.

  Examples of the compound having a functional group capable of reacting with a carboxyl group include an epoxy compound, an oxazoline compound, and an oxetane compound. Specifically, examples of the epoxy compound include novolak type epoxy resin, bisphenol type epoxy resin, alicyclic epoxy resin, triglycidyl isocyanurate, and examples of the oxazoline compound include 1,3-phenylenebisoxazoline. Among these, an alicyclic epoxy resin is preferable from the viewpoint of the characteristics of the obtained amideimide resin and storage stability.

  In addition, the reaction between a amideimide resin having a carboxyl group and a compound having two or more functional groups capable of reacting with a carboxyl group in one molecule is a function capable of reacting with the carboxyl group with respect to 1 mol of the carboxyl group of the amideimide resin. The group is preferably 0.9 mol or less. More preferably, it is 0.8 mol or less, More preferably, it is 0.7 mol or less. By using below these, since the molecular weight of the obtained high molecular weight amidoimide resin can be controlled within an appropriate range (preferably the weight average molecular weight is 1,000 or more and 100,000 or less), the solubility in an organic solvent is not impaired. Moreover, it is preferable that the functional group which can react with a carboxyl group shall be 0.1 mol or more with respect to 1 mol of carboxyl groups which an amide imide resin has. More preferably, it is 0.15 mol or more, More preferably, it is 0.2 mol or more. By using more than these, since the amideimide resin remaining with a low molecular weight can be reduced, heat resistance is not lowered.

  Also in this case, in an organic solvent described later, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, triphenylphosphine and tetraphenylphosphonium. A reaction catalyst such as a phosphorus compound such as bromide, a metal organic acid salt or inorganic acid salt (such as lithium chloride), or a chelate compound can be added and reacted.

  The reaction temperature here is preferably 50 to 150 ° C. The more preferable upper limit of the reaction temperature is 130 ° C., more preferably 120 ° C., and the reaction at this temperature or lower can further reduce the concern about gelation due to side reactions. Further, a more preferable lower limit of the reaction temperature is 55 ° C, and more preferably 60 ° C. By setting it above this temperature, the reaction proceeds promptly.

  In the present invention, a amideimide resin containing a radically polymerizable unsaturated bond is obtained by reacting a carboxyl group of an amideimide resin or a high molecular weight amideimide resin with a radical polymerizable monomer having a functional group capable of reacting with the carboxyl group. It can also be.

  Examples of the functional group capable of reacting with a carboxyl group include an isocyanate group, a vinyl ether group, an epoxy group, an oxazoline group, an aziridine group, and an oxetanyl group. Specific examples of the radical polymerizable monomer include isocyanate ethyl (meth) acrylate, (Meth) acrylic acid 2- (vinyloxyethoxy) ethyl, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isopropenyl-2-oxazoline, N- (meth) acryloylaziridine and the like, one of these Or 2 or more types can be used.

  As an organic solvent used as a solvent of the amide imide resin composition of the present invention, a polar solvent containing neither a nitrogen atom nor a sulfur atom is a main component (preferably 90% by mass in the total organic solvent) from the viewpoint of reducing the burden on the environment. Or more, more preferably 95% by mass or more, particularly preferably 99% by mass or more and 100% by mass or less. Use of such a general-purpose solvent facilitates application in various fields such as the electrical and electronic industry.

  The organic solvent in the present invention does not react with the environmental aspect, carboxylic acid anhydride or isocyanate group, from the viewpoint of handleability of the amideimide resin composition containing the organic solvent, storage stability, for example, an ether type having no hydroxyl group, Examples include esters and ketones, and ether solvents are particularly preferable.

  As the ether solvent, known solvents can be used. For example, ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, and the like. Polyethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether; ethylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate 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 monoethyl ether acetate, triethylene glycol monobutyl ether acetate; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, Polypropylene glycol dialkyl ethers such as propylene glycol dimethyl ether, tripropylene glycol diethyl ether and tripropylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate Dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol And polypropylene glycol monoalkyl ether acetates such as nobutyl ether acetate;

  The amount of the organic solvent used is 900 parts by mass or less, more preferably 500 parts by mass or less, with respect to 100 parts by mass of the amideimide resin of the present invention. A preferable lower limit is 30 parts by mass or more, more preferably 60 parts by mass or more with respect to 100 parts by mass of the amidoimide resin. By controlling to the above numerical range, the handleability and storage stability of the composition, and further the efficiency during the coating operation are improved.

  The amideimide resin composition of the present invention can be obtained by a production method having a step of obtaining an amideimide resin by the production method of the present invention and a step of blending the amideimide resin and other components (blending step).

  In the present invention, a resin composition comprising an amideimide resin and an organic solvent can be applied and dried, but the composition may further contain a reactive diluent. By setting it as such a composition, the coating film (cured material) which has a crosslinked structure through a heat | fever and photoreaction will be obtained, and it will become a more excellent characteristic.

  Examples of the reactive diluent include a radical polymerizable resin and a radical polymerizable monomer.

  As the radical polymerizable resin, unsaturated polyester, urethane acrylate, polyester acrylate, epoxy acrylate, or the like can be used.

  As the radical polymerizable monomer, either a monofunctional monomer (one radical polymerizable double bond) or a polyfunctional monomer (two or more radical polymerizable double bonds) can be used. Since the radically polymerizable monomer is involved in the polymerization, it can be used as a solvent for various reactions in addition to improving the properties of the resulting cured product, and further the viscosity of the resin composition can be adjusted. When using a radically polymerizable resin and / or a radically polymerizable monomer, the preferred amount used is 300 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the amideimide resin of the present invention. A preferable lower limit value is 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the amidoimide resin.

  Specific examples of the radical polymerizable monomer include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- ( 2-chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmethylmaleimide, N- (2,4,6-tribromophenyl) Maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- (2-methoxyphenyl) maleimide, N- (2,4,6 -Trichlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimi N-substituted maleimide group-containing monomers such as N- (1-hydroxyphenyl) maleimide; styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, p-hydroxystyrene, divinylbenzene, diallyl phthalate, diallylbenzene Aromatic vinyl monomers such as phosphonate; vinyl ester monomers such as vinyl acetate and vinyl adipate; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxymethyl (meth) acrylamide, pentaerythritol mono (meta) Acrylate, dipentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, glycerol mono (meth) acrylate, (di) ethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris [2- (meth) (Acryloyloxyethyl) triazine, dendritic acrylate and other (meth) acrylic monomers; n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl (Hydroxy) alkyl vinyl (thio) ethers such as ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 4-hydroxybutyl vinyl ether; 2- (vinyloxyethoxy) ethyl (meth) acrylate, ( 2- (isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, etc. A vinyl (thio) ether having a radical polymerizable double bond of the above; an acid anhydride group-containing monomer such as maleic anhydride, or a monomer obtained by ring-opening modification of an acid anhydride group with alcohols, amines, water, etc. Mer; N- Examples thereof include N-vinyl monomers such as vinylpyrrolidone and N-vinyloxazolidone; compounds having one or more double bonds capable of radical polymerization, such as allyl alcohol and triallyl cyanurate.

  These are appropriately selected according to the use and required characteristics, and can be used alone or in combination of two or more.

  The composition comprising the amidoimide resin composition of the present invention and a reactive diluent is obtained by using a known thermal polymerization initiator such as benzoyl peroxide or cumene hydroperoxide or a known photopolymerization initiator, Radical polymerization by heat or light becomes possible.

  In the amide imide resin composition of the present invention, if necessary, fillers such as talc, clay, barium sulfate, coloring pigments, antifoaming agents, coupling agents, leveling agents, sensitizers, release agents, You may add well-known additives, such as a lubricant, a plasticizer, antioxidant, a ultraviolet absorber, a flame retardant, a polymerization inhibitor, a thickener. Further, various reinforcing fibers can be used as reinforcing fibers to form a fiber-reinforced composite material.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are not intended to limit the present invention, and all modifications that do not depart from the spirit of the present invention are included in the technical scope of the present invention. Is done. In the following examples, physical properties were evaluated as follows.
1. Chemical structure: FT-IR (manufactured by Thermo Scientific, NEXUS670) was used for analysis.
2. Acid value: About 0.3 g of each solution is precisely weighed, dissolved in a mixed solvent of 90 g of acetone / 10 g of water, and 0.1N KOH aqueous solution is used as a titrant, and acid is measured by an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.) The value was measured.
3. Weight average molecular weight (Mw): The weight average molecular weight (Mw) was measured by GPC (gel permeation chromatography) method using HLC-8220 GPC (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.
4). Thermomechanical properties (TMA): To 100 parts of each solution, 19.3 parts of a cresol novolac epoxy resin (epoxy equivalent 209.9, softening point 95.5 ° C.) (solid weight ratio 70/30), triphenylphosphine ( Curing catalyst) 0.6 part and 41.5 parts diethylene glycol monoethyl ether acetate were mixed to prepare a thermosetting resin solution. It was applied to a polyethylene terephthalate film so that the film thickness after drying was about 80 μm, dried at 70 ° C. for 20 minutes, cured at 200 ° C. for 1 hour and cooled, and then the peeled cured coating film was cut out to a width of 5 mm. A sample for measurement was obtained. Using a thermomechanical analyzer Bruker AXS TMA 4000 (Bruker AXS Co., Ltd.), thermal analysis was performed by a tensile mode at a distance between chucks of 20 mm, and evaluation was performed by a linear expansion coefficient (CTE ₁₅₀ to ₂₀₀ ) at 150 to 200 ° C.
5). Flexibility: A thermosetting resin solution was prepared in the same manner as in the thermomechanical property (TMA) evaluation. It apply | coated so that the film thickness after drying might be set to about 20 micrometers on the copper plate of thickness 0.5mm, it was dried at 70 degreeC for 20 minutes, and was hardened at 200 degreeC for 1 hour, and it was set as the test board | substrate. Using this test substrate, the flexibility of the cured coating film at a mandrel diameter of 10 mm was evaluated by a cylindrical mandrel method.
Synthesis example 1
In a vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube, 247 g of diethylene glycol monoethyl ether acetate, 4 g (0.03 mol) of adipic acid, 162 g (0.84 mol) of trimellitic anhydride, and 133 g of isophorone diisocyanate (0.6 mol) was added, the temperature was raised to 140 ° C., and the reaction was carried out at this temperature for 20 hours. The system became a brown clear liquid, and the disappearance of 2260 cm −1, which is the characteristic absorption of the isocyanate group, was confirmed by infrared spectrum measurement. 55 g of diethylene glycol monoethyl ether acetate was added to obtain a diethylene glycol monoethyl ether acetate solution containing 45% of the amide imide resin A-1 of the present invention. The acid value was 124 mg KOH / g (in terms of solid content), and the weight average molecular weight (Mw) in terms of polystyrene was 1600.
Synthesis example 2
Using the same apparatus as in Synthesis Example 1, 198 g of diethylene glycol monoethyl ether acetate, 22 g (0.15 mol) of adipic acid, 115 g (0.6 mol) of trimellitic anhydride, and 100 g (0.45 mol) of isophorone diisocyanate were added. The temperature was raised to 0 ° C., and the reaction was carried out at this temperature for 20 hours. The system became a brown clear liquid, and the disappearance of 2260 cm −1, which is the characteristic absorption of the isocyanate group, was confirmed by infrared spectrum measurement. 44 g of diethylene glycol monoethyl ether acetate was added to obtain a diethylene glycol monoethyl ether acetate solution containing 45% of the amide imide resin A-2 of the present invention. The acid value was 170 mgKOH / g (in terms of solid content) and the polystyrene-equivalent weight average molecular weight (Mw) was 1300.
Comparative Synthesis Example 1
Using the same apparatus as in Synthesis Example 1, 248 g of diethylene glycol monoethyl ether acetate, 6 g (0.03 mol) of pyromellitic dianhydride, 162 g (0.84 mol) of trimellitic anhydride, and 133 g (0.6 mol) of isophorone diisocyanate The mixture was heated to 140 ° C. and reacted at this temperature for 20 hours. The system became a brown clear liquid, and the disappearance of 2260 cm −1, which is the characteristic absorption of the isocyanate group, was confirmed by infrared spectrum measurement. 55 g of diethylene glycol monoethyl ether acetate was added to obtain a diethylene glycol monoethyl ether acetate solution containing 45% of comparative amideimide resin B-1. The acid value was 122 mgKOH / g (in terms of solid content), and the weight average molecular weight (Mw) in terms of polystyrene was 1200.
Comparative Synthesis Example 2
Using the same apparatus as in Synthesis Example 1, 282 g of diethylene glycol monoethyl ether acetate, 66 g (0.45 mol) of adipic acid, 115 g (0.6 mol) of trimellitic anhydride, and 167 g (0.75 mol) of isophorone diisocyanate were added. The temperature was raised to ° C. When the reaction was carried out for about 10 hours, a large amount of insoluble precipitates were formed in the system and became non-uniform, so the reaction was terminated.
Using the amideimide resins A-1 to A-2 of the present invention obtained in Synthesis Examples and the comparative amideimide resin B-1 obtained in Comparative Synthesis Example 1, thermomechanical properties and flexibility were evaluated. The results are shown in Table 1.

ａ：多価カルボン酸化合物のモル数（ｍｏｌ）
ｂ：カルボン酸無水物構造を有する化合物のモル数（ｍｏｌ）
ｃ：イソシアネート化合物のモル数（ｍｏｌ）
ＣＴＥ_{１５０〜２００}：１５０〜２００℃における線膨張率（ｐｐｍ／Ｋ）

本発明のアミドイミド樹脂Ａ−１〜Ａ−２は熱機械特性が良好であり、多価カルボン酸化合物を使用していない比較用アミドイミド樹脂Ｂ−１よりも屈曲性が良好であることがわかった。また、比較合成例２のように多価カルボン酸化合物が多過ぎると溶剤溶解性が不足して目的の樹脂が得られないことから、使用割合として適切な領域があることがわかった。

a: Number of moles of polycarboxylic acid compound (mol)
b: Number of moles of compound having carboxylic anhydride structure (mol)
c: Number of moles of isocyanate compound (mol)
CTE _150-200 : linear expansion coefficient at 150-200 ° C. (ppm / K)

It has been found that the amideimide resins A-1 to A-2 of the present invention have good thermomechanical properties and are more flexible than the comparative amideimide resin B-1 that does not use a polyvalent carboxylic acid compound. . Moreover, since there was insufficient solvent solubility and the target resin was not obtained when there were too many polycarboxylic acid compounds like the comparative synthesis example 2, it turned out that there exists a suitable area | region as a usage rate.

  The amideimide resin and amideimide resin composition of the present invention are excellent in handleability and heat resistance but do not develop brittleness. Therefore, it can be suitably used for applications such as films, paints, and electrical / electronic devices.

Claims (7)

There in an amide-imide resin containing a constitutional unit derived from the aliphatic dicarboxylic acid compound (a), a compound having a carboxylic acid anhydride structure (b), and an isocyanate compound having two or more isocyanate groups per molecule (c) Each component satisfies the following relationships (i) and (ii):
(I) the molar ratio of the isocyanate compound (c) (aliphatic dicarboxylic acid compound (a) + carboxylic acid compound having an anhydride structure (b)) ((c) / ((a) + (b))) Is 0.45 to 0.75.
(Ii) an aliphatic dicarboxylic acid compound (a) with a compound having a carboxylic acid anhydride structure molar ratio of (b) ((a) / (b)) is 0.01 to 0.5. The aliphatic dicarboxylic acid compound (a) is at least one selected from the group consisting of succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid The amide imide resin of Claim 1 which is a compound. And amide-imide resin according to claim 1 or 2, amide-imide resin composition characterized by containing an organic solvent. The amide imide resin composition according to claim 3 , wherein the organic solvent is a polar solvent containing neither a nitrogen atom nor a sulfur atom. Hardened | cured material formed by hardening | curing the amideimide resin of Claim 1 or 2 , or the amideimide resin composition of Claim 3 or 4 . Aliphatic dicarboxylic acid compounds (a), a compound having a carboxylic acid anhydride structure (b), and an isocyanate compound having two or more isocyanate groups in one molecule each component the following relationship (c) (i) And a method for producing an amide-imide resin, which is mixed and reacted so as to satisfy (ii).
(I) the molar ratio of the isocyanate compound (c) (aliphatic dicarboxylic acid compound (a) + carboxylic acid compound having an anhydride structure (b)) ((c) / ((a) + (b))) Is 0.45 to 0.75.
(Ii) an aliphatic dicarboxylic acid compound (a) with a compound having a carboxylic acid anhydride structure molar ratio of (b) ((a) / (b)) is 0.01 to 0.5. The aliphatic dicarboxylic acid compound (a) is at least one selected from the group consisting of succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid The manufacturing method of the amide imide resin of Claim 6 which is a compound.