JPH10338810A - Thermoset resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in solubility in various solvents, storage stability and curing characteristics and capable of giving cured products having high softening temperature and excellent heat resistance, transparency, electrical insulation properties, humidity resistance, wet-heat resistance, adhesiveness and mechanical properties by including a polycarbodiimide and a thiirane compound. SOLUTION: The polymer (polycarbodiimide) (A) having repeating units represented by the formula: -N=C=N-R' (wherein R' is a divalent organic group) is obtained by the decarboxylation condensation of a polyisocyanate compound and is a thermoplastic resin which shows excellent heat resistance because the carbodiimide groups in the molecule are crosslinked when heated. The organic polyisocyanate used in the synthesis is exemplified by phenylene-1,3- diisocyanate. The thiirane compound (B) has at least one thiiranyl group in the molecule and has a molecular weight of 70-20,000 and is obtained by replacing the oxygen atom in the oxirane ring of an oxirane compound by a sulfur atom. 100 pts.wt. component A is incorporated with 5-1,000 pts.wt. component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD [0001] The present invention relates to solubility in a solvent,
Excellent storage stability and curing properties, and high heat resistance,
The present invention relates to a thermosetting resin composition useful in a wide range of fields including electronic circuit components and semiconductor devices.

[0002]

2. Description of the Related Art Today, electronic circuit components or semiconductor devices are important in a wide range of fields.
For the device, a thermosetting resin excellent in heat resistance, moisture resistance, moisture and heat resistance, adhesive strength, storage stability, workability, etc. is required, but in the case of epoxy resins that have been mainly used conventionally, In particular, it has a drawback that it has poor wet heat resistance. On the other hand, as a technique for improving the wet heat resistance of an epoxy resin, a technique of blending a polycarbodiimide with an epoxy resin as a curing agent (Japanese Patent Publication No. 1-7411) is known. In this technique, a carbodiimide group and an epoxy group are used. Have low reactivity and require high temperatures for curing. As a method of lowering the curing temperature of the epoxy resin / polycarbodiimide composition and shortening the curing time, for example, Japanese Patent Application Laid-Open No. 5-239427 discloses an epoxy resin and a polycarbodiimide with an epoxy resin curing agent. Paste or powder compositions containing a curing agent for polycarbodiimide have been proposed. However,
This composition has too high reactivity between the active hydrogen-containing compound used as a curing agent for the epoxy resin and the carbodiimide group in the polycarbodiimide, for example, it is difficult to prepare a paste-like composition or even if it can be prepared. There is a problem that storage stability is remarkably inferior. Further, as a polycarbodiimide / epoxy compound-based composition which has good storage stability even in a solution form, a varnish form and a paste form and can be cured at a low temperature, JP-A-8-81545 discloses a method in which a carboxylic acid anhydride is grafted onto polycarbodiimide. A thermosetting resin composition composed of a modified polycarbodiimide and an epoxy compound is disclosed. However, reflecting rapid progress in the field of electronic circuit components and semiconductor devices in recent years, heat can be cured in a shorter time and at a lower temperature, and has excellent heat resistance, moisture resistance, moisture heat resistance, adhesive strength, and the like. There is a need for a curable resin composition.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent solubility in various solvents, excellent storage stability and curing properties, and a high softening temperature of a cured product, excellent heat resistance, transparency and electrical insulation. An object of the present invention is to provide a thermosetting resin composition having excellent heat resistance, moisture resistance, wet heat resistance, adhesiveness, mechanical properties, and the like.

[0004]

Means for Solving the Problems The present invention provides: (A) a general formula (1) -N = C = NR ^1- (1) (where R ¹ represents a divalent organic group) A thermosetting resin composition comprising a polymer having a repeating unit represented by the following formula (hereinafter referred to as "polycarbodiimide") and (B) a thiirane compound.

Hereinafter, the present invention will be described in detail. Polycarbodiimide The polycarbodiimide used in the present invention is a resin obtained by decarboxylation of a polyisocyanate compound, and its production method is described in, for example, Die Ma by DJ Lyman et al.
Chem., 67 , 1 (1963), J. Am. C by E. Deyer et al.
hem. Soc., 80 , 5495 (1958), LM Alberion et al., J. A.
ppl. Polym. Sci., 21 , 1999 (1977), TWCampbell, J. Org. Chem., 28 , 2069 (1963), JP-A-51-615.
No. 99 and the like. These polycarbodiimides are thermosetting resins having excellent heat resistance, with the carbodiimide groups in the molecules being crosslinked by heating. The method for synthesizing the polycarbodiimide used in the present invention is not particularly limited, and the polycarbodiimide may be, for example, a catalyst that promotes a carbodiimidation reaction of an organic polyisocyanate with an isocyanate group (hereinafter, referred to as a “carbodiimidation catalyst”). ").). As the organic polyisocyanate used in the synthesis of the polycarbodiimide, an organic diisocyanate is preferable. Examples of such organic diisocyanates include phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 1-ethoxyphenylene-2,4-diisocyanate, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, biphenylene-4,4'-diisocyanate, 3,3'-dimethoxybiphenylene-4,4 '-Diisocyanate,
3,3′-dimethylbiphenylene-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-4,4 ′
-Diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, naphthylene-1,
5-diisocyanate, cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate,
-Methylcyclohexylene-2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclohexane-1,3-bis (methyl Isocyanate), cyclohexane-1,4-bis (methyl isocyanate),
Isophorone diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate,
Hexamethylene-1,6-diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester, and the like, and a reaction between a stoichiometric excess of these organic diisocyanates and a bifunctional active hydrogen-containing compound. Both terminal isocyanate prepolymers can be exemplified. The organic diisocyanates may be used alone or in combination of two or more.

Other organic polyisocyanates optionally used together with organic diisocyanates include, for example, phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, diphenylmethane-2, 5,4'-triisocyanate, triphenylmethane-2,4 ', 4 "-triisocyanate, triphenylmethane-4,4', 4"-
Triisocyanate, diphenylmethane-2,4
2 ', 4'-tetraisocyanate, diphenylmethane-2,5,2', 5'-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methylisocyanate), 3 , 5-Dimethylcyclohexane-1,3,5-
Tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methyl isocyanate), dicyclohexylmethane-2,4,2 '
-Triisocyanate, dicyclohexylmethane-2,
By reaction of a trifunctional or higher organic polyisocyanate such as 4,4′-triisocyanate or a stoichiometric excess of the trifunctional or higher organic polyisocyanate with a bifunctional or higher polyfunctional active hydrogen-containing compound The resulting terminal isocyanate prepolymer can be exemplified. The other organic polyisocyanate can be used alone or as a mixture of two or more, and the amount used is usually 0 to 40 parts by weight, preferably 0 to 20 parts by weight, per 100 parts by weight of the organic diisocyanate. Department.

In addition, when synthesizing a polycarbodiimide, an organic monoisocyanate is added as required, and when the organic polyisocyanate contains the other organic polyisocyanate, the molecular weight of the obtained polycarbodiimide is appropriately regulated. By using an organic diisocyanate in combination with an organic monoisocyanate, a polycarbodiimide having a relatively low molecular weight can be obtained. Examples of such organic monoisocyanates include alkyl monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, lauryl isocyanate, and stearyl isocyanate; cyclohexyl isocyanate, 4-methylcyclohexyl isocyanate, Cycloalkyl monoisocyanates such as 5-dimethylcyclohexyl isocyanate; phenyl isocyanate, o-tolyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, 2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, 2-chlorophenyl isocyanate, 4- Chlorophenyl isocyanate, 2-
Trifluoromethylphenyl isocyanate, 4-trifluoromethylphenyl isocyanate, naphthalene-
Aryl monoisocyanates such as 1-isocyanate can be mentioned. The organic monoisocyanate may be used alone or in combination of two or more. The amount of the organic monoisocyanate varies depending on the desired molecular weight of the polycarbodiimide, the presence or absence of the other organic polyisocyanate, and the like. It is usually 0 to 40 parts by weight, preferably 0 to 20 parts by weight, per 100 parts by weight of the isocyanate component.

The carbodiimidization catalyst includes, for example, 1-phenyl-2-phospholene-1-oxide,
1-phenyl-3-methyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-sulfide, 1-phenyl-3-methyl-2-phospholene-1-
Sulfide, 1-ethyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-sulfide, 1-ethyl-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- Phosphorene compounds such as methyl-3-methyl-2-phospholene-1-sulfide and the like and 3-phospholene isomers thereof; pentacarbonyliron, nonacarbonyldiiron, tetracarbonylnickel, hexacarbonyltungsten, hexacarbonylchromium and the like Metal carbonyl complex; acetylene of metals such as beryllium, aluminum, zirconium, chromium, and iron Acetone complex; trimethyl phosphate, can be mentioned triethyl phosphate, triisopropyl phosphate, tri -t- butyl phosphate, phosphate esters such as triphenyl phosphate. The carbodiimidization catalyst may be used alone or
More than one species can be mixed and used,
Per 100 parts by weight of all organic isocyanate components,
It is 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight.

The synthesis reaction of polycarbodiimide can be carried out without solvent or in a suitable solvent. The solvent may be any solvent capable of dissolving the polycarbodiimide by heating during the synthesis reaction, such as 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-
Trichloroethane, 1,1,2-trichloroethane,
1,1,1,2-tetrachloroethane, 1,1,2,2
-Tetrachloroethane, pentachloroethane, hexachloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-
Halogenated hydrocarbon solvents such as trichlorobenzene and trichloromethylbenzene; dioxane, anisole, tetrahydrofuran, tetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol monomethyl ether; Ether solvents such as diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether and triethylene glycol monomethyl ether; cyclohexanone, 2-acetylcyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4- Methylcyclohexano , Cycloheptanone, 1-decalone, 2-decalone, 2,4-dimethyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2-methyl -
3-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone,
2,6-dimethyl-4-heptanone, 2-octanone,
Ketone solvents such as 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, and 4-decanone; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and cumene; N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N-methyl-3-
Pyrrolidone, N-acetyl-3-pyrrolidone, N-benzyl-3-pyrrolidone, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide Amide solvents such as N, N-dimethylacetamide and N-methylpropionamide; other aprotic polar solvents such as dimethylsulfoxide; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-n-propoxyethyl acetate , 2-n-butoxyethyl acetate, 2-phenoxyethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-
Acetate solvents such as propyl ether acetate and diethylene glycol mono-n-butyl ether acetate can be exemplified. These solvents can be used alone or in combination of two or more. The amount of the solvent used in the synthesis reaction of the polycarbodiimide is such that the concentration of all the organic isocyanate components is usually 0.5 to 60% by weight, preferably 5 to 50% by weight. In this case, if the concentration of all organic isocyanate components is too high,
The resulting polycarbodiimide may gel during the synthesis reaction, and if the concentration of all organic isocyanate components is too low, the reaction rate will be slow and productivity will be reduced. The temperature of the synthesis reaction of polycarbodiimide is appropriately selected according to the type of the organic isocyanate component and the carbodiimidization catalyst, and is usually 20 to 200 ° C. In the polycarbodiimide synthesis reaction, the organic isocyanate component may be added in its entirety before the reaction, or a part or all of it may be added continuously or stepwise during the reaction.

Further, in the present invention, a compound capable of reacting with an isocyanate group is added at an appropriate reaction stage from an early stage to a late stage of a polycarbodiimide synthesis reaction,
Seal the terminal isocyanate group of polycarbodiimide,
The molecular weight of the obtained polycarbodiimide can be adjusted, and the molecular weight of the obtained polycarbodiimide can be regulated to a predetermined value by adding the polycarbodiimide late in the synthesis reaction. Examples of such a compound capable of reacting with an isocyanate group include methanol, ethanol, n-propanol, n-butanol, n-octanol, benzyl alcohol, 2-phenylethanol, cyclopentanol, cyclohexanol, and 2-methoxyethanol. Alcohols such as, 2-ethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; phenol;
o-cresol, m-cresol, p-cresol,
2,3-xylenol, 2,4-xylenol, 2,5
Phenols such as -xylenol, 2,6-xylenol, 3,4-xylenol and 3,5-xylenol; acetone oxime, butanone oxime, 3-methylbutanone oxime, 3,3-dimethylbutanone oxime,
Pentanone oxime, 3-pentanone oxime, 4-methyl-2-pentanone oxime, cyclopentanone oxime, 2,2,4-trimethylcyclopentanone oxime, 2,4,4-trimethylcyclopentanone oxime, cyclohexanone Aliphatic, alicyclic or aromatic monooximes such as oxime and acetophenone oxime; amines such as dimethylamine, diethylamine and benzylamine; lactams such as pyrrolidone and ε-caprolactam; diethyl malonate, ethyl acetoacetate and the like And the like. Among these compounds, phenols and amines are particularly preferred. The polycarbodiimide synthesized as described above is separated from the solution as needed. In this case, as a method for separating polycarbodiimide, for example, a polycarbodiimide solution is added to a non-solvent inert to the polycarbodiimide, and the resulting precipitate or oil is separated and collected by filtration or decantation. how to;
A method of separating and collecting by spray drying; a method of separating and collecting by utilizing the change in solubility of the obtained polycarbodiimide with respect to the solvent used in the synthesis, that is, immediately after the synthesis, the polycarbodiimide dissolved in the solvent is not used. In the case of precipitation by lowering the temperature of the system, a method of separating / collecting from the turbid liquid by filtration or the like can be mentioned, and these separation / collecting methods can be appropriately combined.

In the present invention, the polycarbodiimide has a number average molecular weight in terms of polystyrene (hereinafter referred to as "Mn") determined by gel permeation chromatography (GPC).
That. ) Is usually from 400 to 500,000, preferably from 1,000 to 200,000, particularly preferably 2,
000 to 100,000.

Modified Polycarbodiimide In the present invention, a modified polycarbodiimide obtained by chemically modifying the polycarbodiimide synthesized as described above can be used as at least a part of the polycarbodiimide. As the modified polycarbodiimide, a resin obtained by grafting one or more compounds having a graft reactive group and a carboxylic anhydride group (hereinafter, referred to as “reactive compound”) to polycarbodiimide is preferable. By using such a modified polycarbodiimide, the compatibility with other components contained in the thermosetting resin composition of the present invention is further improved, and the curing time of the composition can be further reduced. And the adhesion can be further improved. Here, the graft reactive group in the reactive compound means a group which reacts with polycarbodiimide to give a modified polycarbodiimide in which a residue having a carboxylic acid anhydride group of the reactive compound is grafted. Such a graft-reactive group may be any functional group having active hydrogen, such as a carboxyl group or a primary or secondary amino group. These graft-reactive groups can have one or more identical or different groups in the reactive compound. Further, one or more carboxylic acid anhydride groups in the reactive compound can be present. Such a reactive compound can be an aromatic compound, an aliphatic compound or an alicyclic compound, and a cyclic compound may be a carbocyclic compound or a heterocyclic compound.

Examples of the reactive compound include trimellitic anhydride, benzene-1,2,3-tricarboxylic anhydride, naphthalene-1,2,4-tricarboxylic anhydride, and naphthalene-1,4,5. -Tricarboxylic anhydride,
Naphthalene-2,3,6-tricarboxylic anhydride, naphthalene-1,2,8-tricarboxylic anhydride, 4- (4
-Carboxybenzoyl) phthalic anhydride, 4- (4-
Aromatic tricarboxylic anhydrides such as carboxyphenyl) phthalic anhydride and 4- (4-carboxyphenoxy) phthalic anhydride: monomethyl ester of pyromellitic monoanhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic monoanhydride monomethyl ester, 3,3 ',
Monoalkyl esters of aromatic tetracarboxylic monoanhydride such as monomethyl ester of 4,4'-biphenyltetracarboxylic monoanhydride; 3-carboxymethylglutaric anhydride, butane-1,2,4-tricarboxylic acid −
Aliphatic tricarboxylic anhydrides such as 1,2-anhydride and propene-1,2,3-tricarboxylic acid-1,2-anhydride; 3-amino-4-cyano-5-methylphthalic anhydride; -Amino-4-cyano-5,6-diphenylphthalic anhydride, 3-methylamino-4-cyano-5-methylphthalic anhydride, 3-methylamino-4-cyano-
Amino aromatic dicarboxylic anhydrides such as 5,6-diphenylphthalic anhydride; aminosuccinic anhydride, 4-amino-1,2-butanedicarboxylic anhydride, 4-aminohexahydrophthalic anhydride, N And aminoaliphatic dicarboxylic anhydrides such as -methylaminosuccinic anhydride, 4-methylamino-1,2-butanedicarboxylic anhydride, and 4-methylaminohexahydrophthalic anhydride. Among these reactive compounds, trimellitic anhydride is particularly preferred. The reactive compounds can be used alone or in combination of two or more.

Next, a method for synthesizing the modified polycarbodiimide will be described. The modified polycarbodiimide includes at least one kind of polycarbodiimide having a repeating unit represented by the general formula (1) and at least one kind of a reactive compound.
The seed can be synthesized by grafting (hereinafter, referred to as “denaturation reaction”) at an appropriate temperature in the presence or absence of an appropriate catalyst. The amount of the reactive compound used in the modification reaction is appropriately adjusted depending on the type of the polycarbodiimide and the reactive compound, the use of the obtained thermosetting resin composition, and the like. The proportion of the graft-reactive group in the reactive compound is usually 0.01 to 1 mol, preferably 0.02 to 0.8 mol, per 1 mol of the repeating unit represented. In this case, if the proportion of the graft-reactive group is less than 0.01 mol, the effect of shortening the curing time and the effect of improving the compatibility with other components tend to be insufficient. The inherent properties of carbodiimide may be impaired. In the modification reaction, the graft reactive group in the reactive compound and the polycarbodiimide represented by the general formula (1)
The reaction with the repeating unit represented by the formula (1) proceeds quantitatively, and a graft reaction appropriate for the amount of the reactive compound used is achieved. The denaturation reaction can be carried out without a solvent, but is preferably carried out in a suitable solvent. Such a solvent is not particularly limited as long as it is inert to the polycarbodiimide and the reactive compound and can dissolve them, and examples thereof include the above-mentioned solvent used for the synthesis of polycarbodiimide. Examples thereof include ether solvents, amide solvents, ketone solvents, aromatic hydrocarbon solvents, and other aprotic polar solvents. These solvents can be used alone or in combination of two or more. When the solvent used in the synthesis of the polycarbodiimide can be used for the modification reaction, the polycarbodiimide solution obtained by the synthesis can be used as it is. The amount of solvent used in the denaturation reaction is
Usually, 10 to 1 per 100 parts by weight of the total amount of the reaction raw materials
It is 0000 parts by weight, preferably 50 to 5,000 parts by weight. The temperature of the denaturation reaction is appropriately selected depending on the types of the polycarbodiimide and the reactive compound.
It is 100 ° C. or lower, preferably −10 to + 80 ° C.

The Mn of the modified polycarbodiimide obtained as described above is usually from 500 to 1,000,000.
0, preferably 1,000 to 400,000, more preferably 2,000 to 200,000. The modified polycarbodiimide is usually used as a solution for preparing the thermosetting resin composition of the present invention, but may be used separately from the solution. As a method for separating the modified polycarbodiimide obtained as a solution at the time of the synthesis from the solvent, a method similar to the above-described method for separating polycarbodiimide can be exemplified. The polycarbodiimide and the modified polycarbodiimide thus obtained are excellent in heat resistance, electric insulation, impact resistance and the like, and can impart excellent properties to the thermosetting resin composition of the present invention. It is.

The thiirane compounds Next, thiirane compounds used in the present invention is a compound having at least one thiiranyl group in the molecule may have a functional group other than the thiiranyl group. The molecular weight of the thiirane compound used in the present invention is not particularly limited, but is usually 70 to 20,000. The thiirane compound can be synthesized exclusively by substituting the oxygen atom of the oxirane ring in the oxirane compound with a sulfur atom. As a method for synthesizing thiirane compounds, for example, J.
J. Polym. Sci. Polym. Phys., By M. Charlesworth
17 , 329 (1979), a method of reacting an oxirane compound with a thiocyanate, RDS
The method shown in J. Org.Chem., 26 , 3467 (1961) by chuetz et al. can include a method of reacting an oxirane compound with thiourea, and a synthesis method from a cyclic carbonate. J. Org. Che by S.Seales et al.
m., 27 , 2832 (1962).

Specific examples of the thiirane compound used in the present invention are described in Chem. Rev. 66 , 297 (1.
966) in Table-I. Specific examples of the other thiirane compounds include epoxy group-containing polymerizable unsaturated compounds such as glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, and 3,4-epoxycyclohexyl methacrylate; One or more (co) polymers of an unsaturated compound, a copolymer of one or more of the epoxy group-containing polymerizable unsaturated compounds and one or more of other polymerizable unsaturated compounds, a glycidyl ester type epoxy resin , Aromatic glycidylamine type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, liquid rubber modified epoxy resin, bisphenol type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, etc. Representative glycidyl ether type epoxy resins Thiirane compounds an oxygen atom of the oxirane ring in the oxirane compound is substituted with a sulfur atom and the like. In the present invention,
In order to have a sufficient crosslinked structure and obtain an excellent cured product,
Of the thiirane compounds, compounds having two or more thiylanyl groups in the molecule are preferably used. The thiirane compounds can be used alone or as a mixture of two or more, and the amount of the thiirane compound used is polycarbodiimide and / or
Alternatively, the amount is usually 5 to 1,000 parts by weight, preferably 10 to 500 parts by weight, per 100 parts by weight of the modified polycarbodiimide. In this case, if the amount of the thiirane compound is less than 5 parts by weight, the curing speed of the composition tends to decrease, and if it exceeds 1,000 parts by weight, the heat resistance of the cured product tends to decrease.

Thermosetting Resin Composition The thermosetting resin of the present invention contains the above-mentioned polycarbodiimide and / or modified polycarbodiimide and the above-mentioned thiirane compound as essential components. Can be blended. Such additives include, for example, antioxidants, heat stabilizers, antistatic agents,
Examples thereof include a flame retardant, a colorant, a lubricant, an anti-fogging agent, an adhesion improving agent, and a fungicide. Furthermore, fillers such as clay, zeolite, talc, mica, silica, graphite, alumina, calcium carbonate, wollastonite, kaolin; glass, carbon, alumina, potassium titanate, aluminum borate, silicon carbide, silicon nitride, silicon nitride, Fibers such as aromatic polyamide, polyamideimide, polyimide, wholly aromatic polyester, ultrahigh molecular weight polyethylene, high-strength polyacrylonitrile, and high-strength polyvinyl alcohol, or reinforcing agents such as whiskers can also be blended. Further, the reinforcing agent may be used in the form of a woven fabric, a non-woven fabric or the like and impregnated with the thermosetting resin composition of the present invention. The thermosetting resin composition of the present invention itself has excellent curing properties, but if desired, a carbodiimide group in a polycarbodiimide and / or a modified carbodiimide, a reactive functional group in a modified carbodiimide, or A curing catalyst, a curing accelerator, a curing aid, and the like having reactivity with one or more thiiranyl groups in the thiirane compound may be blended.

The thermosetting resin composition of the present invention can be prepared by a method of mixing a polycarbodiimide and / or a modified carbodiimide with a thiirane compound together with various additives optionally used in a suitable solvent, and a method of solid-state polymerization. A polycarbodiimide and / or a modified carbodiimide and a thiirane compound can be prepared by, for example, a method of kneading without any solvent while heating, if necessary, together with various additives that may be used. The solvent used in preparing the composition is not particularly limited as long as it is inert to polycarbodiimide, modified polycarbodiimide, and thiirane compound and can dissolve them.

Properties and Applications of the Thermosetting Resin Composition The thermosetting resin composition of the present invention not only has excellent curing properties, solubility in various solvents and storage stability as a solution, but also has a curable property. The product is excellent in heat resistance, transparency, electrical insulation, mechanical properties, etc., and has low water absorption, excellent moisture resistance, excellent heat and moisture resistance, and excellent adhesion to various substrates. Therefore, the thermosetting resin composition of the present invention can be used particularly suitably as a protective film or an electric insulating film of various electronic circuit components, semiconductor devices, electric devices, and the like, and is required to have heat resistance. It is also useful as an adhesive or paint. Further, the thermosetting resin composition of the present invention is applied to an appropriate substrate which has been subjected to a mold release treatment in advance, and a thermosetting film is formed. A curable film can be obtained, and the thermosetting film is useful as a heat-resistant adhesive film for electric equipment and electronic parts. Alternatively, the thermosetting film that has been forcibly peeled off from the substrate is cured, or the thermosetting film is heated and cured on an appropriate substrate that has been subjected to a mold release treatment, and then the cured film is forcibly removed from the substrate. The cured film can be obtained by the specific peeling. Further, a prepreg obtained by impregnating a solution of the thermosetting resin composition of the present invention into a suitable cloth such as a glass cloth and then drying, or a prepreg obtained by impregnating a suitable cloth such as a glass cloth with the composition without solvent is used. Is useful as a laminated material such as a copper-clad laminate, and the thermosetting resin composition of the present invention is also useful as a thermosetting molding material in the form of powder, pellets, and the like.
The substrate used when forming a thermosetting film or a cured film from the thermosetting resin composition of the present invention is not particularly limited, for example, iron, nickel, stainless steel, titanium, aluminum, copper , Metals such as various alloys; silicon nitride, silicon carbide, sialon, aluminum nitride, boron nitride, boron carbide, zirconium oxide, titanium oxide, alumina, silica, and ceramics such as mixtures thereof; Si, Ge, Semiconductors such as SiC, SiGe, and GaAs; ceramic materials such as glass and ceramics; and heat-resistant resins such as aromatic polyamide, polyamideimide, polyimide, and wholly aromatic polyester. The substrate may be subjected to a release treatment in advance, if desired, and a chemical treatment with a silane coupling agent, a titanium coupling agent, or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or the like. Appropriate pretreatment such as vacuum deposition can also be performed. When applying the thermosetting resin composition of the present invention to the substrate, the composition is prepared as a solution as necessary, and then spin-coated, roll-coated, cast-coated, dip-coated An appropriate coating means such as a spray coating method or the like can be employed. Further, the coating thickness can be appropriately adjusted by selecting a coating means and adjusting the solid content concentration and viscosity of the composition solution. The thickness of the thermosetting film or the cured film formed from the thermosetting resin composition of the present invention can be appropriately selected, but is usually 0.1 to 1
It is preferably from 000 μm, preferably from 1 to 1,000 μm. Further, the thermosetting resin composition of the present invention may be a mixture obtained without solvent, or a mixture obtained by separating and collecting from a solvent, by a known molding method such as an injection molding method, a transfer molding method, an extrusion molding method, and a compression molding method. Molded by the method, it can be used as various industrial products and industrial parts.

[0021]

Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention is not limited to these embodiments at all unless it exceeds the gist. Parts in Examples and Comparative Examples are based on weight. Synthesis Example 1 <Synthesis of polycarbodiimide> diphenylmethane-4,
50 g of 4 'diisocyanate (MDI) and 2.6 g of phenyl isocyanate were reacted in 200 g of toluene in the presence of 0.044 g of 1-phenyl-3-methyl-2-phospholene-1-oxide at 110 ° C. under reflux for 5 hours to obtain a polystyrene. A solution of carbodiimide was obtained. Then, the solution was cooled to room temperature to precipitate polycarbodiimide, and then separated and collected by filtration to obtain a polycarbodiimide (P-MDI) powder having Mn of 9,800. <Synthesis of Modified Polycarbodiimide> After dissolving 30 g of the polycarbodiimide powder in 120 g of toluene under heating, 2.8 g of trimellitic anhydride dissolved in 12 g of acetone as a reactive compound was heated at a reaction system temperature of 8 g.
The solution was kept at 0 ° C. and added dropwise over 30 minutes. Thereafter, the reaction was further carried out for 30 minutes, and the reaction product was cooled to room temperature to precipitate a reaction product, which was separated and collected by filtration to obtain a powder of a modified polycarbodiimide having Mn of 4,500. When this modified polycarbodiimide was analyzed by infrared spectroscopy, it was found that absorption (wave number 2,150) specific to the carbodiimide unit was observed.
~ 2,100 cm ^-1 ) and absorption specific to carboxylic anhydride groups (wave number 1,850 to 1,780 cm ^-1 ). This modified polycarbodiimide was converted to P-MDI /
TMA.

Synthesis Example 2 <Synthesis of polycarbodiimide> 50 g of tolylene diisocyanate (TDI) and 3.8 g of phenyl isocyanate were mixed with 200 g of cyclohexanone in 1-phenyl-3.
-Methyl-2-phospholene-1-oxide 0.031 g
At 80 ° C. for 4 hours in the presence of
A solution of polycarbodiimide (P-TDI) was obtained. <Synthesis of Modified Polycarbodiimide> 5.5 g of trimellitic anhydride was added as a reactive compound to the polycarbodiimide solution and reacted at 20 ° C. for 3 hours to obtain a solution of a modified polycarbodiimide having Mn of 4,300. I got When this modified polycarbodiimide was analyzed by infrared spectroscopy, it was found that the absorption specific to the carbodiimide unit (wave number 2,150 to 2,100 cm ^-1 ) and the absorption specific to the carboxylic anhydride group (wave number 1,850 to 1,1). 780 cm ^-1 ). This modified polycarbodiimide is referred to as P-TDI / TMA.

Synthesis Example 3 <Synthesis of Thiirane Compound> In a flask having a capacity of 1 liter, 100 g (1.029 mol) of potassium thiocyanate was dissolved in 400 ml of methanol and kept at 40 ° C. Glycidyl ester type epoxy resin (trade name: Epicoat 191P, manufactured by Yuka Shell Epoxy)
A solution in which 100 g (0.588 mol as an epoxy group) was dissolved in 400 ml of methanol was added dropwise over 30 minutes, and then a solution in which 20 g of potassium thiocyanate was dissolved in 100 ml of methanol was added to continue the reaction. At this time, the reaction solution was emulsified about two and a half hours after the start of the reaction, and after three hours, a precipitate (gel) was confirmed. Therefore, the reaction was stopped. Next, the reaction solution was poured into 500 ml of water, and the organic layer was extracted with 600 ml of methylene chloride, followed by filtration and drying over magnesium sulfate. After that, methylene chloride was removed,
98 g of a thiirane compound were obtained. This thiirane compound is
TR-1.

Synthesis Example 4 <Synthesis of Thiirane Compound> In a flask having a capacity of 1 liter, 49 g (0.5 mol) of sulfuric acid was added to 500 ml of distilled water, kept at 50 ° C., and 79 g of thiourea was added thereto.
(1 mol) was dissolved. Next, 154 g (0.8 mol as an epoxy group) of a glycidyl ether type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co.) was added over 1 hour, and the reaction was continued at 50 ° C. for 5 hours. During the reaction, the generated thyuronium salt precipitated as a white solid. Then, the precipitate was filtered, and water 1
Wash with liters to remove excess acid. Next, after drying the thyuronium salt with ventilation, sodium carbonate 10
6 g (1 mol) was added to a solution prepared by dissolving in 750 ml of water, reacted at 60 ° C. for 6 hours, and the precipitated white solid was collected by filtration. The white solid was washed with methanol and dried to obtain 155 g of a thiirane compound. This thiirane compound is designated as TR-2.

[0025]

【Example】

Examples 1 to 6 and Comparative Examples 1 to 5 Using the carbodiimide compound or modified carbodiimide compound synthesized according to Synthesis Examples 1 and 2 and the thiirane compound or epoxy compound synthesized according to Synthesis Examples 3 to 4, the compounding ratio shown in Table 1 To prepare a thermosetting resin composition. For each of the obtained thermosetting resin compositions, the curing time when cured at the curing temperature shown in Table 1 and the glass transition temperature (Tg) of the cured product were measured by the following methods. Tables 1 and 2 show the measurement results. As a result, the composition comprising the polycarbodiimide or the modified polycarbodiimide and the thiirane compound has an extremely high curing rate as compared with the composition comprising the polycarbodiimide or the modified polycarbodiimide and the epoxy compound, and has the same glass transition temperature. It became clear to have. <Measurement of curing time> About 10 uncured thermosetting resin compositions
mg was sealed in a solid pan for differential scanning calorimetry (DSC) and charged into a TA Instruments differential scanning calorimeter DSC910 set to a constant temperature at a predetermined curing temperature, and the heat generated by the curing reaction was detected. The time at which the reaction was stopped was taken as the end point of the reaction, and the time until the end point of the reaction was measured. <Measurement of glass transition point> A solution obtained by dissolving an uncured thermosetting resin composition in cyclohexanone at a concentration of about 20% by weight is cast on a polyester film, and is heated on a hot plate at 120 ° C for about 20 minutes. After drying, it was cured in an oven at a predetermined curing temperature to obtain a cured film having a thickness of about 100 microns. From this cured film, 2
A rectangular test piece (mm × 15 mm) was cut out, and the coefficient of thermal expansion was measured in a tensile mode using a thermomechanical analyzer TMA / SS150 manufactured by Seiko Denshi Co., Ltd. at a temperature rising rate of 10 ° C./min. Was taken as the glass transition point.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

The thermosetting resin composition of the present invention has excellent curing properties and an equivalent glass transition temperature as compared with a composition comprising a polycarbodiimide or a modified polycarbodiimide and an epoxy compound. In addition, it has excellent solubility and storage stability in various solvents, and retains the original transparency, electrical insulation, moisture resistance, moisture and heat resistance, adhesiveness, mechanical properties, etc. of polycarbodiimide, electronic circuit components, It can be used very suitably in a wide range of fields including semiconductor devices.

Claims (1)

[Claims] (A) having a repeating unit represented by the following general formula (1): -N = C = NR ^1- (1) (wherein, R ¹ represents a divalent organic group) A thermosetting resin composition comprising a polymer and (B) a thiirane compound.