JP3456265B2 - Manufacturing method of thermosetting resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
With a functional group and excellent water resistance, heat resistance, mechanical strength, etc.
The present invention relates to a method for producing a recarbodiimide-based thermosetting resin. [0002] 2. Description of the Related Art Polycarbodiimide is a polyisocyanate.
A heat-resistant resin obtained by the decarboxylation condensation of
The method of manufacture is, for example, Die by D.J.Lyman et al.
Makromol. Chem., 67, 1 (1963), J. Am. C by E. Dyer et al.
hem. Soc., 80,5495 (1958), J. A. by L.M.Alberino et al.
ppl.Polym.Sci., 21, 1999 (1977), T.W.
J. Org. Chem., 28, 2069 (1963) and JP-A-51-61.
No. 599, for example. Polycarbodiimide
Means that the carbodiimide group in the molecule is thermally crosslinked by heating
Therefore, application as thermosetting resin with excellent heat resistance
Is expected. However, polycarbodiimides
Takes a considerable amount of time to fully heat cure
There is a problem, and in the state dissolved in a solvent
Gelation of the polymer gradually progresses even in a cool and dark place.
It is extremely difficult to store in solution for a long time.
It is a major obstacle to industrial use.
You. Therefore, for example, Japanese Patent Application Laid-Open No. 2-29316,
As disclosed in JP-A-4-279618, etc.
Preservation of polycarbodiimide by devising the medium and polymerization conditions
Attempts have been made to improve stability.
Storage stability of polycarbodiimide solution
Is about 3 weeks at room temperature, about 3 months at 5 ° C,
Not always enough. In addition, these publications
The polycarbodiimide obtained by the method described
Very poor solubility in medium and shortens curing time
From the viewpoint of industrial use.
There is a title. Therefore, polycarbodiimide is added to the molecule.
Mix with a crosslinking agent having two or more active hydrogen groups and heat
Attempts to shorten the heat curing time by
Proposed in Japanese Patent Publication No. 5-6564 and Japanese Patent Publication No. 5-6565
Have been. In addition, polycarbodiimide is converted to an epoxy compound.
Product (JP-A-62-1714), cyanate ester
(JP-A-2-218751), vinyl compounds (particularly
And JP-A 52-146490).
Attempts to mix use have also been proposed. However, this
In these methods, the storage stability of the polycarbodiimide itself is
Not only is not improved, but also a highly active
Storage in a solution state due to the mixture of
There are drawbacks such as loss of stability. [0003] SUMMARY OF THE INVENTION The present invention provides
It was made as a result of intensive examination in view of
The purpose is to achieve the high heat resistance and high performance inherent in polycarbodiimide.
With mechanical strength, the curing reaction proceeds quickly in a short time,
Polycarbodiimide with excellent storage stability especially in solution state
It is an object of the present invention to provide a method for producing a thermosetting resin. [0004] The gist of the present invention is that of the general formula
(1) Embedded image (Where R¹Represents a divalent organic group. )
At least one kind of polycarbodiimide having a repeating unit
ToCarboxyl groups and primary or secondary amines
And a group selected from the group consisting of Embedded image (Where R ^Two Is an aliphatic, alicyclic or aromatic trivalent
Shows an organic group. A) a compound having the group represented by
Lylic acid, methacrylic acid, cinnamic acid, p-aminostyrene
, 2-t-butylaminoethyl (meth) acrylate
G, p-methylaminostyrene, vinylphenol, Embedded image (Where each R ^Three May be the same or different, and hydrogen
Represents an atom or a methyl group, i is an integer of 1 to 30
You. ), Embedded image (Where R ^Three Represents a hydrogen atom or a methyl group, and j is 2
Is an integer of up to 30. ), Embedded image (Where R ^Three Represents a hydrogen atom or a methyl group, and k represents 2
Is an integer of up to 30. ), Embedded image (Where R ^Three Represents a hydrogen atom or a methyl group. ),common
Bini Embedded image (Where R ^Three Represents a hydrogen atom or a methyl group. ) Group
Chosen fromHas a graft reactive group and a crosslinkable group
At least one compound is grafted at an appropriate temperature.
And a method for producing a thermosetting resin. Hereinafter, the present invention will be described in detail.
This will clarify the objects, configurations and effects of the present invention.
Would. <Polycarbodiimide> First, represented by the general formula (1)
Polycarbodiimides having repeating units are, for example, organic
The polyisocyanate is replaced with a carbodii group having an isocyanate group.
Catalyst for promoting the imidization reaction (hereinafter referred to as “carbodiimidation
Catalyst. " Synthesized by reaction in the presence of
can do. For the synthesis of this polycarbodiimide
As organic polyisocyanates to be used, organic diiso
Cyanates are preferred. Such organic diisocyanates
As phenylene-1,3-diisocyanate, for example,
Phenylene-1,4-diisocyanate, 1-methyl
Toxiphenylene-2,4-diisocyanate, 1-meth
Tylphenylene-2,4-diisocyanate, 2,4-
Tolylene diisocyanate, 2,6-tolylene diisocyanate
Anate, 1,3-xylylene diisocyanate, 1,
4-xylylene diisocyanate, biphenylene-4,
4'-diisocyanate, 3,3'-dimethoxybiphe
Nylene-4,4'-diisocyanate, 3,3'-dimene
Cylbiphenylene-4,4'-diisocyanate, diph
Phenylmethane-2,4'-diisocyanate, diphenyl
Methane-4,4'-diisocyanate, 3,3'-di
Methoxydiphenylmethane-4,4'-diisocyanate
G, 3,3'-dimethyldiphenylmethane-4,4'-
Diisocyanate, naphthylene-1,5-diisocyane
, Cyclobutylene-1,3-diisocyanate, silicone
Clopentylene-1,3-diisocyanate, cyclohexane
Xylene-1,3-diisocyanate, cyclohexyl
1,4-diisocyanate, 1-methylcyclohexene
Silene-2,4-diisocyanate, 1-methylcyclo
Hexylene-2,6-diisocyanate, 1-isocyanate
Nate-3,3,5-trimethyl-5-isocyanate
Methylcyclohexane, cyclohexane-1,3-bis
(Methyl isocyanate), cyclohexane-1,4-
Bis (methyl isocyanate), isophorone diisocyanate
, Dicyclohexylmethane-2,4'-diisocyate
Anate, dicyclohexylmethane-4,4'-diiso
Cyanate, ethylene diisocyanate, tetramethyle
1,4-diisocyanate, hexamethylene-1,
6-diisocyanate, dodecamethylene-1,12-di
Isocyanate, lysine diisocyanate methyl ester
And the stoichiometric excess of these organic diisocyanates
Obtained by reacting the excess with a bifunctional active hydrogen containing compound.
Such as a double-ended isocyanate prepolymer
Can be. The organic diisocyanate alone or
Two or more kinds can be used as a mixture. Also, if
Other materials used with organic diisocyanates
For example, phenyl-1,1,
3,5-triisocyanate, diphenylmethane-2,
4,4'-triisocyanate, diphenylmethane-
2,5,4'-triisocyanate, triphenylmeta
2,4 ', 4 "-triisocyanate, triphenyl
Methane-4,4 ', 4 "-triisocyanate, diph
Phenylmethane-2,4,2 ', 4'-tetraisocyane
, Diphenylmethane-2,5,2 ', 5'-tetra
Isocyanate, cyclohexane-1,3,5-trii
Socyanate, cyclohexane-1,3,5-tris
(Methyl isocyanate), 3,5-dimethylcyclohexane
Xan-1,3,5-tris (methyl isocyanate
G), 1,3,5-trimethylcyclohexane-1,
3,5-tris (methyl isocyanate), dicyclo
Xylmethane-2,4,2'-triisocyanate, di
Cyclohexylmethane-2,4,4'-triisocyane
Tri- or more functional polyisocyanates such as
Stoichiometric excess of trifunctional or higher polyisocyanate
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. As the carbodiimidization catalyst, for example, 1
-Phenyl-2-phospholene-1-oxide, 1-phenyl
Nil-3-methyl-2-phospholene-1-oxide, 1
-Phenyl-2-phospholene-1-sulfide, 1-f
Enyl-3-methyl-2-phospholene-1-sulfy
1-ethyl-2-phospholene-1-oxide, 1-
Ethyl-3-methyl-2-phospholene-1-oxide,
1-ethyl-2-phospholene-1-sulfide, 1-d
Tyl-3-methyl-2-phospholene-1-sulfide,
1-methyl-2-phospholene-1-oxide, 1-methyl
3-methyl-2-phospholene-1-oxide, 1-
Methyl-2-phospholene-1-sulfide, 1-methyl
-3-methyl-2-phospholene-1-sulfide and the like,
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 and the like can be mentioned. This
These carbodiimidation catalysts may be used alone or in combination of two or more.
Can be used as a mixture.
Per 100 parts by weight of the total of the isocyanate,
0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight
Parts. The synthesis reaction of polycarbodiimide is carried out without solvent.
It can be carried out below or in a suitable solvent. Poly
The solvent used in the carbodiimide synthesis reaction
For example, 1,1-dichloroethane, 1,2-dichloroethane
Loethane, 1,1,1-trichloroethane, 1,1,2
-Trichloroethane, 1,1,1,2-tetrachloroe
Tan, 1,1,2,2-tetrachloroethane, pentac
Loroethane, hexachloroethane, 1,1-dichloroethane
Tylene, 1,2-dichloroethylene, trichloroethylene
, Tetrachloroethylene, chlorobenzene, o-dic
Lorobenzene, m-dichlorobenzene, p-dichlorobe
Benzene, 1,2,4-trichlorobenzene, trichloro
Halogenated hydrocarbon solvents such as methylbenzene; dioxa
, Anisole, tetrahydrofuran, tetrahydropi
Orchid, diethylene glycol dimethyl ether, diethyl
Len glycol diethyl ether, diethylene glycol
Rudipropyl ether, diethylene glycol dibutyl
Ether, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene
Glycol monopropyl ether, diethylene glycol
Monobutyl ether, triethylene glycol monomer
Ether solvents such as tyl ether; N-methyl-2-pi
Loridone, N-acetyl-2-pyrrolidone, N-benzyl
2-pyrrolidone, N-methyl-3-pyrrolidone, N
-Acetyl-3-pyrrolidone, N-benzyl-3-pyrro
Lidone, formamide, N-methylformamide, N,
N-dimethylformamide, N-ethylformamide,
N, N-diethylformamide, acetamide, N-meth
Tilacetamide, N, N-dimethylacetamide, N
Amide solvents such as -methylpropionamide; dimethyl
Aprotic polar solvents such as sulfoxide; 2-methoxy
Ethyl acetate, 2-ethoxyethyl acetate, 2
-Propoxyethyl acetate, 2-butoxyethyl acetate
Acetate, 2-phenoxyethyl acetate, diethyl
Glycol monomethyl ether acetate, diethyl
Glycol monoethyl ether acetate, diethyl
Glycol monopropyl ether acetate, diethyl
Acetates such as lenglycol monobutyl ether acetate
Tate 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
Examples include ketone solvents such as nonone and 4-decanone.
it can. These solvents may be used alone or as a mixture of two or more.
Can be used. Synthesis of polycarbodiimide
In the reaction, the solvent is the concentration of the organic polyisocyanate.
But usually 0.5 to 60% by weight, preferably 5 to 50
It is used in a proportion that will be the amount%. Organic polyisocyanate
If the concentration exceeds 60% by weight, it may form
Polycarbodiimide may gel during the synthesis reaction
If less than 0.5% by weight, the reaction rate is slow.
And productivity decreases. In addition, the synthesis of polycarbodiimide
The reaction temperature is controlled by the organic polyisocyanate or carbodiyl
It is appropriately selected according to the kind of the imidation catalyst.
0-200 ° C. For synthesis reaction of polycarbodiimide
During the reaction, the entire amount of the organic polyisocyanate is added before the reaction.
Or part or all of them during the reaction,
It may be added continuously or stepwise. In addition, Polica
Appropriate reaction from the early stage to the late stage of the rubodiimide synthesis reaction
In the reaction step, the terminal isocyanate group of polycarbodiimide
A compound capable of reacting with polycarbodiimide powder
The ends can be sealed and the molecular weight adjusted. like this
Examples of compounds that can react with various isocyanate groups include, for example,
Methanol, ethanol, isopropanol, cyclo
Alcohols such as hexanol; dimethylamine, die
Amines such as tylamine and benzylamine;
Socyanate, tolyl isocyanate, cyclohexyl
Monoisocyanates such as isocyanate and butyl isocyanate
Anates and the like can be mentioned. Synthesized polycarbonate
Rubodiimide is optionally separated from the solution. This
In the case of, as a method for separating polycarbodiimide, for example,
The polycarbodiimide solution was added to the polycarbodiimide.
And added to an inert non-solvent, and the resulting precipitate or
Separate and collect oil by filtration, decantation, etc.
Method of separation and collection by spray drying
Can be. Polycarbodiimide of the present invention
Styrene-equivalent number average molecular weight (hereinafter referred to as "Mn")
Is appropriately determined depending on the Mn of the resulting thermosetting resin, the application, and the like.
Selected, usually 400-500,000, preferred
1,000 to 200,000, particularly preferably 2,
000 to 100,000. [0008] The thermosetting resin of the present invention comprises
Polycarbodii having a repeating unit represented by the formula (1)
A graft-reactive group and a cross-link
Having a functional groupspecificCompound (hereinafter referred to as “graft
Compound. " At least one of them)
It is manufactured by shifting. Where the grafting reaction
The reactive group reacts with the polycarbodiimide to form a crosslinkable group.
The residue of the graft reactive compound having a group is
It means a group to be grafted to diimide. Such a group
Raft-reactive groups include carboxyl and primary
And a secondary amino group and a hydroxyl group.
Further, a crosslinkable group means that the crosslinkable group
React with each other and / or with the polycarbodiimide chain,
Means a group that results in a cured resin. Such a crosslinkable group
Is a polymerizable unsaturated group, a general formula (2) [0009] Embedded image (Where R^TwoIsAliphatic, alicyclic or aromatic
IncenseShows a trivalent organic group. List the group represented by)
Can be. Specific examples of such a graft reactive compound
As the following compounds and compounds
it can. <Compound> The compound is a carboxyl group, primary or secondary
Grafting reactivity selected from the group of amino group and hydroxyl group
Having a group and a polymerizable unsaturated group as a crosslinkable group.
is there. Such compounds include acrylic acid, meta
Crylic acid, cinnamic acid, p-aminostyrene, 2-t-butyl
Tylaminoethyl (meth) acrylate, p-methyla
Minostyrene, vinylphenol, [0012] Embedded image (Where each R^ThreeAre the same but different
Represents a hydrogen atom or a methyl group, and i represents 1 to 30
Is an integer. ), [0014] Embedded image (Where R^ThreeRepresents a hydrogen atom or a methyl group
And j is an integer of 2 to 30. ), [0016] Embedded image (Where R^ThreeRepresents a hydrogen atom or a methyl group
And k is an integer of 2 to 30. ), [0018] Embedded image (Where R^ThreeRepresents a hydrogen atom or a methyl group
Show. ), [0020] Embedded image (Where R^ThreeRepresents a hydrogen atom or a methyl group
Show. ). These compounds
In particular, acrylic acid, methacrylic acid, 2-hydroxy
Til (meth) acrylate is preferred. The compound
Can be used alone or as a mixture of two or more.
Wear. <Compound> Compounds may also contain carboxyl groups and primary or
Is a graft-reactive group selected from the group of secondary amino groups
And a group represented by the general formula (2) as a crosslinkable group.
Compound. Such compounds include, for example,
1,2,3-propanetricarboxylic anhydride,
2,4-butanetricarboxylic anhydride, hexahydroto
Trica such as limellitic anhydride and trimellitic anhydride
Acid anhydrides of rubonic acids; aminosuccinic anhydride, 4-A
Mino-1,2-butanedicarboxylic anhydride, 4-amino
Hexahydrophthalic anhydride, 4-aminophthalic anhydride
Acid anhydrides of primary amino group-containing dicarboxylic acids such as products;
N-methylaminosuccinic anhydride, 4-methylamino-
1,2-butanedicarboxylic anhydride, 4-methylamino
Hexahydrophthalic anhydride, 4-methylaminophthal
No acid of secondary amino group-containing dicarboxylic acids such as acid anhydride
Waters and the like can be mentioned. These compounds
In particular, trimellitic anhydride is particularly preferred. The compound
Can be used alone or as a mixture of two or more
it can. In the present invention, a thermosetting resin is produced.
The reaction can be carried out without solvent, but
It is preferable to carry out in an appropriate solvent. Such solvent
Is, for example, the polycarbodiimide, graft-reactive
Inert to both of the compounds and dissolve them
As far as possible, there is no particular limitation.
Is the aforesaid A.C.
Ter solvents, amide solvents, aprotic polar solvents,
And the like. In addition, the reaction
Solvents used during the synthesis of recarbodiimide can be used.
The polycarbodiimide obtained by the synthesis
The solution can be used as it is. These solvents
Can be used alone or as a mixture of two or more.
And the amount used per 100 parts by weight of the reactants
Usually, 10 to 10,000 parts by weight, preferably 50 to 5,
000 parts by weight. In the present invention, the thermosetting resin
The reaction temperature during production depends on polycarbodiimide and
Selected appropriately according to the type of reactive compound.
In the case of a compound, it is usually 200 ° C. or lower, preferably −
10 to + 100 ° C., and in the case of a compound,
It is 100 ° C. or lower, preferably −10 to + 80 ° C. Book
Of the graft-reactive compound in the thermosetting resin in the invention
The amount of grafting depends on the type of the compound or polycarbodiimide,
It is adjusted according to the desired properties of the thermosetting resin,
Usually, per mole of the repeating unit represented by the general formula (1),
0.01 to 1 mol, preferably 0.02 to 0.8 mol
is there. When the graft amount of the graft reactive compound is 0.01
If it is less than 100 mm, the structure of the resulting thermosetting resin will be
Thermosetting because it is not much different from rubodiimide itself
It is necessary to heat for a long time to cure the resin
This is industrially disadvantageous.
The original properties of the carbodiimide may be impaired.
You. The thermosetting resin obtained as described above is a graph
The graft reactive group in the reactive compound is polycarbodiyl.
Reacts in at least a portion of the repeating units of the mid;
Substantially grafted with the residue of the compound having a bridging group
It is a resin having a non-crosslinked structure. The thermosetting resin
The crosslinkable group remains in the
Between graft-reactive groups and crosslinkable groups in compounds
Based on difference in reactivity to bodimide. In the present invention
To graft the compound to the polycarbodiimide
Thermosetting resin (hereinafter referred to as “thermosetting resin”)
Resin A ". ) The graft structure of each
The nature group is illustrated below together with the reaction process. [0024] Embedded image [0025] Embedded image [0026] Embedded image[0027] Embedded image In the thermosetting resin A, each graft structure
Is randomly distributed in the polycarbodiimide and the formula
The structures of (A) to (D) are either one type alone or 2
More than one species can be produced simultaneously, the structure of formulas (F) and (G)
Means that only one or both are generated
As a result, the structures of formulas (H) to (K) have only one type.
Or both can be generated simultaneously. In addition, the polycarbo
Manufactured by grafting compounds to diimides
Thermosetting resin (hereinafter referred to as "thermosetting resin B").
The graft structure of
Is shown below together with the reaction process.
You. [0029] Embedded image In the thermosetting resin B, each graft structure
Is randomly distributed in the polycarbodiimide and the formula
The structures of (N) to (Q) may be any one of them or 2
More than one species can be produced simultaneously. The compound graph
If the reactive group is a primary or secondary amino group
For the graft structure of the compound, refer to the reaction process of the compound.
I want to be illuminated. Thermosetting resin produced by the present invention,
Polycarbodiate before grafting with graft-reactive compounds
It has an essentially different structure from imide, and
Therefore, its properties are significantly different from those of the polycarbodiimide.
With excellent storage stability in solution state
It is. The thermosetting resin in the present invention is a polycarbonate.
Residue of graft-reactive compound grafted on rubodiimide
Since the group has a crosslinkable group, it can be appropriately heated to a temperature.
It can be more thermoset. Moreover, this thermosetting reaction
Is rapid and the heat in conventional polycarbodiimide
It can solve the practical problem of slow curing speed.
Wear. Further, the cured product of the thermosetting resin in the present invention,
Low water absorption, adhesion, electrical insulation, chemical stability, resistance
Excellent heat resistance, moisture resistance, mechanical strength, etc. According to the invention
Mn of thermosetting resin manufactured is basically
And grafting reactivity of polycarbodiimides used
Depending on the type of compound and the amount of grafting, thermosetting resin
It is appropriately selected according to the characteristics and use of the device. Made according to the invention
The thermosetting resin used is separated as a solution or from a solvent.
Used separately, but obtained as a solution during its manufacture
As a method of separating the thermosetting resin from the solvent, for example,
The solution of the thermosetting resin is mixed with a non-solvent inert to the resin.
The precipitate or oil produced by the
Separation / collection by stationing; Spray drying
There can be mentioned a method of separating and collecting more. [0031]Mixing and curing of thermosetting resin The thermosetting resin produced according to the present invention may have
Various additives can be blended. Such an attachment
Additives include, for example, antioxidants, heat stabilizers, and ultraviolet absorbers.
Collecting agents, light stabilizers, antistatic agents, flame retardants, coloring agents, lubricants,
Antifogging agents, adhesion improvers, antifungal agents and the like can be mentioned.
You. In addition, clay, zeolite, talc, mica,
Lica, graphite, alumina, calcium carbonate, straw
Filler such as stone, glass, carbon, aluminum
Na, potassium titanate, aluminum borate, silicon carbide
Silicon, silicon nitride, aromatic polyamide, polyamideimid
, Polyimide, wholly aromatic polyester, ultra high molecular weight polyester
Polyethylene, high-strength polyacrylonitrile, high-strength poly
Reinforcement of fibers such as vinyl alcohol or whiskers
Materials can also be blended. Also, these reinforcements
Used in the form of woven fabric, non-woven fabric, knitted fabric, etc.
The textile may be impregnated with a thermosetting resin for use.
The thermosetting resin produced according to the present invention is optionally used
After compounding the above additives, when curing,
It may be heated to an appropriate temperature.
Initiators or catalysts can also be used. in this case
Is usually 100 to 500 ° C, preferably 1 to 500 ° C.
50-400 ° C. When curing, use a thermosetting resin
Can be used alone or in combination of two or more.
Wear. Curing the thermosetting resin produced by the present invention
Examples of the polymerization initiator or catalyst used when
For example, in the case of thermosetting resin A, for example, azoisobutyroni
Tolyl, azobisisocyanovaleric acid, 2,2'-azobi
(2-amidinopropane) hydrochloride
Compounds: hydrogen peroxide, ammonium persulfate, potassium persulfate
Inorganic peroxides such as lium and sodium persulfate;
Nzoyl, di-t-butyl peroxide, cumenehydride
Organic peroxides such as peroxides;
Lucari metal (bis) sulfite, (bis) ammonium sulfite
Red consisting of a combination with a reducing agent such as
Catalysts and the like. Made according to the invention
Thermosetting resin is usually used as a solution varnish,
Heat-resistant adhesives, heat-resistant paints, heat-resistant protective films for electronic materials, etc.
It is extremely useful. As a solvent used in the varnish
Is inert to the thermosetting resin, and
Is not particularly limited as long as it can dissolve
For example, N, N-dimethylformamide, N, N-di
Methylacetamide, N-methyl-2-pyrrolidone, di
Ethylene glycol dimethyl ether, tetrahydrof
Orchids, dioxane, anisole, etc.
Can be selected as appropriate. These solvents are
Used in an amount that will result in a resin concentration of 10 to 60% by weight.
Is preferred. If the resin concentration is less than 10% by weight,
Film thickness becomes thin and mechanical strength becomes insufficient
If it exceeds 60% by weight, the solution viscosity
And the applicability tends to be impaired. The varnish
When applying to the adherend, substrate, substrate, etc.
Coating method, roll coating method, casting coating method, dip coating method, spraying
Appropriate coating means such as a coating method can be adopted. Ma
The thickness of the coating is determined by selecting the coating method and the solid content of the polymer solution.
It can be controlled appropriately by adjusting the concentration and viscosity.
However, it is usually 0.1 to 10000 μm.
The varnish is applied to an appropriate substrate and dried to form a resin thin film.
After formation, forcibly peel off the thin film from the substrate
Thereby, a thermosetting film can be formed. This
Thermosetting films such as
Useful as adhesive film, for example, high capacity reliability
Semiconductor devices with excellent productivity and high productivity
be able to. When forming the heat resistant adhesive film
The substrate is not particularly limited, but for example,
Glass plate, silicon wafer, stainless plate, polyes
Tell film or the like can be used. Also heat resistant
To enable easy release of the adhesive film from the substrate
Therefore, it is possible to release these substrate surfaces in advance.
Wear. The varnish was applied to an appropriate substrate and cured.
Afterwards, a cured film formed by forcibly peeling off the substrate
Is also useful as a general heat-resistant film. Further
Non-solvent type thermosetting resin that does not substantially contain a solvent
Is in the form of powder, pellets, etc.
It can also be used as a paint or the like. The non-solvent type
Thermosetting resins are also useful as heat-resistant molding materials and the like.
For example, by heating under pressure in a suitable mold,
Can be processed into a cured molded article, or a blowing agent
And cured by heating to form a cured foam.
It can also be shaped. [0032] The present invention will be described below with reference to Examples and Comparative Examples.
As will be further described, the present invention is not limited to the gist thereof.
Therefore, the present invention is not limited to these embodiments. each
In Examples and Comparative Examples, storage stability and tensile
The strength was evaluated according to the following method.Storage stability Thermosetting resin (Examples 1 to 23) or polycarbodiy
The amide (Comparative Examples 1 to 3) was added to each solvent shown in Tables 1 to 3 at a concentration of 2
The solution dissolved at 0% by weight was added at room temperature or-
Store in a cool, dark place at 10 ° C.
The period during which there was no observation was visually observed and judged.Tensile strength Thermosetting resin (Examples 1 to 23) or polycarbodiy
The amide (Comparative Examples 1 to 3) was added to each solvent shown in Tables 1 to 3 at a concentration of
The surface of the solution dissolved to be 0% by weight is released in advance.
Spin on the treated glass plate using a spinner
After that, it was heated and cured at 250 ° C for 15 minutes,
50 μm (Examples 1 to 23), 5 μm (Comparative Examples 1 and 2)
Alternatively, a cured film having a thickness of 10 μm (Comparative Example 3) was formed. That
Later, these cured films were forcibly peeled off from the glass plate to obtain
The tensile strength of the cured film thus obtained was measured. Example 1Synthesis of polycarbodiimide 50 g of tolylene diisocyanate (TDI)
In 200 g of Sanone, 1-phenyl-3-methyl-2-
80 ° C. in the presence of 0.28 g of phosphorene-1-oxide
And react for 4 hours with polycarbodiimide (P-TDI) (M
n = 5,000).Production of thermosetting resin A 6.9 g of acrylic acid is added to the solution,
After reacting for hours, the reaction solution is developed in acetone,
A powdery thermosetting resin A (Mn = 5,800) was obtained.
Grafting of acrylic acid on the obtained thermosetting resin A
The amount is 1 mol equivalent of the repeating unit represented by the general formula (1).
Was 0.5 mol. Also, the thermosetting resin A has a red color.
The external absorption spectrum shows the absorption characteristic of the carbodiimide unit.
(Wave number 2,150-2,100cm^-1) And alkenyl
Absorption peculiar to the group (wave number 3,090-3,010cm^-1)
Indicated. This thermosetting resin A has a storage stability and
And tensile strength were evaluated. Table 1 shows the evaluation results. Example 2Production of thermosetting resin A 8.3 g of methacrylic acid was used instead of acrylic acid
Except that, in the same manner as in Example 1, the powdery thermosetting resin
A (Mn = 5,900) was obtained. Thermosetting resin obtained
The grafting amount of methacrylic acid in A is represented by the general formula
0.5 mol per mol of the repeating unit represented by (1)
there were. Also, the infrared absorption spectrum of the thermosetting resin A
Is the absorption specific to the carbodiimide unit (wave number 2,150
~ 2,100cm^-1) And alkenyl groups
(Wave number 3,090-3,010cm^-1)showed that. This heat
Evaluation of storage stability and tensile strength of curable resin A
Valued. Table 1 shows the evaluation results. Example 3Production of thermosetting resin A Instead of using acrylic acid, 14.0 g of cinnamic acid was used.
Other than that, in the same manner as in Example 1, the powdery thermosetting resin A
(Mn = 6,600) was obtained. The obtained thermosetting resin A
The grafting amount of cinnamic acid in the formula (1)
0.5 mole per mole of repeating unit represented.
The infrared absorption spectrum of the thermosetting resin A is
Absorption (wave number 2,150-2,1) peculiar to the bodimide unit
00cm^-1) And absorption specific to alkenyl groups (wavenumber 3,
090-3,010cm^-1)showed that. This thermosetting resin
For A, storage stability and tensile strength were evaluated. Comment
The results are shown in Table 1. Example 4Production of thermosetting resin A To the solution of P-TDI obtained in the same manner as in Example 1, 2-H
12.5 g of droxyethyl methacrylate was added, and 6
After reacting at 0 ° C for 5 hours, the reaction solution is placed in acetone.
Expanded and powdered thermosetting resin A (Mn = 6,400)
I got 2-hydroxy in the obtained thermosetting resin A
The amount of grafting of the ethyl methacrylate is represented by the general formula
0.5 mol per mol of the repeating unit represented by (1)
there were. Also, the infrared absorption spectrum of the thermosetting resin A
Is the absorption specific to the carbodiimide unit (wave number 2,150
~ 2,100cm^-1) And alkenyl groups
(Wave number 3,090-3,010cm^-1)showed that. This heat
Evaluation of storage stability and tensile strength of curable resin A
Valued. Table 1 shows the evaluation results. Example 5Production of thermosetting resin A Instead of 2-hydroxyethyl methacrylate, 2-
Using 13.8 g of hydroxypropyl methacrylate
Except that, in the same manner as in Example 4, the powdery thermosetting resin
A (Mn = 6,500) was obtained. Thermosetting resin obtained
Group A of 2-hydroxypropyl methacrylate in A
The amount of raft is represented by the repeating unit 1 represented by the general formula (1).
It was 0.5 mole per mole. In addition, the thermosetting resin
The infrared absorption spectrum of A is unique to carbodiimide units
Absorption (wave number 2,150-2,100cm^-1) And al
Absorption peculiar to kenyl group (wave number 3,090-3,010 cm
^-1)showed that. Storage stability of this thermosetting resin A
The properties and tensile strength were evaluated. Table 1 shows the evaluation results.
You. Example 6Production of thermosetting resin A Instead of 2-hydroxyethyl methacrylate, 2-
Other than using 11.2 g of hydroxyethyl acrylate
Is a powdered thermosetting resin A in the same manner as in Example 4.
(Mn = 6,300) was obtained. The obtained thermosetting resin A
Grafting of 2-hydroxyethyl acrylate
The amount is 1 mol equivalent of the repeating unit represented by the general formula (1).
Was 0.5 mol. Also, the thermosetting resin A has a red color.
The external absorption spectrum shows the absorption characteristic of the carbodiimide unit.
(Wave number 2,150-2,100cm^-1) And alkenyl
Absorption peculiar to the group (wave number 3,090-3,010cm^-1)
Indicated. This thermosetting resin A has a storage stability and
And tensile strength were evaluated. Table 1 shows the evaluation results. Example 7Production of thermosetting resin A Instead of 2-hydroxyethyl methacrylate, 2-
After using 12.6 g of hydroxypropyl acrylate
Outside, in the same manner as in Example 4, the powdery thermosetting resin A
(Mn = 6,400) was produced. The resulting thermosetting tree
Of 2-hydroxypropyl acrylate in Fat A
The amount of raft is represented by the repeating unit 1 represented by the general formula (1).
It was 0.5 mole per mole. In addition, the thermosetting resin
The infrared absorption spectrum of A is unique to carbodiimide units
Absorption (wave number 2,150-2,100cm^-1) And al
Absorption peculiar to kenyl group (wave number 3,090-3,010 cm
^-1)showed that. Storage stability of this thermosetting resin A
The properties and tensile strength were evaluated. Table 1 shows the evaluation results.
You. Example 8Production of thermosetting resin A Instead of 2-hydroxyethyl methacrylate, use a pen
Using 28.7 g of taerythritol triacrylate
Except that, in the same manner as in Example 4, the powdery thermosetting resin
A (Mn = 8,250) was obtained. Thermosetting resin obtained
A of pentaerythritol triacrylate in A
The amount of raft is represented by the repeating unit 1 represented by the general formula (1).
It was 0.5 mole per mole. In addition, the thermosetting resin
The infrared absorption spectrum of A is unique to carbodiimide units
Absorption (wave number 2,150-2,100cm^-1) And al
Absorption peculiar to kenyl group (wave number 3,090-3,010 cm
^-1)showed that. Storage stability of this thermosetting resin A
The properties and tensile strength were evaluated. Table 1 shows the evaluation results.
You. Example 9Production of thermosetting resin A 2-t was added to the P-TDI solution obtained in the same manner as in Example 1.
-Add 17.8 g of butylaminoethyl methacrylate
After reacting at 80 ° C for 6 hours, the reaction solution was
Thermosetting resin A (Mn = 7.0)
00). 2-t in the obtained thermosetting resin A
-Butylaminoethyl methacrylate graft amount,
Per mole of the repeating unit represented by the general formula (1)
0.5 mole. In addition, infrared absorption of the thermosetting resin A
The absorption spectrum shows the absorption (wavelength)
Number 2,150-2,100cm^-1) And alkenyl groups
Specific absorption (wave number 3,090-3,010cm^-1)
Was. With respect to the thermosetting resin A, storage stability and evacuation
The tensile strength was evaluated. Table 1 shows the evaluation results. Example 10Production of thermosetting resin A Instead of 2-t-butylaminoethyl methacrylate
2-tert-butylaminoethyl acrylate 16.5
g in the same manner as in Example 9 except that g was used.
A curable resin A (Mn = 6,900) was obtained. The heat gained
2-t-butylaminoethyl acrylate in the curable resin A
The graft amount of the relate is represented by the general formula (1).
It was 0.5 mol per mol of the repeating unit. Also,
The infrared absorption spectrum of thermosetting resin A is carbodiimid
Absorbance peculiar to each unit (wave number 2,150-2,100c
m^-1) And alkenyl groups (wave number 3,09)
0-3,010cm^-1)showed that. This thermosetting resin A
Then, storage stability and tensile strength were evaluated. Evaluation
The results are shown in Table 1. Embodiment 11Synthesis of polycarbodiimide Diphenylmethane-4,4'-diisocyanate (MDI)
50 g of 1-phenylene in 200 g of cyclohexanone
Ru-3-methyl-2-phospholene-1-oxide 0.2
The reaction was carried out at 80 ° C for 4 hours in the presence of
A solution of diimide (P-MDI) (Mn = 5,000) was obtained.Production of thermosetting resin A 4.0 g of acrylic acid was added to the solution,
After reacting for hours, the reaction solution is developed in acetone,
A powdery thermosetting resin A (Mn = 5,400) was obtained.
Grafting of acrylic acid on the obtained thermosetting resin A
The amount is 1 mol equivalent of the repeating unit represented by the general formula (1).
Was 0.5 mol. Also, the thermosetting resin A has a red color.
The external absorption spectrum shows the absorption characteristic of the carbodiimide unit.
(Wave number 2,150-2,100cm^-1) And alkenyl
Absorption peculiar to the group (wave number 3,090-3,010cm^-1)
Indicated. This thermosetting resin A has a storage stability and
And tensile strength were evaluated. Table 1 shows the evaluation results. Example 12Production of thermosetting resin A 4.7 g of methacrylic acid was used instead of acrylic acid
Except that, in the same manner as in Example 11, the powdery thermosetting resin
Fat A (Mn = 5,500) was obtained. The resulting thermosetting tree
The graft amount of methacrylic acid in Fat A is determined by the general formula
0.5 mol per mol of the repeating unit represented by (1)
there were. Also, the infrared absorption spectrum of the thermosetting resin A
Is the absorption specific to the carbodiimide unit (wave number 2,150
~ 2,100cm^-1) And alkenyl groups
(Wave number 3,090-3,010cm^-1)showed that. This heat
Evaluation of storage stability and tensile strength of curable resin A
Valued. Table 1 shows the evaluation results. Example 13Production of thermosetting resin A 2-PDI was added to the P-MDI solution obtained in the same manner as in Example 11.
Add 7.1 g of hydroxyethyl methacrylate and add 6 g
After reacting at 0 ° C for 5 hours, the reaction solution is placed in acetone.
Expanded and powdered thermosetting resin A (Mn = 5,700)
I got 2-hydroxy in the obtained thermosetting resin A
The amount of grafting of the ethyl methacrylate is represented by the general formula
0.5 mol per mol of the repeating unit represented by (1)
there were. Also, the infrared absorption spectrum of the thermosetting resin A
Is the absorption specific to the carbodiimide unit (wave number 2,150
~ 2,100cm^-1) And alkenyl groups
(Wave number 3,090-3,010cm^-1)showed that. This heat
Evaluation of storage stability and tensile strength of curable resin A
Valued. Table 1 shows the evaluation results. Example 14Production of thermosetting resin A Instead of 2-hydroxyethyl methacrylate, 2-
After using 7.9 g of hydroxypropyl methacrylate
Outside, in the same manner as in Example 13, the powdered thermosetting resin
A (Mn = 5,850) was obtained. Thermosetting resin obtained
Group A of 2-hydroxypropyl methacrylate in A
The amount of raft is represented by the repeating unit 1 represented by the general formula (1).
It was 0.5 mole per mole. In addition, the thermosetting resin
The infrared absorption spectrum of A is unique to carbodiimide units
Absorption (wave number 2,150-2,100cm^-1) And al
Absorption peculiar to kenyl group (wave number 3,090-3,010 cm
^-1)showed that. Storage stability of this thermosetting resin A
The properties and tensile strength were evaluated. Table 1 shows the evaluation results.
You. Example 15Production of thermosetting resin A 2-PDI was added to the P-MDI solution obtained in the same manner as in Example 11.
10.1 g of t-butylaminoethyl methacrylate was added.
And reacted at 80 ° C for 6 hours.
Tons of powdered thermosetting resin A (Mn = 6,
100). 2- in the obtained thermosetting resin A
Grafting amount of t-butylaminoethyl methacrylate
Is equivalent to 1 mol of the repeating unit represented by the general formula (1).
0.5 mol. In addition, the infrared of the thermosetting resin A
The absorption spectrum shows the absorption characteristic of the carbodiimide unit.
(Wave number 2,150-2,100cm^-1) And alkenyl
Absorption peculiar to the group (wave number 3,090-3,010cm^-1)
Indicated. This thermosetting resin A has a storage stability and
And tensile strength were evaluated. Table 1 shows the evaluation results. Embodiment 16Synthesis of polycarbodiimide Dicyclohexylmethane-4,4'-diisocyanate
(HMDI) 50 g of 1-phenyl-3-methyl-2-phos
At 180 ° C. in the presence of 2.50 g of holene-1-oxide
After reacting for 8 hours, polycarbodiimide (P-HMDI) (M
n = 5,000).Production of thermosetting resin A Dissolve the P-HMDI in 200 g of anisole and add
4.2 g of lylic acid was added and reacted at 20 ° C. for 3 hours.
The reaction solution is developed in acetone and powdered thermosetting
Resin A (Mn = 5,400) was obtained. The obtained thermosetting properties
The amount of acrylic acid grafted on the resin A is represented by the general formula
0.5 mol per mol of the repeating unit represented by (1)
there were. Also, the infrared absorption spectrum of the thermosetting resin A
Is the absorption specific to the carbodiimide unit (wave number 2,150
~ 2,100cm^-1) And alkenyl groups
(Wave number 3,090-3,010cm^-1)showed that. This heat
Evaluation of storage stability and tensile strength of curable resin A
Valued. Table 2 shows the evaluation results. Example 17Production of thermosetting resin A 5.0 g of methacrylic acid was used instead of acrylic acid
Other than the above, a powdery thermosetting resin was prepared in the same manner as in Example 16.
Fat A (Mn = 5,500) was obtained. The resulting thermosetting tree
The graft amount of methacrylic acid in Fat A is determined by the general formula
0.5 mol per mol of the repeating unit represented by (1)
there were. Also, the infrared absorption spectrum of the thermosetting resin A
Is the absorption specific to the carbodiimide unit (wave number 2,150
~ 2,100cm^-1) And alkenyl groups
(Wave number 3,090-3,010cm^-1)showed that. This heat
Evaluation of storage stability and tensile strength of curable resin A
Valued. Table 2 shows the evaluation results. Example 18Production of thermosetting resin A The solution of P-HMDI obtained in the same manner as in Example 16 was added with 2-
7.6 g of hydroxyethyl methacrylate was added, and 6
After reacting at 0 ° C for 5 hours, the reaction solution is placed in acetone.
Expanded and powdered thermosetting resin A (Mn = 5,800)
I got 2-hydroxy in the obtained thermosetting resin A
The amount of grafting of the ethyl methacrylate is represented by the general formula
0.5 mol per mol of the repeating unit represented by (1)
there were. Also, the infrared absorption spectrum of the thermosetting resin A
Is the absorption specific to the carbodiimide unit (wave number 2,150
~ 2,100cm^-1) And alkenyl groups
(Wave number 3,090-3,010cm^-1)showed that. This heat
Evaluation of storage stability and tensile strength of curable resin A
Valued. Table 2 shows the evaluation results. Example 19Production of thermosetting resin A Instead of 2-hydroxyethyl methacrylate, 2-
After using 7.6 g of hydroxypropyl methacrylate
Outside, in the same manner as in Example 16, the powdered thermosetting resin
A (Mn = 5,900) was obtained. Thermosetting resin obtained
Group A of 2-hydroxypropyl methacrylate in A
The amount of raft is represented by the repeating unit 1 represented by the general formula (1).
It was 0.5 mole per mole. In addition, the thermosetting resin
The infrared absorption spectrum of A is unique to carbodiimide units
Absorption (wave number 2,150-2,100cm^-1) And al
Absorption peculiar to kenyl group (wave number 3,090-3,010 cm
^-1)showed that. Storage stability of this thermosetting resin A
The properties and tensile strength were evaluated. Table 2 shows the evaluation results.
You. Example 20Production of thermosetting resin A The solution of P-HMDI obtained in the same manner as in Example 16 was added with 2-
10.8 g of t-butylaminoethyl methacrylate was added.
And reacted at 80 ° C for 6 hours.
Tons of powdered thermosetting resin A (Mn = 6,
100). 2- in the obtained thermosetting resin A
Grafting amount of t-butylaminoethyl methacrylate
Is equivalent to 1 mol of the repeating unit represented by the general formula (1).
0.5 mol. In addition, the infrared of the thermosetting resin A
The absorption spectrum shows the absorption characteristic of the carbodiimide unit.
(Wave number 2,150-2,100cm^-1) And alkenyl
Absorption peculiar to the group (wave number 3,090-3,010cm^-1)
Indicated. This thermosetting resin A has a storage stability and
And tensile strength were evaluated. Table 2 shows the evaluation results. Embodiment 21Production of thermosetting resin B Instead of acrylic acid, trimellitic anhydride 18.5
g in the same manner as in Example 1 except that g was used.
A curable resin B (Mn = 7,100) was obtained. The heat gained
Grafting of trimellitic anhydride on curable resin B
The amount is 1 mol equivalent of the repeating unit represented by the general formula (1).
Was 0.5 mol. Also, the thermosetting resin A has a red color.
The external absorption spectrum shows the absorption characteristic of the carbodiimide unit.
(Wave number 2,150-2,100cm^-1) And carboxylic acid
Absorption specific to anhydride groups (wave number 1,850 to 1,780 cm
^-1)showed that. Storage stability of this thermosetting resin B
The properties and tensile strength were evaluated. Table 2 shows the evaluation results.
You. Example 22Production of thermosetting resin B Instead of acrylic acid, trimellitic anhydride 10.5
g in the same manner as in Example 11 except that g was used.
A thermosetting resin B (Mn = 6,100) was obtained. Got
Graph of trimellitic anhydride in thermosetting resin B
The amount is 1 mol of the repeating unit represented by the general formula (1).
0.5 mol / mol. In addition, the thermosetting resin A
The infrared absorption spectrum shows the absorption characteristic of the carbodiimide unit.
Yield (wave number 2,150-2,100cm^-1) And carvone
Absorption (wave number 1,850 to 1,780) peculiar to the acid anhydride group
cm^-1)showed that. This thermosetting resin B has a low storage stability.
The qualitative and tensile strength were evaluated. Table 2 shows the evaluation results.
You. Example 23Production of thermosetting resin B Instead of acrylic acid, trimellitic anhydride 11.3
g in the same manner as in Example 16 except that g was used.
A thermosetting resin B (Mn = 6,200) was obtained. Got
Graph of trimellitic anhydride in thermosetting resin B
The amount is 1 mol of the repeating unit represented by the general formula (1).
0.5 mol / mol. In addition, the thermosetting resin A
The infrared absorption spectrum shows the absorption characteristic of the carbodiimide unit.
Yield (wave number 2,150-2,100cm^-1) And carvone
Absorption (wave number 1,850-1,780) peculiar to acid anhydride group
cm^-1)showed that. This thermosetting resin B has a low storage stability.
The qualitative and tensile strength were evaluated. Table 2 shows the evaluation results.
You. Comparative Example 1 Storage stability of P-TDI obtained in the same manner as in Example 1.
And the tensile strength was evaluated. Table 3 shows the evaluation results. Comparative Example 2 Storage stability of P-MDI obtained in the same manner as in Example 11
The properties and tensile strength were evaluated. Table 3 shows the evaluation results.
You. Comparative Example 3 Storage stability of P-HMDI obtained in the same manner as in Example 16
The properties and tensile strength were evaluated. Table 3 shows the evaluation results.
You. [0037] [Table 1][0038] [Table 2][0039] [Table 3] [0040] The thermosetting resin produced according to the present invention
Is particularly excellent in storage stability as a solution,
Good solubility in seed solvents and excellent curability
In addition, the cured product has low water absorption,
Insulation, chemical stability, moisture resistance, heat resistance, mechanical strength, etc.
Is excellent. Therefore, the heat produced by the present invention
Curable resins can be used as adhesives, coatings, especially as heat-resistant varnishes.
Very suitable for use as a protective film for materials, electronic materials, etc.
With excellent thermosetting film and cured molding
It can be easily processed into products and the like. Embedded image

────────────────────────────────────────────────── (5) References JP-A-59-120630 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 CAPLUS (STN ) REGISTRY (STN)

Claims (1)

(57) [Claims] [Claim 1] The general formula (1) (Wherein R ¹ represents a divalent organic group). At least one of the polycarbodiimides having a repeating unit represented by the formula ( ¹ ) has a carboxyl group and a primary or secondary amino group.
And a group selected from the group consisting of a group represented by the general formula (2) : (Where R ² is an aliphatic, alicyclic or aromatic trivalent
Shows an organic group. ) , A compound having a group represented by
Luic acid, cinnamic acid, p-aminostyrene, 2-t-butyl
Aminoethyl (meth) acrylate, p-methylamino
Styrene, vinyl phenol, ## STR3 ## (Where each R ³ may be the same or different,
Represents an atom or a methyl group, i is an integer of 1 to 30
You. ), Embedded image (Where R ³ represents a hydrogen atom or a methyl group, and j is 2
Is an integer of up to 30. ), [Of 5] (Where R ³ represents a hydrogen atom or a methyl group, and k is 2
Is an integer of up to 30. ), ## STR00006 ## (Here, R ³ represents a hydrogen atom or a methyl group.)
Bini [Chemical 7] Wherein R ³ represents a hydrogen atom or a methyl group. At least one kind of a compound having a graft-reactive group and a cross-linkable group selected from the group is grafted at an appropriate temperature. Production method of conductive resin.