JP3470464B2 - Thermosetting resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a specific modified polycarbohydrate.
Contains diimide, solubility in various solvents and solution
As well as excellent storage stability, the cured product is
For moisture resistance, transparency, heat resistance, electrical insulation, mechanical properties, etc.
The present invention relates to an excellent novel thermosetting resin composition. [0002] Polycarbodiimides are polyisocyanate
A resin obtained by the decarboxylation condensation of a salt compound.
Is manufactured by, for example, Die Makromo by DJLyman et al.
l. Chem., 67, 1 (1963); J. Am. Chem. by E. Deyer et al.
Soc., 80,5495 (1958), J. Appl.
Polym. Sci., 21, 1999 (1977), J. Or by TWCampbell
g. Chem., 28, 2069 (1963), JP-A-51-61599.
It is disclosed in gazettes and the like. Polycarbodiimide is heated
Can crosslink carbodiimide groups in the molecule
Application as a thermosetting resin with excellent heat resistance
Expected. However, polycarbodiimides
It takes a considerable amount of time, even at high temperatures, to fully cure.
There is a problem of doing. In addition, polycarbodiimide is
Low solubility in seed solvents, and cool and dark in solution
Agglomeration of polymer progresses gradually in
Thermosetting resin is difficult to store
That the excellent characteristics of the product are fully utilized in practical use
The current situation is that it cannot be said. Therefore, polycarbodiimide
To improve the curing speed by mixing various compounds
Attempts have been made, for example, in Japanese Patent Application Laid-Open No. 61-235414.
In this report, a compound containing active hydrogen was mixed with polycarbodiimide.
Combined thermosetting resin compositions have been proposed. But
However, in this method, the inherent heat resistance of polycarbodiimide
However, there is a drawback that is deteriorated. Japanese Patent Laid-Open No. 4-161
No. 426 discloses that polycarbodiimides include polyisocyanates.
A thermosetting resin composition mixed with a nitrate compound has been proposed.
However, this composition still has a curing temperature of 250
° C, which is not enough to improve the curing properties.
You. Moreover, these resin compositions can be stored as a solution.
The stability is not improved at all. On the other hand, polycarbodiimide
Thermosetting resin mixed with epoxy compound and curing catalyst
Compositions are also known, for example, from JP-A-62-1714.
In the publication, a tertiary amine is used as a curing catalyst.
JP-A-342713 discloses a halogenated zinc as a curing catalyst.
It is possible to use lead or a mixture of it and onium salts
Proposed. However, of these methods,
In the former case, the tertiary amine is a cross-linked polycarbodiimide
Because it has the property of accelerating the reaction,
The problem is that the preservation stability deteriorates on the contrary,
In the latter, the storage stability of the resin composition is improved.
Not only halogen, zinc, etc. derived from the curing catalyst
Remain as migrating impurities,
It can not be used in problem areas, especially in the field of electronic components,
The range of use will be severely restricted. That is, the conventional
Thermosetting resin composition containing polycarbodiimide as a main component
Is used as a solution with heat resistance, electrical insulation, mechanical properties, etc.
Properties balance with storage stability and curing properties
It is not always satisfactory in terms of. [0003] The object of the present invention is to provide a poly-
The inherent heat resistance, electrical insulation and mechanical properties of carbodiimide
Solubility and solution in various solvents without impairing
Excellent storage stability and use a curing catalyst
Hardens easily under mild conditions
The material is resistant to moisture, transparency, chemical stability and various substrates
Polycarbodiimide thermosetting resin with excellent adhesive properties
It is to provide a fat composition. The present invention provides: (A) a general formula (1): -N = C = NR ¹ -... (1) (However, R ¹ Represents a divalent organic group. )
Graft-reactive groups to polycarbodiimides having units
And a compound having a carboxylic anhydride group (hereinafter referred to as “reaction
Compound ". Resin) grafted with one or more of
(Hereinafter referred to as “modified polycarbodiimide”),
Containing (B) epoxy compound
And a curable resin composition. Below, the book
The invention will be described in detail. Thereby, the object and structure of the present invention are
The results and effects will be clear. [0005] Modified polycarbodiimide <Polycarbodiimide> First, the polycarbodiimide used for the synthesis of the modified polycarbodiimide is used.
The method for synthesizing carbodiimide is not particularly limited.
Is, for example, an organic polyisocyanate
Catalyst that promotes the carbodiimidization reaction of
It is referred to as a "rubodiimidation catalyst." ) In the presence of
By doing so, polycarbodiimide can be synthesized
You. The organic polymer used in the synthesis of this polycarbodiimide
As the isocyanate, an organic diisocyanate is preferred.
Good. Examples of such organic diisocyanates include
For example, phenylene-1,3-diisocyanate, phenyle
1,4-diisocyanate, 1-methoxyphenylene
2,4-diisocyanate, 1-methylphenylene
-2,4-diisocyanate, 2,4-tolylenediiso
Cyanate, 2,6-tolylene diisocyanate, 1,
3-xylylene diisocyanate, 1,4-xylylene
Diisocyanate, biphenylene-4,4'-diisocyanate
Anate, 3,3'-dimethoxybiphenylene-4,
4'-diisocyanate, 3,3'-dimethylbiphenyl
Len-4,4'-diisocyanate, diphenylmethane
-2,4'-diisocyanate, diphenylmethane-
4,4'-diisocyanate, 3,3'-dimethoxydi
Phenylmethane-4,4'-diisocyanate, 3,
3'-dimethyldiphenylmethane-4,4'-diisocy
Anate, naphthylene-1,5-diisocyanate,
Clobutylene-1,3-diisocyanate, cyclopen
Tylene-1,3-diisocyanate, cyclohexylene
-1,3-diisocyanate, cyclohexylene-1,
4-diisocyanate, 1-methylcyclohexylene-
2,4-diisocyanate, 1-methylcyclohexyl
-2,6-diisocyanate, 1-isocyanate-
3,3,5-trimethyl-5-isocyanatomethyl
Chlorohexane, cyclohexane-1,3-bis (methyl
Isocyanate), cyclohexane-1,4-bis (meth
Tyl isocyanate), isophorone diisocyanate,
Dicyclohexylmethane-2,4'-diisocyanate
G, dicyclohexylmethane-4,4'-diisocyane
, Ethylene diisocyanate, tetramethylene-
1,4-diisocyanate, hexamethylene-1,6-
Diisocyanate, dodecamethylene-1,12-diiso
Cyanate, lysine diisocyanate methyl ester, etc.
Or the stoichiometric excess of these organic diisocyanates
Obtained by reacting a compound with a bifunctional active hydrogen-containing compound
Both terminal isocyanate prepolymer and the like can be mentioned.
Wear. The organic diisocyanates may be used alone or in combination.
These can be used in combination. Also, sometimes
Other organic polymers used with organic diisocyanates
As the lysocyanate, for example, phenyl-1,3,3
5-triisocyanate, diphenylmethane-2,4
4'-triisocyanate, diphenylmethane-2,
5,4'-triisocyanate, triphenylmethane-
2,4 ', 4 "-triisocyanate, triphenylmeth
Tan-4,4 ', 4 "-triisocyanate, diphenyl
Methane-2,4,2 ', 4'-tetraisocyanate
G, diphenylmethane-2,5,2 ', 5'-tetri
Socyanate, cyclohexane-1,3,5-triiso
Cyanate, cyclohexane-1,3,5-tris (meth
Tyl isocyanate), 3,5-dimethylcyclohexa
1,3,5-tris (methyl isocyanate)
1,3,5-trimethylcyclohexane-1,3,5-
Tris (methyl isocyanate), dicyclohexylme
Tan-2,4,2'-triisocyanate, dicyclohexane
Xylmethane-2,4,4'-triisocyanate
Trifunctional or higher organic polyisocyanate,
Stoichiometric excess of organic polyisocyanate over
By reaction with bifunctional or higher polyfunctional active hydrogen-containing compounds
Obtained terminal isocyanate prepolymer, etc.
be able to. The other organic polyisocyanate is simply
It can be used alone or as a mixture of two or more.
Was used per 100 parts by weight of organic diisocyanate.
0 to 40 parts by weight, preferably 0 to 20 parts by weight
It is. Furthermore, in the synthesis of polycarbodiimide
Add organic monoisocyanate as needed
With the organic polyisocyanate, the other organic poly isocyanate
When containing isocyanate, the resulting polycarbodi
The molecular weight of imide can be appropriately regulated, and
Use diisocyanate with organic monoisocyanate
As a result, a relatively low molecular weight polycarbodiimide is obtained.
Can be With such organic monoisocyanates
For example, methyl isocyanate, ethyl isocyanate
, N-propyl isocyanate, n-butyl iso
Cyanate, lauryl isocyanate, stearyl iso
Alkyl monoisocyanates such as cyanate; cyclo
Hexyl isocyanate, 4-methylcyclohexylyl
Socyanate, 2,5-dimethylcyclohexyl isocyanate
Cycloalkyl monoisocyanates such as anates;
Phenyl isocyanate, o-tolyl isocyanate, m
-Tolyl isocyanate, p-tolyl isocyanate,
2-methoxyphenyl isocyanate, 4-methoxyphenyl
Phenyl isocyanate, 2-chlorophenyl isocyanate
, 4-chlorophenylisocyanate, 2-trif
Fluoromethylphenyl isocyanate, 4-trifluoro
L-methylphenyl isocyanate, naphthalene-1-a
Aryl monoisocyanates such as socyanates
Can be The organic monoisocyanate is used alone
Or two or more types can be used in combination.
The amount used depends on the desired molecular weight of the polycarbodiimide,
Depends on the presence of organic polyisocyanate
Usually, per 100 parts by weight of the organic polyisocyanate component,
0 to 40 parts by weight, preferably 0 to 20 parts by weight. [0006] Examples of carbodiimidization catalysts include:
For example, 1-phenyl-2-phospholene-1-oxide, 1
-Phenyl-3-methyl-2-phospholene-1-oxy
1-phenyl-2-phosphoren-1-sulfide,
1-phenyl-3-methyl-2-phospholene-1-sul
Fido, 1-ethyl-2-phospholene-1-oxide,
1-ethyl-3-methyl-2-phospholene-1-oxy
1-ethyl-2-phosphoren-1-sulfide, 1
-Ethyl-3-methyl-2-phospholene-1-sulfy
1-methyl-2-phospholene-1-oxide, 1-
Methyl-3-methyl-2-phospholene-1-oxide,
1-methyl-2-phospholene-1-sulfide, 1-methyl
Tyl-3-methyl-2-phospholene-1-sulfide,
Phosphorene compounds such as these 3-phospholene isomers;
Iron pentacarbonyl, diiron nonacarbonyl, tetracalcium
Bonyl nickel, hexacarbonyl tungsten, hex
Metal carbonyl complexes such as sacarbonyl chromium;
Metals such as aluminum, zirconium, chromium, and iron
Acetylacetone complex of trimethyl phosphate, g
Triethyl phosphate, triisopropyl phosphate
G, tri-t-butyl phosphate, triphenyl phosphate
Phosphate esters such as fate can be mentioned. Said
Carbodiimidization catalysts may be used alone or in combination of two or more.
It can be used as
Usually, 0.001 to 100 parts by weight of the anate component
It is 30 parts by weight, preferably 0.01 to 10 parts by weight. The synthesis reaction of polycarbodiimide is carried out without solvent.
It can also be carried out below or in a suitable solvent. The melting
As a medium, polycarbodiimide is produced by heating during the synthesis reaction.
Any solvent can be used as long as it can dissolve
Loroethane, 1,2-dichloroethane, 1,1,1-tol
Lichloroethane, 1,1,2-trichloroethane, 1,
1,1,2-tetrachloroethane, 1,1,2,2-te
Trachloroethane, pentachloroethane, hexachloro
Ethane, 1,1-dichloroethylene, 1,2-dichloro
Ethylene, trichloroethylene, tetrachloroethylene
Chlorobenzene, o-dichlorobenzene, m-dic
Lorobenzene, p-dichlorobenzene, 1,2,4-to
Halo such as Lichlorobenzene and Trichloromethylbenzene
Genated hydrocarbon solvents: dioxane, anisole, tet
Lahydrofuran, tetrahydropyran, diethylene glycol
Chole dimethyl ether, diethylene glycol diethyl
Diether, diethylene glycol dipropyl ether
, Diethylene glycol dibutyl ether, diethyl
Glycol monomethyl ether, diethylene glycol
Lumonoethyl ether, diethylene glycol monopro
Pill ether, diethylene glycol monobutyl ether
D, triethylene glycol monomethyl ether, etc.
-Tel solvents: cyclohexanone, 2-acetylcyclo
Hexanone, 2-methylcyclohexanone, 3-methyl
Cyclohexanone, 4-methylcyclohexanone, cyclo
Roheptanone, 1-decalone, 2-decalone, 2,4-
Dimethyl-3-pentanone, 4,4-dimethyl-2-pe
Tanthanone, 2-methyl-3-hexanone, 5-methyl-
2-hexanone, 2-heptanone, 3-heptanone, 4
-Heptanone, 2-methyl-3-heptanone, 5-methyl
Ru-3-heptanone, 2,6-dimethyl-4-heptano
2-octanone, 3-octanone, 2-nonanone,
3-nonanone, 5-nonanone, 2-decanone, 3-deca
Ketone solvents such as nonone and 4-decanone; benzene, tol
Aromatic coal such as ene, xylene, ethylbenzene, cumene, etc.
Hydrogenated solvent: N-methyl-2-pyrrolidone, N-acetate
Tyl-2-pyrrolidone, N-benzyl-2-pyrrolidone
, N-methyl-3-pyrrolidone, N-acetyl-3-
Pyrrolidone, N-benzyl-3-pyrrolidone, formua
Amide, N-methylformamide, N, N-dimethylform
Muamide, N-ethylformamide, N, N-diethyl
Formamide, acetamide, N-methylacetamide
, N, N-dimethylacetamide, N-methylpropyl
Amide solvents such as onamides; dimethyl sulfoxide
Aprotic polar solvent; 2-methoxyethyl acetate
G, 2-ethoxyethyl acetate, 2-propoxye
Cyl acetate, 2-butoxyethyl acetate, 2-
Phenoxyethyl acetate, diethylene glycol
Nomethyl ether acetate, diethylene glycol
Noethyl ether acetate, diethylene glycol
Propyl ether acetate, diethylene glycol
Acetate solvents such as monobutyl ether acetate
Can be mentioned. The solvents may be used alone or in combination of two or more.
The above can be mixed and used. Polycarbodiimi
In the synthesis reaction of amide, the solvent is all organic isocyanate
The concentration of the component is usually 0.5 to 60% by weight, preferably
It is used at a ratio of 5 to 50% by weight. All organic isoshi
If the concentration of the anate component is too high,
Bodiimide may gel during the synthesis reaction.
Even if the concentration of all organic isocyanate components is too low
Speed slows down and productivity drops. The temperature of the synthesis reaction of polycarbodiimide is as follows:
Types of organic isocyanate components and carbodiimidization catalysts
The temperature is appropriately selected depending on the temperature.
You. During the synthesis reaction of polycarbodiimide,
The cyanate component may be added in its entirety before the reaction, or
Indicates that all or part of the
May be added. In the present invention, isocyanate
A compound capable of reacting with a carboxy group
It is added at an appropriate reaction stage from the early stage to the late stage of the synthesis reaction.
To block the terminal isocyanate group of polycarbodiimide
Control the molecular weight of the resulting polycarbodiimide.
And later in the polycarbodiimide synthesis reaction.
Addition, the molecular weight of the resulting polycarbodiimide is specified
It can be regulated to a value. Such isocyanates
Compounds that can react with a group include, for example, methanol,
Tanol, isopropanol, cyclohexanol, etc.
Alcohols: dimethylamine, diethylamine, ben
Examples thereof include amines such as zylamine. More than
The polycarbodiimide synthesized as described above can be used as needed.
Separated from the solution. In this case, polycarbodiimi
For example, polycarbodiimide solution
In a non-solvent inert to the polycarbodiimide
And the resulting precipitate or oil is filtered or decanted.
Separation and collection by stationing; Spray drying
Method of separating and collecting; of the obtained polycarbodiimide
Utilization of temperature-dependent solubility change in solvent used for synthesis
Method, i.e., immediately after synthesis, dissolve in the solvent.
Understanding polycarbodiimide lowers system temperature
Separated from the turbid liquid by filtration, etc.
・ Methods of collection and the like can be mentioned.
Can be combined as appropriate. Book
Gel permeation of polycarbodiimide in the invention
Polystyrene determined by ion chromatography (GPC)
The number average molecular weight in terms of len (hereinafter, referred to as “Mn”) is
Usually 400-500,000, preferably 1,000
~ 200,000, particularly preferably 2,000 ~ 10
It is 0000. <Reactive compound> Next, the reaction used for the synthesis of the modified polycarbodiimide
The reactive compound has a graft reactive group and a carboxylic anhydride group.
Wherein the compound is an aromatic compound,
Can be an aliphatic or alicyclic compound,
Cyclic compounds, both carbocyclic and heterocyclic
Good. The graft reactive group in the reactive compound is
Reacts with carbodiimide to form a carboxylic anhydride group.
Modified polycarbo grafted with reactive compound residues
Means a group that results in a diimide. Such a graft
The reactive group may be any functional group having active hydrogen.
For example, carboxyl groups or primary or secondary
And an amino group of This reactive compound
The same or different graft-reactive groups
One or more carboxylic acid anhydride groups
Can be one or more. Such reactivity
Compounds include, for example, trimellitic anhydride, benzene
-1,2,3-tricarboxylic anhydride, naphthalene-
1,2,4-tricarboxylic anhydride, naphthalene-1,
4,5-tricarboxylic anhydride, naphthalene-2,3
6-tricarboxylic anhydride, naphthalene-1,2,8-
Tricarboxylic anhydride, 4- (4-carboxybenzoyi
R) phthalic anhydride, 4- (4-carboxyphenyl)
Phthalic anhydride, 4- (4-carboxyphenoxy) phenyl
Aromatic tricarboxylic anhydrides such as tallic anhydride: pyro
Meric acid monoanhydride monomethyl ester, 3,3 ',
4,4'-benzophenonetetracarboxylic monoanhydride
Nomethyl ester, 3,3 ', 4,4'-biphenylte
Aromatic compounds such as monomethyl ester of tracarboxylic acid monoanhydride
Tetracarboxylic monoanhydride monoalkyl esters; 3
-Carboxymethyl glutaric anhydride, butane-1,
2,4-tricarboxylic acid-1,2-anhydride, propene
Fats such as 1,2,3-tricarboxylic acid-1,2-anhydride
Aromatic tricarboxylic anhydrides; 3-amino-4-cyano-
5-methylphthalic anhydride, 3-amino-4-cyano-
5,6-diphenylphthalic anhydride, 3-methylamino
-4-cyano-5-methylphthalic anhydride, 3-methyl
Amino-4-cyano-5,6-diphenylphthalic anhydride
Aromatic dicarboxylic anhydrides such as products;
Cyanic anhydride, 4-amino-1,2-butanedicarboxylic acid
Anhydride, 4-aminohexahydrophthalic anhydride, N-
Methylaminosuccinic anhydride, 4-methylamino-1,
2-butanedicarboxylic anhydride, 4-methylaminohexyl
Aminoaliphatic dicarboxylic acids such as sahydrophthalic anhydride
Anhydrides can be mentioned. These reactive compounds
Among them, trimellitic anhydride is particularly preferred. Said anti
The reactive compounds may be used alone or as a mixture of two or more.
Can be <Synthesis of Modified Polycarbodiimide> Next, a method for synthesizing modified polycarbodiimide will be described.
I do. The modified polycarbodiimide is represented by the general formula (1)
Polycarbodiimide having a repeating unit represented by
At least one of the reactive compounds in the presence of a suitable catalyst.
Or grafting at an appropriate temperature in the absence of
Reaction. " )
Wear. In this case, the polycarbodiimide alone or
Two or more kinds can be used as a mixture. For denaturation reaction
The amount of the reactive compound used is polycarbodiimide or
Depending on the type of the compound, the use of the thermosetting resin composition, etc.
Although appropriately adjusted, general formula (1) of polycarbodiimide
1 mole of the repeating unit represented by
The graft-reactive group is 0.01 to 1 mol, preferably 0.1 to 1 mol.
It is used so as to be 02 to 0.8 mol. In this case,
If the ratio of the raft-reactive groups is less than 0.01 mol, the final
Long time to cure the thermosetting resin composition obtained
Heating is required, or as a solution of the resin composition
The effect of improving storage stability may be insufficient.
Over 1 mole, the inherent properties of polycarbodiimide
It may be damaged. In the denaturation reaction,
Graft-reactive groups in reactive compounds and polycarbodiimides
The reaction with the repeating unit represented by the general formula (1) is quantitative
And the graft reaction is commensurate with the amount of the reactive compound used.
Response is achieved. The denaturation reaction can be performed without solvent.
However, it is preferable to carry out the reaction in a suitable solvent.
No. Such solvents include polycarbodiimides and
Inactive against soluble compounds and will dissolve them
Is not particularly limited as long as it is
Is the ether used in the synthesis of polycarbodiimide.
Solvent, amide solvent, ketone solvent, aromatic hydrocarbon
Elemental solvents, aprotic polar solvents, etc.
You. These solvents may be used alone or in combination of two or more.
Can be used. In addition, polycarbodi
When the solvent used during the synthesis of the imide can be used,
The polycarbodiimide solution obtained by the synthesis is
It can be used as it is. Use of solvents in denaturation reactions
The dose is usually 1 part per 100 parts by weight of the total reactants.
0 to 10,000 parts by weight, preferably 50 to 5,000 parts
Parts by weight. The temperature of the denaturation reaction is polycarbodiimide
And appropriately selected according to the type of the reactive compound,
Usually, 100 ° C. or lower, preferably −10 to + 80 ° C.
You. Modified polycarbodiimide obtained as described above
Mn is usually 500 to 1,000,000, preferably
1,000 to 400,000, more preferably
2,000 to 200,000. As above
The resulting modified polycarbodiimide is usually prepared as a solution.
Used for preparing the thermosetting resin composition of the present invention,
It may be used separately from the liquid. During the synthesis,
The resulting modified polycarbodiimide from the solvent
As a method, the separation method of the polycarbodiimide described above and
A similar method can be used. Modification in the present invention
Polycarbodiimide is used for graft reaction in reactive compounds.
When the functional group is a polycarbodiimide repeating unit (-N = C = NR ¹ -)
And react with the residue having a carboxylic anhydride group of the compound.
Having a structure in which the group is grafted, before the modification reaction
Has a structure essentially different from that of polycarbodiimide
Things. Therefore, the modified polycarbodiimide is
The properties are different from those of the polycarbodiimide before
Mixed with the epoxy compound described below and heated
Carboxylic acid anhydride in modified polycarbodiimide
Even if a curing catalyst is not used by the action of
At a temperature of 0 to 350 ° C, preferably 150 to 300 ° C.
It has the property of easily curing. Moreover, modified polycarbodi
Imides dissolve easily in various solvents,
Storage stability as a solution even in the presence of epoxy compounds
Is extremely excellent. Such modified polycarbo
Of a resin composition containing a diimide and an epoxy compound
Curing properties and modified polycarbodiimide or it
Stability of Mixtures of Epoxy and Epoxy Compounds as Solutions
Is a conventional polycarbodiimide-based thermosetting resin composition
To eliminate the major drawbacks of
Make a significant contribution. [0011] Epoxy compound The epoxy compound in the present invention has an epoxy group in the molecule.
Is a compound having at least one functional group other than an epoxy group.
May have a group, and its molecular weight is not particularly limited.
However, it is, for example, 70 to 20,000. like this
Suitable epoxy compounds include, for example, glycidol,
Sidyl acrylate, glycidyl methacrylate, 3,
4-epoxycyclohexyl acrylate, 3,4-E
Poxycyclohexyl methacrylate and various epoxies
Resins and the like can be mentioned. Preferred epoxy compounds
Is an epoxy resin, an example of which is bisphenol
Epoxy resin, novolak epoxy resin, Creso
Glycidyl typified by Lunovolak type epoxy resin
Ether type epoxy resins; glycidyl ester type epoxy
Xy resins; aromatic glycidylamine type epoxy resin
Alicyclic epoxy resins; heterocyclic epoxy resins;
Liquid rubber-modified epoxy resins can be mentioned. Previous
The epoxy compounds may be used alone or in combination of two or more.
It can be used in a modified polycarbohydrate.
Usually, 5 to 500 parts by weight, preferably 100 parts by weight of imide
The preferred amount is 10 to 300 parts by weight. In this case, Epoki
When the amount of the compound is less than 5 parts by weight, the curing speed is improved.
The effect tends to decrease and exceeds 500 parts by weight
, The heat resistance of the cured product tends to decrease. [0012] Preparation of thermosetting resin composition The thermosetting resin composition of the present invention includes the modified polycarbodiene.
Imide and epoxy compounds as essential components
However, various additives can be blended as needed.
You. Such additives include, for example, antioxidants, heat
Stabilizers, antistatic agents, flame retardants, colorants, lubricants, antifoggants,
Examples include an adhesion improver and a fungicide. Further
, Clay, zeolite, talc, mica, silica,
Graphite, alumina, calcium carbonate, wollastonite
Filler such as glass, carbon, alumina, titanium
Potassium phosphate, aluminum borate, silicon carbide,
Iodine, aromatic polyamide, polyamide imide, polyimid
, Wholly aromatic polyester, ultra high molecular weight polyethylene,
High strength polyacrylonitrile, high strength polyvinyl alcohol
Compound fiber or whisker, etc.
You can also. Also, the reinforcing material may be woven, non-woven, knitted
Used in the form of fabrics such as
It can also be used by impregnating with a substance. In addition, the present invention
Thermosetting resin composition itself has excellent curing properties
But optionally modified polycarbodiimide
Carbodiimide group and / or acid anhydride group
Is a hard resin having reactivity with the epoxy group in the epoxy compound.
Catalyst, curing accelerator, curing aid, etc.
No. The thermosetting resin composition of the present invention comprises a modified polycarbodiene.
Imide and epoxy compounds, optionally used
With various additives, a method of mixing in an appropriate solvent,
Modified polycarbodiol separated from solvent and collected as solid
An imide and an epoxy compound may be used
With the seed additive, if necessary, heating without solvent
Can be prepared by, for example, a method of kneading. The pair
The solvent used in the preparation of the product is a modified polycarbohydrate.
Inert to diimide and epoxy compounds,
And as long as they can be dissolved,
Absent. Such solvents include, for example, polycarbodii
The above ether solvents and amide solvents used for the synthesis of amides
Solvent, ketone solvent, aromatic hydrocarbon solvent, non-prototype
Polar solvents and the like. These solvents
Can be used alone or as a mixture of two or more.
Wear. The amount of the solvent used when preparing the composition is modified.
100 total of polycarbodiimide and epoxy compound
10 to 10,000 parts by weight per part by weight is preferable.
And preferably 20 to 5,000 parts by weight. Of the present invention
The thermosetting resin composition may be used as a solution,
A mixture obtained without solvent may be used as it is. [0013] Properties and applications of thermosetting resin composition The thermosetting resin composition of the present invention has excellent curing characteristics as described above.
Properties, solubility in various solvents and storage stability as a solution
Not only has the cured product, transparency, electrical insulation
Excellent properties, chemical stability, heat resistance, mechanical properties, etc.
Low water absorption, excellent moisture resistance, and adhesion to various substrates
Also excellent in properties. Therefore, the thermosetting tree of the present invention
The fat composition is particularly suitable for protecting various electric devices and electronic components.
Can be used very suitably for films, electrical insulation films, etc.
It is also useful as an adhesive or paint that requires heat resistance.
is there. Further, the thermosetting resin composition of the present invention is previously subjected to a release treatment.
To a suitable cured substrate to form a thermosetting film.
By forcing the film off the substrate before curing,
A thermosetting film can be obtained. The thermosetting film is
Available as heat-resistant adhesive film for electrical equipment and electronic parts
It is for. Alternatively, it was forcibly separated from the substrate
The thermosetting film is cured or a pre-released
After heating and curing the thermosetting film on the substrate,
The cured film is forcibly removed from the substrate
Can be obtained. Further, the thermosetting tree of the present invention
Oil solution is impregnated into a suitable cloth such as glass cloth.
Prepreg dried after drying, or the resin without solvent
Pre-impregnated with the composition impregnated in a suitable cloth such as glass cloth
Pregs are useful for laminated materials such as copper-clad laminates.
The resin composition may be thermosetting in the form of powder, pellets, or the like.
It is also useful as a curable molding material. Thermosetting tree of the present invention
When molding thermosetting film or cured film from fat composition
The substrate used is not particularly limited.
Iron, nickel, stainless steel, titanium, aluminum,
Metals such as copper and various alloys; silicon nitride, silicon carbide, silicon
Aron, aluminum nitride, boron nitride, boron carbide,
Zirconium oxide, titanium oxide, alumina, silica,
Ceramics such as mixtures thereof; Si, Ge, SiC, SiGe, GaAs
semiconductors such as s; ceramic materials such as glass and ceramics;
Lamide, polyamide imide, polyimide, wholly aromatic polyester
A heat-resistant resin such as a ester can be used. Said
The substrate should be pre-released if desired
Silane coupling agent, titanium coupling
Chemical treatment with a coating agent, plasma treatment, ion press
Coating, sputtering, gas phase reaction, vacuum deposition
Such an appropriate pretreatment can be performed. Thermosetting of the present invention
When applying the hydrophilic resin composition to the substrate, the composition
Into a solution as needed, spin coating, roll
Appropriate method such as coating method, casting coating method, dip coating method, spray coating method
Can be adopted. Also, the coating thickness
Is to select the application method, the solid content concentration and viscosity of the composition solution.
By adjusting, it can be controlled appropriately. Departure
There is a thermosetting film formed from bright thermosetting resin composition
Alternatively, the thickness of the cured film can be appropriately selected.
Usually 0.1 to 10,000 μm, preferably 1 to 1.0
00 μm. Furthermore, the thermosetting resin composition of the present invention
Are separated without solvent or separated and collected from the solvent.
Injection molding, transfer molding, pressing
Molding by known molding methods such as extrusion molding and compression molding.
It can also be used as various industrial products and industrial parts.
it can. The present invention will be further described with reference to the following examples.
You. Provided, however, that the present invention
However, the present invention is not limited to the embodiment. Example 1 Synthesis of polycarbodiimide Diphenylmethane-4,4'-diisocyanate (MDI)
50 g and 3.1 g of phenyl isocyanate
In 200 g of hexanone, 1-phenyl-3-methyl-
In the presence of 0.044 g of 2-phospholene-1-oxide,
After reacting at 80 ° C for 4 hours, polycarbodiimide (P-MD
I) A solution of (Mn = 3,500) was obtained. Synthesis of modified polycarbodiimide To the polycarbodiimide solution, a reactive compound
Add 3.8 g of limellitic anhydride and add 3 hours at 20 ° C
Reacted, modified polycarbodiimide having Mn of 3,800
Was obtained. As a result of infrared spectroscopy,
Bodiimide is an infrared absorber unique to carbodiimide units
(Wave number 2,150-2,100cm ^-1 ) And carboxylic acid
Infrared absorption (wave number 1,850 to 1,78) specific to anhydride
0cm ^-1 ) Was confirmed. Preparation of thermosetting resin composition solution In the modified polycarbodiimide solution, an epoxy compound and
Diglycidyl ether derivative of bisphenol A
(Product name Epicoat 828, manufactured by Yuka Shell Epoxy)
The epoxy resin (resin a) consisting of
20 g was added to 20 g of polycarbodiimide solids.
After that, the mixture was filtered under pressure using a filter having a pore size of 1 μm.
Furthermore, the total solid content concentration of the thermosetting resin composition with respect to the solution is
Cyclohexanone was added so as to be 20% by weight,
A thermosetting resin composition solution was prepared. Molding of cured film The thermosetting resin composition solution, a pre-released glass
Spin coating using a spinner on a substrate
After forming the film, it is cured by heating at 200 ° C for 15 minutes.
To obtain a cured film. Next, the cured film is forcibly removed from the substrate.
To form a cured film having a thickness of 50 μm. Evaluation Solution storage stability: The thermosetting resin composition solution
Stored at room temperature.
Was evaluated. A B-type rotational viscometer was used for the viscosity measurement.
The thermosetting resin composition solution of Example 1
Even after storage for 3 months, the solution viscosity is 30 cp (Centipoi)
No change in appearance), and appearance such as gelation even after storage for 3 months
There was no change and it could be stored stably. Tensile strength: The tensile strength of the cured film is determined by JI
It was measured according to SK6911 or C2318. 5% weight loss temperature: Thermogravimetric analysis of the cured film
Temperature rise rate in air at 10 ° C / min using a device (TGA)
Was measured. Table 1 shows the evaluation results. Examples 2 to 4 Preparation of thermosetting resin composition solution Except that the amount of epoxy compound used was changed to the amount shown in Table 1.
Are the same as in Example 1, respectively.
Was prepared. Molding of cured film Using each of the above thermosetting resin composition solutions, each Example
In the same manner as in Example 1, a cured film having a thickness of 50 μm was formed. Evaluation About each said thermosetting resin composition solution and each cured film
Each was evaluated in the same manner as in Example 1. Evaluation results
Are shown in Table 1. Examples 5 to 7 Synthesis of modified polycarbodiimide Except that the amount of the reactive compound used was changed to the amount shown in Table 1.
Are modified polycarbodiyls in the same manner as in Example 1, respectively.
A solution of the mid was obtained. Each modified polycarbodiimide obtained
Table 1 shows the amounts of Mn and reactive compounds used. Preparation of thermosetting resin composition solution Except for using the solution of each modified polycarbodiimide,
Thermosetting resin composition solution in the same manner as in Example 1
Was prepared. Molding of cured film Using each of the above thermosetting resin composition solutions, each Example
In the same manner as in Example 1, a cured film having a thickness of 50 μm was formed. Evaluation About each said thermosetting resin composition solution and each cured film
Each was evaluated in the same manner as in Example 1. Evaluation results
Are shown in Table 1. Comparative Example 1 Preparation of thermosetting resin composition solution Instead of the modified polycarbodiimide solution of Example 1,
Except that the polycarbodiimide solution of Example 1 was used,
A thermosetting resin composition solution was prepared in the same manner as in Example 1. Molding of cured film Using the thermosetting resin composition solution, as in Example 1
Thus, a cured film having a thickness of 50 μm was formed. Evaluation About the thermosetting resin composition solution and the cured film,
And evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
Show. [Table 1] Embodiment 8 Synthesis of polycarbodiimide 50 g of tolylene diisocyanate (TDI) and phenyl iso
2.3 g of cyanate in 200 g of cyclohexanone
And 1-phenyl-3-methyl-2-phospholene-1-
Reacted at 80 ° C. for 4 hours in the presence of 0.29 g of oxide
And polycarbodiimide (P-TDI) (Mn = 3,800)
Was obtained. Synthesis of modified polycarbodiimide In the polycarbodiimide solution, trimellitic anhydride
5.5 g was added and reacted at 20 ° C. for 3 hours.
A solution of 4,300 modified polycarbodiimides was obtained. Red
As a result of external spectroscopy, the modified polycarbodiimide was found to be
Infrared absorption (wave number 2,150) specific to rubodiimide units
~ 2,100cm ^-1 ) And red, characteristic of carboxylic anhydride
Outside line absorption (wave number 1,850-1,780cm ^-1 )
It was confirmed. Preparation of thermosetting resin composition solution Except for using the modified polycarbodiimide solution,
A thermosetting resin composition solution was prepared in the same manner as in Example 1. Molding of cured film Using the thermosetting resin composition solution, as in Example 1
Thus, a cured film having a thickness of 50 μm was formed. Evaluation About the thermosetting resin composition solution and the cured film,
And evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.
Show. Example 9 Synthesis of polycarbodiimide Dicyclohexylmethane-4,4'-diisocyanate
(HMDI) 50 g of 1-phenyl-3-methyl-2-phos
8 ° C. at 180 ° C. in the presence of 1.8 g of holene-1-oxide
After reacting for an hour, cool down to
(P-HMDI) (Mn = 5,000) was obtained. Synthesis of modified polycarbodiimide 200 ml of anisole
Dissolved in toluene, and 3.7 g of trimellitic anhydride was added to this.
And reacted at 20 ° C. for 3 hours.
A solution of the modified polycarbodiimide was obtained. Infrared spectroscopy
As a result, the modified polycarbodiimide is a carbodiimide
Infrared absorption (wave number 2,150-2,100
cm ^-1 ) And infrared absorption (wave
Number 1,850 ~ 1,780cm ^-1 )
Was. Preparation of thermosetting resin composition solution Except for using the modified polycarbodiimide solution,
A thermosetting resin composition solution was prepared in the same manner as in Example 1. Molding of cured film Using the thermosetting resin composition solution, as in Example 1
Thus, a cured film having a thickness of 50 μm was formed. Evaluation About the thermosetting resin composition solution and the cured film,
And evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.
Show. Comparative Example 2 Preparation of thermosetting resin composition solution Instead of the modified polycarbodiimide solution of Example 1,
Except that the polycarbodiimide solution of Example 8 was used,
A thermosetting resin composition solution was prepared in the same manner as in Example 1. Molding of cured film Using the thermosetting resin composition solution, implemented
A cured film having a thickness of 50 μm was formed in the same manner as in Example 1. Evaluation About the thermosetting resin composition solution and the cured film,
And evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.
Show. Comparative Example 3 Preparation of thermosetting resin composition solution Instead of the modified polycarbodiimide solution of Example 1,
A solution obtained by dissolving the polycarbodiimide of Example 9 in anisole
Thermosetting resin in the same manner as in Example 1 except that the liquid was used.
A composition solution was prepared. Molding of cured film Example 1 except that the thermosetting resin composition solution was used.
A cured film having a film thickness of 50 μm was formed in the same manner as described above. Evaluation About the thermosetting resin composition solution and the cured film,
And evaluated in the same manner as in Example 1. Table 2 shows the evaluation results.
Show. [Table 2] Embodiment 10 Synthesis of polycarbodiimide Diphenylmethane-4,4'-diisocyanate (MDI)
50 g and 3.1 g of phenyl isocyanate
1-phenyl-3-methyl-2-phos in 200 g
In the presence of 0.044 g of holene-1-oxide, 110
The reaction was carried out at reflux for 5 hours.
MDI). The solution is cooled to room temperature and
Precipitate carbodiimide, filter and separate and collect.
A powder of polycarbodiimide having n of 9,800 was obtained. Synthesis of modified polycarbodiimide 30 g of the polycarbodiimide powder was heated under toluene
120 g of acetone, and acetone 12 as a reactive compound.
g of trimellitic anhydride dissolved in the reaction system
Was maintained at 80 ° C., and the mixture was added dropwise over 30 minutes. Sa
After reacting for 30 minutes, cool to room temperature
The substance was precipitated, filtered and separated and collected, and Mn was 4,50.
Thus, a powder of modified polycarbodiimide was obtained. Infrared spectroscopy
As a result of the measurement, the modified polycarbodiimide
Infrared absorption (wave number 2,150-2,1
00cm ^-1 ) And infrared absorption characteristic of carboxylic anhydride
(Wave number 1,850-1,780cm ^-1 )
I accepted. Preparation of thermosetting resin composition solution As a solution of the modified polycarbodiimide,
20 g of rubodiimide powder to 160 g of cyclohexanone
Except for using the dissolved solution, the same as in Example 1
A thermosetting resin composition solution was prepared. Molding of cured film 30 minutes at 200 ° C. using the thermosetting resin composition solution
Except that the film was cured by heating during
A cured film having a thickness of 50 μm was formed. Evaluation About the thermosetting resin composition solution and the cured film,
And evaluated in the same manner as in Example 1. In addition, the cured film
of Moist heat Environmental testing (PCT) (121 ° C, 100% humidity
And standing for 240 hours) before and after volume resistivity and surface resistivity
Was evaluated in accordance with JIS K6911. In addition,
An erosion test was performed as follows. Electric corrosion test: Fabrication of substrate for electric corrosion test-Copper-clad glass epoxy substrate
(Product name R-1705SX; manufactured by Matsushita Electric Works, Ltd.)
200μm pitch by lithography etching
(Copper wire width / space = 100μm / 100μm), copper thickness
A 13 μm comb-shaped electrode was fabricated as a lower electrode. This
Extremely, using a spinner the thermosetting resin composition
After spin coating to form a thermosetting coating, 120 ° C
At 150 ° C. for 30 minutes, followed by 200 ° C.
Cured by heating for 30 minutes with a film thickness of 50 μm
Were laminated. On this cured film, a sputtering method is used.
A copper layer (2 μm thick)
Etching is performed to produce the upper electrode.
Board. Electrolytic corrosion test-
Hot water bath (product name: HAST SYSTEM TPC-212;
(Manufactured by KK), 133 ° C, 3 atm, bias voltage 5
Under the condition of V, digital super high resistance / micro ammeter R8340A
(Advantest) and measure the current value.
Was evaluated until the value of 1 became larger than 1 μA. Comment
The results are shown in Table 3. Example 11 Synthesis of modified polycarbodiimide 30 g of the polycarbodiimide powder of Example 10 was heated
Dissolves in 120 g of cyclohexanone with
Trimellitic anhydride dissolved in 12 g of acetone
2.8 g was charged for 30 minutes while maintaining the temperature of the reaction system at 80 ° C.
It dripped over. After further reaction for 30 minutes,
Thus, a solution of the modified polycarbodiimide No. 00 was obtained. Infrared
As a result of light measurement, the modified polycarbodiimide
Infrared absorption (wave number 2,150 to 2,
100cm ^-1 ) And the infrared absorption characteristic of carboxylic acid anhydrides.
Yield (wave number 1,850 ~ 1,780cm ^-1 )
confirmed. Preparation of thermosetting resin composition solution Except for using the solution of the modified polycarbodiimide,
A thermosetting resin composition solution was prepared in the same manner as in Example 10.
Was. Molding of cured film Except for using the thermosetting resin composition solution,
In the same manner as in Example 10, a cured film having a thickness of 50 μm was formed. Evaluation About the thermosetting resin composition solution and the cured film,
And evaluated in the same manner as in Example 10. Table showing the evaluation results
3 is shown. Example 12 Preparation of thermosetting resin composition 20 g of the modified polycarbodiimide powder of Example 10 and Epo
20 g of xy resin (resin a) is mixed at 70 ° C. without solvent.
By kneading, a paste-like thermosetting resin composition was prepared. Molding of cured plate The thermosetting resin composition as it is, at 120 ° C. for 60 minutes
To obtain a sheet or film pre-cured product
Was. This pre-cured product is heated at 150 ° C. for 30 minutes,
Press molding at 00 ° C for 30 minutes to form a 3 mm thick plate
Was formed. Production of substrate for electrolytic corrosion test Instead of forming a thermosetting coating film using the spinner of Example 10.
Instead, place the pre-cured material on the electrode and separate it in advance.
Molded polyethylene terephthalate film (brand name
5kg / cm via Miner) ^Two The weight of
Except that the curing treatment was carried out with the beam, the electrolytic corrosion test of Example 10 and
Similarly, a substrate for an electrolytic corrosion test was prepared. Evaluation Various physical properties of the plate-like cured product are measured according to ASTM standard or JI
The evaluation was performed in accordance with the S standard. Further, the substrate for the electrolytic corrosion test
Was subjected to an electrolytic corrosion test in the same manner as in Example 10.
Table 4 shows the evaluation results. Comparative Examples 4 and 5 Preparation of thermosetting resin composition solution Whether epoxy resin (resin a) is used (Comparative Example 4)
Except for using polycarbodiimide (Comparative Example 5)
Is a thermosetting resin composition solution in the same manner as in Example 10.
Prepared. Molding of cured film Except for using the thermosetting resin composition solution,
In the same manner as in Example 10, a cured film having a thickness of 50 μm was formed. Evaluation About the thermosetting resin composition solution and the cured film,
And evaluated in the same manner as in Example 10. Table 3 shows the evaluation results.
Shown in [Table 3] [Table 4] Embodiment 13 Preparation of thermosetting resin composition solution 20 g of the modified polycarbodiimide powder of Example 10 was added.
After dissolving in 30 g of cyclohexanone under heat,
Thermosetting resin composition by adding 20 g of resin (resin a)
Was prepared. Production of adhesive film The thermosetting resin composition solution was subjected to the release treatment in advance.
Gap on polyethylene terephthalate film
After applying using a 300μm doctor blade,
On a hot plate at 80 ° C. for 20 minutes, then 120
Heated at ° C for 60 minutes. Then, after cooling to room temperature,
A thermosetting film with a thickness of about 32 μm is
Peel from phthalate film to make adhesive film
did. Adhesion evaluation A 130 μm-thick polyimide film
Lum (trade name Kapton; manufactured by Dupont Toray) and the copper
Sandwiched between the copper surface on the glazed epoxy board and 100
g / cm ^Two At 150 ° C. for 30 minutes, followed by 20
Heat at 0 ° C. for 60 minutes. Then, polyimide film
The peel strength from the copper surface of JIS H8630 and C
6481, adhesion strength tester (Yamamoto Plating Test Equipment Co., Ltd.)
Was 1.8 kgf / cm. Example 14 Production of laminated adhesive film A copper foil was laminated with the thermosetting resin composition solution of Example 13 by laminating.
Coated polyimide film (trade name: IFI-RM10; Nikka
50 gap on the polyimide surface of
After applying using a 0 μm doctor blade,
On a plate at 80 ° C. for 20 minutes, then at 120 ° C.
Heat for 60 minutes to form a thermosetting resin layer with a thickness of about 50 μm.
To produce a laminated adhesive film. Adhesion evaluation A thermosetting resin layer is formed on the laminate adhesive film.
On the copper-clad glass epoxy board with the
100g / cm ^Two Weight at 150 ° C for 30 minutes
While heating at 200 ° C. for 60 minutes. Then copper foil
Copper-clad glass of polyimide film laminated with
When the peel strength from the copper surface of the epoxy board was measured,
It was 1.9 kgf / cm. Example 15 Production of adhesive film Except for using the thermosetting resin composition solution of Example 11,
An adhesive film having a thickness of about 35 μm was obtained in the same manner as in Example 13.
Was made. Adhesion evaluation The adhesion was evaluated in the same manner as in Example 13. Evaluation results
Are shown in Table 5. Example 16 Production of laminated adhesive film Except for using the thermosetting resin composition solution of Example 11,
In the same manner as in Example 14, a thermosetting resin having a thickness of about 52 μm
A laminate adhesive film having a fat layer was produced. Adhesion evaluation The adhesion was evaluated in the same manner as in Example 14. Evaluation results
Are shown in Table 5. Example 17 Production of adhesive film The paste-like thermosetting resin composition of Example 12 was mixed with two sheets.
The previously released polyethylene terephthalate filter
5kg / cm ^Two While pressing at a pressure of 12
Heat at 0 ° C. for 60 minutes. Then cooled down to room temperature
The thermosetting film is made of polyethylene terephthalate
Adhesive film about 150μm thick, peeled from film
Was prepared. Adhesion evaluation The adhesion was evaluated in the same manner as in Example 13. Evaluation results
Are shown in Table 5. Example 18 Production of laminated adhesive film The paste-like thermosetting resin composition of Example 12 was mixed with the copper
Place on foil laminated polyimide film, 2 pieces
Of the polyethylene terephthalate pre-released
5kg / cm sandwiched between films ^Two While pressing at the pressure of 1
Heat at 20 ° C. for 60 minutes. Then cooled down to room temperature
Then, peel off the polyethylene terephthalate film,
Laminate having thermosetting resin layer about 120μm thick
An adhesive film was produced. Adhesion evaluation The adhesion was evaluated in the same manner as in Example 14. Evaluation results
Are shown in Table 5. Comparative Examples 6 and 7 The thermosetting resin composition solution of Comparative Example 4 or Comparative Example 5 was used.
Except that the thickness was approximately the same as in Example 14.
Laminating layers having thermosetting resin layers of 18 μm and about 42 μm
A minate adhesive film was prepared. Adhesion evaluation The adhesion was evaluated in the same manner as in Example 14. Evaluation results
Are shown in Table 5. [Table 5] The thermosetting resin composition of the present invention comprises a polycarbonate.
Original heat resistance, electrical insulation, mechanical properties, etc. of rubodiimide
Without compromising solubility and solution in various solvents
Storage stability and use no curing catalyst.
Easily cured under mild and mild conditions, and the cured product
Is suitable for moisture resistance, transparency, chemical stability,
Excellent in adhesiveness and the like. Therefore, the thermosetting of the present invention
The conductive resin composition is used as a protective film for electrical equipment and electronic parts,
It can be used very suitably as an insulating film, etc.
Or adhesive, paint, thermosetting film, cured film, prepreg,
It is also useful for cured molded products.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideyoshi Fujiwara 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP 8-27270 (JP, A) JP JP-A-58-90561 (JP, A) JP-A-2-175756 (JP, A) JP-A-6-1714 (JP, A) JP-A-4-342713 (JP, A) A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 59/42 C08L 51/08 C08L 63/00-63/10

Claims (1)

(A) General formula (1) -N = C = NR ^1- (1) (where R ¹ represents a divalent organic group). A) a resin obtained by grafting at least one compound having a graft-reactive group and a carboxylic anhydride group onto a polycarbodiimide having a repeating unit represented by the formula (1), and (B) an epoxy compound. Thermosetting resin composition.