JP2019073658A - Method for producing thermosetting resin cured product - Google Patents

Abstract

To provide a resin cured product excellent in both toughness and bending strength.SOLUTION: A method for producing a thermosetting resin cured product using at least an allyl compound (A) having at least two or more allyl groups in one molecule, a maleimide compound (B) having at least two or more maleimide groups in one molecule and a thiol compound (C) having at least two or more thiol groups in one molecule, includes: a first step of mixing the thiol compound (C) and the maleimide compound (B) so that a maleimide group equivalent in the maleimide compound (B) to the thiol group equivalent of 1 in the thiol compound (C) is 1.15 to 6, reacting the compounds to synthesize oligomer; a second step of mixing a raw material containing the oligomer obtained in the first step and the allyl compound (A) to produce a composition; and a third step of heating the composition obtained in the second step at 150°C or higher for 5 hours or more to cure the composition.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a thermosetting resin cured product.

A thermosetting resin containing a bismaleimide group having an unsaturated bond and an imide bond is excellent in electric physical properties and thermal physical properties (also referred to as heat resistance), so various electronic / electrical component materials, structural materials, etc. As widely used in industry. However, although the resin cured product obtained by polymerizing the bismaleimide compound alone is considerably excellent in thermal properties, it is very brittle and inferior in mechanical properties.
A thermosetting resin composition (see Patent Document 1) obtained by reacting an aromatic bismaleimide compound and a diamine compound as a compound for improving the properties of a cured resin consisting only of such a bismaleimide compound (see Patent Document 1), and amino Suggested are thermosetting resin compositions consisting of terminal imide oligomers and bismaleimide compounds (see Patent Document 2) and thermosetting resin compositions consisting of bismaleimide compounds, allyl compounds and thiol compounds (see Patent Document 3) It is done.

Japanese Patent Publication No. 46-23250 Unexamined-Japanese-Patent No. 5-51455 gazette JP, 2016-74902, A

As mentioned above, although the resin composition which combined the bismaleimide compound and other compounds is proposed, the hardened material obtained from the resin composition of patent documents 1 has insufficient toughness. Although the cured products obtained from the resin compositions of Patent Documents 2 and 3 have a certain effect on toughness improvement, they are not sufficient in terms of bending strength.
As described above, all of the cured products obtained from the resin composition containing the conventional bismaleimide compound are not sufficient in terms of the characteristics, and have had a problem in terms of coexistence of toughness and bending strength.

An object of this invention is to provide the resin cured material excellent in both toughness and bending strength in view of the said present condition.

The inventor of the present invention has conducted intensive studies on resin cured products excellent in both toughness and flexural strength, and has at least two or more allyl compounds having at least two or more allyl groups in one molecule, and at least two or more in one molecule. The present inventors focused on a resin cured product using as a raw material a maleimide compound (B) having a maleimide group and a thiol compound (C) having at least two or more thiol groups in one molecule. Then, after the thiol compound (C) and the maleimide compound (B) are mixed in a predetermined ratio and then reacted to synthesize an oligomer, the obtained oligomer and the raw material containing the allyl compound (A) are mixed and obtained. It is found that when the cured mixture is cured under predetermined conditions to produce a cured resin product, the resulting cured resin product becomes excellent in both toughness and flexural strength, and it is possible to solve the above problems clearly. And completed the present invention.

That is, according to the present invention, an allyl compound (A) having at least two or more allyl groups in one molecule, a maleimide compound (B) having at least two or more maleimide groups in one molecule, and at least A method for producing a cured thermosetting resin using at least a thiol compound (C) having two or more thiol groups, wherein the production method is based on 1 thiol group equivalent in the thiol compound (C). A first step of synthesizing an oligomer by mixing a thiol compound (C) and a maleimide compound (B) such that the maleimide group equivalent in the maleimide compound (B) is 1.15-6, The composition obtained in the second step of mixing the oligomer obtained in the first step and the raw material containing the allyl compound (A) into a composition, and the composition obtained in the second step are heated at 150 ° C. or more for 5 hours or more A process for producing a thermosetting resin cured product and a third step of curing by heating.

The maleimide compound (B) preferably has an N-phenylmaleimide structure represented by the following formula (1), and the molecular weight of the compound is preferably less than 1,000.

［式（１）中、Ｒ^１、Ｒ^２は、それぞれ独立しており、水素原子又は１価の炭化水素基である。Ｘは末端にマレイミド基を含む有機基であり、炭化水素基、芳香環を含んでいてもよい。Ｘを構成する芳香環の数は複数であっても良く、複数の芳香環同士はエーテル基、エステル基、アミド基、カルボニル基、アザメチレン基又はアルキレン基を介して結合していてもよく、直接結合していてもよい。］

[In Formula (1), R ¹ and R ² are each independently, and are a hydrogen atom or a monovalent hydrocarbon group. X is an organic group containing a maleimide group at the end, and may contain a hydrocarbon group or an aromatic ring. The number of aromatic rings constituting X may be plural, and the plurality of aromatic rings may be bonded via an ether group, an ester group, an amide group, a carbonyl group, an azamethylene group or an alkylene group, directly It may be combined. ]

The cured product is preferably a cured product for a fiber-reinforced composite material.

The method for producing a thermosetting resin cured product of the present invention is a production method that has the above-mentioned configuration and can produce a cured product of a thermosetting resin excellent in both toughness and flexural strength. The cured product of the thermosetting resin produced by the production method of the present invention is excellent in toughness and flexural strength, and thus it is possible to make a fiber reinforced composite material etc. by making it a prepreg in which the composition before curing is impregnated with reinforcing fibers. It can be used suitably.

Hereinafter, although an example of the present invention is explained concretely, the present invention is not limited only to the following descriptions, and can be suitably changed and applied in the range which does not change the gist of the present invention.

1. Method for Producing Thermosetting Resin Cured Product The method for producing a thermosetting resin cured product of the present invention comprises an allyl compound (A) having at least two or more allyl groups in one molecule, and at least two in one molecule. At least using the maleimide compound (B) having a maleimide group and the thiol compound (C) having at least two or more thiol groups in one molecule, and including the first step to the third step described above Do.
Although it is not clear why the cured product obtained by producing the cured thermosetting resin product by the production method including such steps becomes excellent in both toughness and flexural strength, it is not clear that the allyl compound (A) and maleimide are It is inferred that the difference in reactivity between the reaction with the compound (B) and the reaction with the thiol compound (C) and the maleimide compound (B) influences.
Below, each process which the manufacturing method of the thermosetting resin hardened | cured material of this invention contains is demonstrated first, Then, the material used for the manufacturing method of the thermosetting resin hardened | cured material of this invention is demonstrated.

<First step>
In the first step of the method for producing a thermosetting resin cured product of the present invention, the ratio of the maleimide group equivalent in the maleimide compound (B) is 1.15 to 6 with respect to 1 of the thiol group equivalent in the thiol compound (C) In this step, the thiol compound (C) and the maleimide compound (B) are mixed and reacted to synthesize an oligomer.
Thus, in the first step, an oligomer is prepared using these at a ratio such that the maleimide group equivalent in the maleimide compound (B) is larger than the thiol group equivalent in the thiol compound (C) and within a predetermined range. Synthesize. The effect is exhibited if the ratio of the maleimide group equivalent in the maleimide compound (B) to the thiol group equivalent 1 in the thiol compound (C) is 1.15-6. When the maleimide group equivalent is more than 6, although a slight effect on improvement of bending strength and toughness can be observed, it is practically insufficient. On the other hand, when the maleimide group equivalent is less than 1.15, the molecular weight of the resulting oligomer becomes too large, and the compatibility in the resin decreases, so that the effect of improving the bending strength can not be obtained.

The above-mentioned oligomer is a polymer having a weight average molecular weight of 600 to 200,000.
The weight average molecular weight of the oligomer can be measured by the method described in the examples.

The method of mixing the thiol compound (C) and the maleimide compound (B) in the first step is not particularly limited, and a tumbler, a Henschel mixer, a Banbury mixer, a roll, a brabender, a single screw extruder, a twin screw extruder, a kneader And the like, and a reaction vessel that can be heated and equipped with a mixer and a stirring device can be used.

It is preferable that the reaction temperature at the time of making a thiol compound (C) and a maleimide compound (B) react in a 1st process is 40-120 degreeC. By reacting at such a temperature, the thiol compound (C) and the maleimide compound (B) can be sufficiently reacted. The reaction temperature is more preferably 60 to 100 ° C.

In the first step, the time for which the thiol compound (C) and the maleimide compound (B) are reacted is preferably 30 minutes to 6 hours. By reacting at such a reaction time, the thiol compound (C) and the maleimide compound (B) can be sufficiently reacted. The reaction time is more preferably 1 to 5 hours, still more preferably 2 to 4 hours.

The reaction in the first step may be carried out in a solvent, as necessary, or may be carried out using a catalyst.

The solvent is not particularly limited as long as it has high solubility in the maleimide compound (B), and examples thereof include dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, cyclohexanone, chloroform, dichloromethane, etc. More than species can be used.

Examples of the catalyst include amine compounds such as benzyldimethylamine and triethylamine, imidazole compounds such as 2-ethyl-4-methylimidazole, 2-methylimidazole and 2,4-dimethylimidazole, dicumyl peroxide, α, α'-bis Organic peroxides such as (t-butylperoxy) diisopropylbenzene, azo such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethyl-4-methoxy) valeronitrile A compound etc. are mentioned and 1 type (s) or 2 or more types of these can be used.

It is preferable that the compounding ratio of the said catalyst is 0.1-5 mass% with respect to 100 mass% of thiol compounds (C) used at a 1st process. More preferably, it is 0.1 to 3% by mass.

In the first step, the allyl compound (A) may be contained in the mixture of the thiol compound (C) and the maleimide compound (B), but it is preferable that the content of the allyl compound (A) is small, the thiol compound It is preferable that content of an allyl compound (A) is 1 weight part or less with respect to a total of 100 weight parts of (C) and a maleimide compound (B). The amount is more preferably 0.5 parts by weight or less, still more preferably 0.1 parts by weight or less, and most preferably 0.01 parts by weight or less, which is an area substantially not included.

Second step
The second step in the method for producing a thermosetting resin cured product of the present invention is a step of mixing the oligomer obtained in the first step and the raw material containing the allyl compound (A) to form a composition. Thus, the thiol compound (C) and the maleimide compound (B) are reacted in advance to produce an oligomer, and then the allyl compound (A) is mixed to form a composition, which is one of the features of the production method of the present invention. It is.

In the second step, only the oligomer obtained in the first step and the allyl compound (A) may be mixed, and even if the oligomer obtained in the first step and components other than the allyl compound (A) are further mixed Good. As components other than the oligomer obtained in the first step and the allyl compound (A), for example, a maleimide compound (B) may be further mixed, and addition of a curing catalyst, a solvent, an inorganic filler, a flame retardant and other additives The agents may be mixed. The curing catalyst is different from the catalyst that may be used in the first step described above.

When the maleimide compound (B) is further mixed in the second step, the maleimide compound (B) used in the first step and the second step with respect to the thiol group equivalent 1 in the thiol compound (C) used in the first step Preferably, the difference is added so that the maleimide group equivalent in the total of 2 to 40. By using such a ratio, it is possible to obtain a cured product excellent in toughness and bending strength while maintaining the high heat resistance of the maleimide resin. More preferably, the difference is added to be 3 to 20, and still more preferably, the difference is added to be 4 to 15.

The ratio of the allyl compound (A) used in the second step is the allyl group in the allyl compound (A) relative to the maleimide group equivalent of 1 in the total of the maleimide compounds (B) used in the first step and the second step. It is preferable that it is a ratio used as an equivalent of 0.1-1. By using the allyl compound (A) in such a ratio, a cured product having a good balance of heat resistance and mechanical properties such as flexural strength and toughness can be obtained.
The ratio of the allyl compound (A) used in the second step is more preferably the allyl group in the allyl compound (A) relative to the maleimide group equivalent 1 of the maleimide compound (B) used in the first step and the second step. The equivalent weight is 0.15 to 0.7, and more preferably, a ratio of 0.2 to 0.5 equivalent of the allyl group in the allyl compound (A).

The preferred composition of the composition obtained in the second step is the allyl group of the allyl compound (A) used in the first step and the second step to prepare the composition, the maleimide group of the maleimide compound (B), And the ratio of the number of thiol groups of the thiol compound (C), based on the thiol group of the thiol compound (C), allyl group of the allyl compound (A) / maleimide group of the maleimide compound (B) / The thiol group of the thiol compound (C) is preferably (0.23 / 1.15 / 1) to (10/10/1). More preferably, they are (0.23 / 1.15 / 1) to (3/6/1).

As a curing catalyst, 2-ethyl-4-methylimidazole which is an imidazole compound, 2-methylimidazole, 2,4-dimethylimidazole or the like, dicumyl peroxide which is an organic peroxide, α, α'-bis (t -Butylperoxy) diisopropylbenzene and the like, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethyl-4-methoxy) valeronitrile etc. 1 type or 2 types or more of can be used.

The compounding ratio of the curing catalyst is 0.1 to 10% by weight based on 100% by weight in total of the allyl compound (A), the maleimide compound (B) and the thiol compound (C) contained in the composition obtained in the second step. Is preferred. More preferably, it is 0.1 to 5% by weight, still more preferably 0.1 to 3% by weight.

The solvent is not particularly limited, but, for example, one or more kinds of dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, methyl ethyl ketone, toluene and the like can be used.

As the inorganic filler, natural silica, calcined silica, synthetic silica, amorphous silica, white carbon, alumina, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, zinc borate, zinc stannate, titanium oxide, zinc oxide , Magnesium oxide, boron nitride, aluminum nitride, silicon carbide, barium titanate, strontium titanate, copper, silver, gold, molybdenum, zinc molybdate, natural mica, synthetic mica, aerosil, kaolin, clay, talc, calcined kaolin And calcined clay, calcined talc, wollastonite, short glass fibers, fine glass powder, hollow glass and potassium titanate fibers.

Although the compounding quantity of an inorganic filler is not specifically limited, It is preferable that it is 200 weight part or less with respect to 100 weight part of solid content weight of the whole thermosetting resin composition.

Flame retardants include chlorinated paraffins, phosphoric esters, condensed phosphoric esters, phosphoric acid amides, phosphoric acid amide esters, phosphinates, phosphinate salts, phosphorus-based flame retardants such as ammonium phosphate and red phosphorus, melamine, melamine cyanurate And nitrogen-based flame retardants such as melam, melem, melon and succinoguanamine, flame retardants such as silicone flame retardants, brominated flame retardants, and flame retardant aids such as antimony trioxide, etc. The compounding amount is not particularly limited as long as it does not interfere with the properties of the base resin composition.

Other additives include, for example, UV absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, gloss Agents, polymerization inhibitors, antistatic agents, conductive agents, etc. may be mentioned, and two or more may be mixed.

In the second step, the method for mixing the oligomer obtained in the first step and the raw material containing the allyl compound (A) is not particularly limited, and a tumbler, Henschel mixer, Banbury mixer, roll, brabender, single screw extruder, A twin-screw extruder, a kneader or the like can be used.

<Third step>
The third step in the method for producing a thermosetting resin cured product of the present invention is a step of curing the composition obtained in the second step by heating the composition at 150 ° C. or more for 5 hours or more.
By heating and curing the composition obtained in the second step at such temperature and time, the resulting cured product becomes excellent in both toughness and flexural strength.

Although the molding method of the cured product is not particularly limited, after passing through a process of pressurizing the molten resin composition with heat and injecting and impregnating into the mold, or injecting and impregnating by reducing the pressure in the mold, 5 hours or more at 150 ° C. or more A desired molded product can be obtained by heating.

Although the heating temperature in the third step may be 150 ° C. or higher, it is preferably 160 ° C. or higher in order to obtain a cured product excellent in toughness and flexural strength. The temperature is more preferably 200 ° C. or more, and still more preferably 220 ° C. or more. The upper limit of the heating temperature is not particularly limited, but is preferably 250 ° C. or less in consideration of production cost, efficiency, and the like.

The heating time in the third step may be 5 hours or more, but is preferably 10 hours or more in order to obtain a cured product excellent in toughness and bending strength. More preferably, it is 20 hours or more, and most preferably 30 hours or more. The upper limit of the heating time is not particularly limited, but is preferably 48 hours or less in consideration of production cost, efficiency, and the like.

The third step may be performed at a constant temperature, or may be performed stepwise while changing the temperature. Moreover, the number of times of changing the temperature may be one, or may be two or more.
For example, the third step can be carried out while raising the temperature stepwisely for every fixed time, which is one of the preferred embodiments of the third step in the present invention.
When raising temperature at a fixed rate, it is preferable that the range of the temperature to raise is 10-40 degreeC. More preferably, it is 20-30 degreeC.
The temperature rising rate is preferably 0.1 ° C./min to 100 ° C./min, more preferably 1 ° C./min to 40 ° C./min.
The holding time at each temperature is preferably 0.5 to 5 hours. More preferably, it is 2 to 4 hours.
Moreover, as for the frequency | count of raising temperature, it is more preferable that it is 1-10 times. More preferably, it is 2 to 6 times.

<Other process>
The method for producing a cured thermosetting resin of the present invention may include other steps other than the first step to the third step described above.
Other steps include a step of melting the composition obtained in the second step before the third step, a degassing step performed after the melting step, a step of substituting with an inert gas, and the like.

When the step of melting the composition obtained in the second step is performed, the bubbles contained in the composition can be easily removed in the defoaming step.
The temperature for melting the composition is preferably a temperature at which each component contained in the composition is melted, and is preferably 140 to 180 ° C. More preferably, it is 150-160 ° C.
In the process of melting the composition, the heating time is not particularly limited, and it is preferable to carry out until the components contained in the composition are completely melted.

After carrying out the step of melting the composition obtained in the second step, it is preferable to carry out a degassing step for removing air contained in the melt. By removing air from the melt, it is possible to suppress the inclusion of air bubbles in the cured product obtained by curing the melt.
The method for removing air from the melt is not particularly limited as long as air is removed, but it is preferable to decompress the melt.
In the process of depressurizing the melt, the time for depressurizing is not particularly limited, but it is preferable to carry out until no bubbles are released from the melt.

After the composition obtained in the second step is melted and defoamed, it is preferable that the composition be cured through a step of substituting with an inert gas. By substituting the inert gas, it is possible to suppress the deterioration of the surface of the cured product.
The inert gas is not particularly limited as long as it is a gas which does not react with each component of the resin composition, but nitrogen, argon or the like is preferable.

2. Raw Material Compounds In the following, compounds used as raw materials in the method for producing a cured thermosetting resin of the present invention will be described.
<Allyl compound (A)>
The allyl compound (A) having at least two or more allyl groups in one molecule is not particularly limited as long as it has at least two or more allyl groups in one molecule, but at least two in one molecule. It is preferable that it is a compound which has the above allyl group and one or more aromatic rings. More preferably, they are compounds having at least two or more allyl groups and one or more benzene rings in one molecule.
Examples of compounds having at least two or more allyl groups and one or more benzene rings in one molecule include diallylated bisphenol A, diallyated bisphenol AP, diallyated bisphenol AF, diallyated bisphenol B, diallyated bisphenol BP Diallylated bisphenol compounds such as diallylated bisphenol C, diallylated bisphenol E and diallylated bisphenol F, benzene poly (2-6) carboxylic acid poly (2-6) allyl ester and allylated novolac are preferably used.
In addition, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TM, diallylated bisphenol obtained by diallylizing bisphenol Z, and the like can be mentioned.
As the allyl compound (A), one type of compound may be used, or two or more types of compounds may be used.

As diallylated bisphenol A, 2,2-bis [2- (2-propenyl) -4-hydroxyphenyl] propane represented by the following formula (2), 2,2-bis [3- (2-propenyl)- 4-hydroxyphenyl] propane and 2- [2- (2-propenyl) -4-hydroxyphenyl] -2- [3- (2-propenyl) -4-hydroxyphenyl] propane, and in the following formula (3): The 2,2-bis [4- (2-propenyloxy) phenyl] propane etc. which are shown are mentioned.

As diallylated bisphenol AP, 1,1-bis [2- (2-propenyl) -4-hydroxyphenyl] -1-phenylethane, 1,1-bis [3- (2-propenyl) -4-hydroxyphenyl ] 1-phenylethane, 1- [2- (2-propenyl) -4-hydroxyphenyl] -1- [3- (2-propenyl) -4-hydroxyphenyl] propane and 1,1-bis [4-] (2-propenyloxy) phenyl] -1-phenylethane and the like can be mentioned.

As diallylated bisphenol AF, 2,2-bis [2- (2-propenyl) -4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3- (2-propenyl) -4-hydroxyphenyl] hexa Fluoropropane, 2- [2- (2-propenyl) -4-hydroxyphenyl] -2- [3- (2-propenyl) -4-hydroxyphenyl] hexafluoropropane and 2,2-bis [4- (2) And -propenyloxy) phenyl] hexafluoropropane and the like.

As diallylated bisphenol B, 2,2-bis [2- (2-propenyl) -4-hydroxyphenyl] butane, 2,2-bis [3- (2-propenyl) -4-hydroxyphenyl] butane, 2 -[2- (2-propenyl) -4-hydroxyphenyl] -2- [3- (2-propenyl) -4-hydroxyphenyl] butane and 2,2-bis [4- (2-propenyloxy) phenyl] Butane etc. are mentioned.

As diallylated bisphenol BP, bis [2- (2-propenyl) -4-hydroxyphenyl] diphenylmethane, bis [3- (2-propenyl) -4-hydroxyphenyl] diphenylmethane, [2- (2-propenyl)- 4-hydroxyphenyl] [3- (2-propenyl) -4-hydroxyphenyl] diphenylmethane and bis [4- (2-propenyloxy) phenyl] diphenylmethane and the like can be mentioned.

As diallylated bisphenol C, 2,2-bis [2- (2-propenyl) -3-methyl-4-hydroxyphenyl] propane, 2,2-bis [2- (2-propenyl) -4-hydroxy- 5-Methylphenyl] propane, 2,2-bis [3- (2-propenyl) -4-hydroxy-5-methylphenyl] propane, 2- [2- (2-propenyl) -3-methyl-4-hydroxyl Phenyl] -2- [2- (2-propenyl) -4-hydroxy-5-methylphenyl] propane, 2- [2- (2-propenyl) -3-methyl-4-hydroxyphenyl] -2- [3 -(2-propenyl) -4-hydroxy-5-methylphenyl] propane and 2- [2- (2-propenyl) -4-hydroxy-5-methylphenyl] -2- [3- (2-pro Yl) -4-hydroxy-5-methylphenyl] propane.

As diallylated bisphenol E, 1,1-bis [2- (2-propenyl) -4-hydroxyphenyl] ethane, 1,1-bis [3- (2-propenyl) -4-hydroxyphenyl] ethane, 1 -[2- (2-propenyl) -4-hydroxyphenyl] -1- [3- (2-propenyl) -4-hydroxyphenyl] ethane and 1,1-bis [4- (2-propenyloxy) phenyl] Ethane etc. are mentioned.

As diallylated bisphenol F, bis [2- (2-propenyl) -4-hydroxyphenyl] methane, bis [3- (2-propenyl) -4-hydroxyphenyl] methane, [2- (2-propenyl)- 4-hydroxyphenyl] [3- (2-propenyl) -4-hydroxyphenyl] methane and bis [4- (2-propenyloxy) phenyl] methane and the like can be mentioned.

The number of carboxylic acid groups in the benzene poly (2-6) carboxylic acid poly (2-6) allyl ester is 2-6, and the number of allyl groups bonded to the carboxylic acid group is 2-6, The number of allyl groups is less than or equal to the number of carboxylic acid groups.
Examples of the benzene poly (6) carboxylic acid poly (6) allyl ester include mellitic acid hexaallyl ester and the like, and as the benzene poly (5) carboxylic acid poly (5) allyl ester, benzene pentacarboxylic acid pentaallyl ester and the like And poly (4) carboxylic acid poly (4) allyl esters such as pyromellitic acid tetraallyl ester etc. and benzene poly (3) carboxylic acid poly (3) allyl ester such as trimellitic acid Examples thereof include triallyl ester and trimesic acid triallyl ester, and examples of benzene poly (2) carboxylic acid poly (2) allyl ester include diallyl orthoflate (a structure represented by the following formula (4)), diallyl isophthalate (the following formula (5)), diallyl terephthalate (bottom Formula structure shown in (6)) and the like.
Among these, benzene poly (2) carboxylic acid poly (2) allyl ester [also referred to as diallyl phthalate] such as diallyl orthoflate, diallyl isophthalate, diallyl terephthalate is preferable.

The allylated novolak has a structure represented by the following formula (7).

The value of q in the said Formula (7) is an integer of 1-1000.

Among these, 2,2-bis [2- (2-propenyl) -4-hydroxyphenyl] propane, 2,2-bis [3- (2-propenyl) -4-hydroxyphenyl] propane, 2- [2 2- (2-propenyl) -4-hydroxyphenyl] -2- [3- (2-propenyl) -4-hydroxyphenyl] propane and 2,2-bis [4- (2-propenyloxy) phenyl] propane and the like Diallylized bisphenol A of the following: diallyl orthoflate, diallyl terephthalate, diallyl phthalate such as diallyl isophthalate; allylated novolac; and the like are preferable.

<Maleimide compound (B)>
The maleimide compound (B) in the present invention may be one having at least two or more maleimide groups in one molecule, and has an N-phenylmaleimide structure represented by the following formula (1) and It is preferred that the molecular weight of the compound is less than 1,000.

In formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group. X is an organic group containing a maleimide group at the end, and may contain a hydrocarbon group or an aromatic ring. The number of aromatic rings constituting X may be plural, and the plurality of aromatic rings may be bonded via an ether group, an ester group, an amide group, a carbonyl group, an azamethylene group or an alkylene group, directly It may be combined.

The organic group containing a maleimide group at the end, which is represented by X in the above formula (1), may or may not have an aromatic ring in the structure.
When it has an aromatic ring, examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring and the like, and it may be a heteroaromatic ring containing atoms other than carbon (for example, nitrogen atom, sulfur atom).

上記式（８）〜（９）において、Ｒ^３、Ｒ^４はそれぞれ異なっていてもよく、水素原子、メチル基、エチル基、プロピル基、ブチル基、メトキシ基、エトキシ基、プロポキシ基及びブトキシ基からなる群から選択される１種である。 The structure of X is not particularly limited, but a structure in which an alkylene group (methylene group) is bonded to an N-phenylmaleimide group as shown in the following formula (8) or an N-phenylmaleimide group as shown in the following formula (9) And a structure in which a plurality of benzene rings are linked via an ether group and an alkylene group (dimethyl methylene group: -C (CH ₃ ) _2- ).

In the above formulas (8) to (9), R ³ and R ⁴ may be different from each other, and hydrogen atom, methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, propoxy group and butoxy group 1 type selected from the group consisting of

The maleimide compound having an N-phenylmaleimide structure represented by the above formula (1) preferably has a molecular weight of less than 1,000, more preferably 800 or less, still more preferably 600 or less .

Among these, 4,4'-diphenylmethane bismaleimide (molecular weight 358 calculated from the structural formula) is preferable from the viewpoint of improving the heat resistance of the resin after curing.

<Thiol compound (C)>
The thiol compound (C) which comprises the thermosetting resin composition of this invention has a 2 or more thiol group (it is also called a mercapto group) in 1 molecule.

The structure of the thiol compound (C) is not particularly limited as long as it has two or more thiol groups in one molecule, but it has a structure represented by the following formula (10) preferable.

Z ¹ represented by a circular broken line is an organic group having a cyclic structure and may be any of aromatic, heterocyclic or polycyclic. m is an integer of 2 to 10, and n ¹ is an integer of 0 to 8. m is preferably 2 to 5.
The m R ^{5 s} are each independently selected from an organic group selected from the group consisting of a chain aliphatic group, an aliphatic group containing a cyclic structure and an aromatic group, or a group selected from these groups It is an organic group consisting of a combination of a plurality of organic groups. R ⁵ may be one in which an organic group having a plurality of cyclic structures is bonded by a bond selected from the group consisting of an ester bond, an ether bond, an amide bond and a urethane bond. n ¹ R ⁶ is independently of one another, and is one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a fluoro group, a chloro group, a bromo group and an iodo group.

The thiol compound (C) represented by the above-mentioned formula (10) has an organic group Z ¹ having a cyclic structure, R ⁵ connecting the above organic group Z ¹ and a thiol group, and R linked to the above organic group Z ^{1 It} consists of ^six .

First, a description will be given organic group Z ¹ constituting thiol compound (C).

The organic group Z ¹ having a cyclic structure may be any of aromatic, heterocyclic or polycyclic.

When the organic group Z ¹ is an aromatic group, for example, from the structure represented by the following formula (11) to (14), the structure or the like has been removed any number of the hydrogen atom.

When the organic group Z ¹ is a heterocyclic, examples thereof include those represented by the following formulas (15) to (16).

When the organic group Z ¹ has a structure represented by the above formulas (15) to (16), it is preferable that (-R ⁵ -SH) be bonded to all the nitrogen atoms constituting the ring.

When the organic group Z ¹ is polycyclic, in addition to the structures described above, for example, structures described in the following formulas (17) to (20) can be mentioned. As the Z ^1, also include those removed from spiro compounds optionally 2 to 10 hydrogen atoms.

Subsequently, R ⁵ constituting the thiol compound (C) will be described.

The R ^5, an ester bond, an ether bond, it is preferred that the amide bond and a straight-chain alkylene group which may having 2 to 12 carbon atoms include a bond selected from the group consisting of urethane bond. Preferably, the ester bond, the ether bond, the amide bond and the urethane bond are not directly bonded to the nitrogen atom on the isocyanuric ring and the sulfur atom constituting the thiol group.
Examples of the linear alkylene group having 2 to 12 carbon atoms include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, nonylene group, decylene group, undecylene group, dodecylene group, etc. A propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group or an octylene group is more preferable, and an ethylene group, a propylene group, a butylene group, a pentylene group or a hexylene group is more preferable because of easy availability of raw materials for production.
In the case where an ester bond, an ether bond, the bond such as an amide bond and urethane bond contained in R ^5, carbon atoms to form an ester bond, amide bond and urethane bond can not included in the number of carbon atoms of straight-chain alkylene group. For example, when R ⁵ is a linear C 12 alkylene group containing one ester bond, the carbon number of R ⁵ is 13.

As a C2-C12 linear alkylene group containing an ester bond,
2-oxo-3-oxa-butylene group _{(-CH 2 -CO-O-CH} 2 -), 2- oxa-3-oxo-butylene group _{(-CH 2 -O-CO-CH} 2 -), 2- oxo - 3-oxapentylene group _{(-CH 2 -CO-O-C} 2 H 4 -), 3- oxo-4-oxa-pentylene group _{(-C 2 H 4 -CO-O} -CH 2 -), 2- oxa-3-oxo-pentylene group _{(-CH 2 -O-CO-C} 2 H 4 -), 3- oxa-4-oxo-pentylene group _{(-C 2 H 4 -O-CO} -CH 2 -),
2-oxo-3-oxa-hexylene group _{(-CH 2 -CO-O-n} -C 3 H 6 -), 2 3- oxo-4-oxa-hexylene group _{(-C H 4 -CO-O-} C ₂ H ₄ -), 4- oxo-5-oxa-hexylene group _{(-n-C 3 H 6 -CO} -O-CH 2 -), 2- oxa-3-oxo hexylene group _(-CH 2 -O _{-CO-n-C 3 H 6} -), 3- oxa-4-oxo-hexylene group _{(-C 2 H 4 -O-CO} -C 2 H 4 -), 4- oxa-5-oxo hexylene group _{(-n-C 3 H 6 -O} -CO-CH 2 -), 2- oxo-3- Okisahepuchiren group _{(-CH 2 -CO-O-n} -C 4 H 8 -), 3- oxo-4 Okisahepuchiren group _{(-C 2 H 4 -CO-O} -n-C 3 H 6 -), 4- oxo-5- Okisahepuchiren group (-n _{C 3 H 6 -CO-O-} C 2 H 4 -), 5- oxo-6- Okisahepuchiren group _{(--n C 4 H 8 -CO} -O-CH 2 -), 2- oxa-3 Okisohepuchiren group _{(-CH 2 -O-CO-n} -C 4 H 8 -), 3- oxa-4 Okisohepuchiren group _{(2 -C H 4 -O-CO} -n-C 3 H 6 -), 4- oxa - 5- Okisohepuchiren group _{(-n-C 3 H 6 -O} -CO-C 2 H 4 -), 5- oxa-6-Okisohepuchiren group _{(-n-C 4 H 8 -O} -CO-CH 2 -), 2-oxo-3- Okisaokuchiren group _{(-CH 2 -CO-O-n} -C 5 H 10 -), 3- oxo-4-Okisaokuchiren group _{(-C 2 H 4 -CO-O} -n-C 4 H ₈ -), 4-oxo-5- Okisaokuchiren group _{(--n C 3 H 6 -CO} -O-n C ₃ H ₆ -), 5- oxo-6- Okisaokuchiren group _{(-n-C 4 H 8 -CO} -O-C 2 H 4 -), 6- oxo-7 Okisaokuchiren group _(-n-C 5 H _{10 -CO-O-CH 2 -} ), 2- oxa-3 Okisookuchiren group _{(-CH 2 -O-CO-n} -C 5 H 10 -), 3- oxa-4 Okisookuchiren group _(-C 2 H _{4 -O-CO-n-C} 4 H 8 -), 4- oxa-5 Okisookuchiren group _{(-n-C 3 H 6 -O} -CO-n-C 3 H 6 -), 5- oxa -6 - Okisookuchiren group _{(-n-C 4 H 8 -O} -CO-C 2 H 4 -), 6- oxa-7- Okisookuchiren group _{(-n-C 5 H 10 -O} -CO-CH 2 -),
2-oxo-3- Okisanoniren group _{(-CH 2 -CO-O-n} -C 6 H 12 -), 3- oxo-4-Okisanoniren group _{(-C 2 H 4 -CO-O} -n-C 5 H ₁₀ -), 4-oxo-5- Okisanoniren group _{(-n-C 3 H 6 -CO} -O-n-C 4 H 8 -), 5- oxo-6- Okisanoniren group _(-n-C 4 _{H 8 -CO-O-n-C 3} H 6 -), 6- oxo-7 Okisanoniren group _{(--n C 5 H 10 -CO} -O-C 2 H 4 -), 7- oxo-8- Okisanoniren group _{(-n-C 6 H 12 -CO} -O-CH 2 -), 2- oxa-3 Okisononiren group _{(-CH 2 -O-CO-n} -C 6 H 12 -), 3- oxa-4 Okisononiren group _{(-C 2 H 4 -O-CO} -n-C 5 H 10 -), 4- oxa-5-oxo Nonylene _{(-n-C 3 H 6 -O} -CO-n-C 4 H 8 -), 5- oxa-6-Okisononiren group _{(-n-C 4 H 8 -O} -CO-n-C 3 H ₆ -), 6-oxa-7- Okisononiren group _{(-n-C 5 H 10 -O} -CO-C 2 H 4 -), 7- oxa-8-Okisononiren group _{(-n-C 6 H} 12 -O _-CO-CH 2 -),
2-oxo-3- Okisadeshiren group _{(-CH 2 -CO-O-n} -C 7 H 14 -), 3- oxo-4-Okisadeshiren group _{(-C 2 H 4 -CO-O} -n-C 6 H ₁₂ -), 4-oxo-5- Okisadeshiren group _{(-n-C 3 H 6 -CO} -O-n-C 5 H 10 -), 5- oxo-6- Okisadeshiren group _(-n-C 4 _{H 8 -CO-O-n-C 4} H 8 -), 6- oxo-7 Okisadeshiren group _{(-n-C 5 H 10 -CO} -O-n-C 3 H 6 -), 7- oxo-8- Okisadeshiren group _{(-n-C 6 H 12 -CO} -O-C 2 H 4 -), 8- oxo-9- Okisadeshiren group _{(-n-C 7 H 14 -CO} -O-CH 2 -), 2- oxa-3 Okisodeshiren group _{(-CH 2 -O-CO-n} -C 7 H 14 -), 3- oxa-4 Okisodeshiren group _{(-C 2 H 6 -O-CO} -n-C 6 H 10 -), 4- oxa-5 Okisodeshiren group _{(-n-C 3 H 6 -O} -CO-n-C 5 H 10 - ), 5-oxa-6-Okisodeshiren group _{(-n-C 4 H 8 -O} -CO-n-C 4 H 8 -), 6- oxa-7- Okisodeshiren group _{(-n-C 5 H} 10 -O _{-CO-n-C 3 H 6} -), 7- oxa-8-Okisodeshiren group _{(-n-C 6 H 12 -O} -CO-C 2 H 4 -), 8- oxa-9 Okisodeshiren group (- _{n-C 7 H 12 -O-} CO-CH 2 -), 2- oxo-3-oxa-undecylenic groups _{(-CH 2 -CO-O-n} -C 8 H 16 -), 3- oxo-4-oxa undecylenic groups _{(-C 2 H 4 -CO-O} -n-C 7 H 14 -), 4- oxo-5- Oki Undecylene _{(-n-C 3 H 6 -CO} -O-n-C 6 H 12 -), 5- oxo-6-oxa-undecylenic groups _{(--n C 4 H 8 -CO} -O-n-C 5 H ₁₀ -), 6- oxo-7-oxa-undecylenic groups _{(-n-C 5 H 10 -CO} -O-n-C 4 H 8 -), 7- oxo-8-oxa undecylenic groups (-n-C _{6 H 12 -CO-O-n} -C 3 H 6 -), 8- oxo-9-oxa-undecylenic groups _{(-n-C 7 H 14 -CO} -O-C 2 H 4 -), 9- oxo - 10-oxa-undecylenic groups _{(-n-C 8 H 16 -CO} -O-CH 2 -), 2- oxa-3-oxo-undecylenic groups _{(-CH 2 -O-CO-n} -C 8 H 16 -), 3-oxa-4-oxo-undecylenic group _{(-C 2 H 4 -O-CO} -n-C 7 H 14 -), 4-oxa-5-oxo-undecylenic groups _{(-n-C 3 H 6 -O} -CO-n-C 6 H12 -), 5- oxa-6-oxo-undecylenic groups _(--n C 4 _{H 8 -O-CO-n-C 5} H 10 -), 6- oxa-7-oxo-undecylenic groups _{(--n C 5 H 10 -O} -CO-n-C 4 H 8 -), 7- oxa -8 - oxo undecylenic groups _{(-n-C 6 H 12 -O} -CO-n-C 3 H 6 -), 8- oxa-9-oxo-undecylenic groups _{(-n-C 7 H 14 -O} -CO-C 2 H ₄ -), 9- oxa-10-oxo-undecylenic groups _{(-n-C 8 H 16 -O} -CO-CH 2 -), 2- oxo-3- Okisadodeshiren group _(-CH 2 -CO-O-n -C ₉ H ₁₈ -), 3- oxo-4-Okisadodeshiren group _{(-C 2} H 4 -CO _{-O-n-C 8 H 16} -), 4- oxo-5- Okisadodeshiren group _{(--n C 3 H 6 -CO} -O-n-C 7 H 14 -), 5- oxo-6- Okisadodeshiren group _{(-n-C 4 H 8 -CO} -O-n-C 6 H 12 -), 6- oxo-7 Okisadodeshiren group _{(-n-C 5 H 10 -CO} -O-n-C 5 H 10 - ), 7-oxo-8-Okisadodeshiren group _{(--n C 6 H 12 -CO} -O-n-C 4 H 8 -), 8- oxo-9- Okisadodeshiren group _{(-n-C 7} H 14 -CO _{-O-n-C 3 H 6} -), 9- oxo-10-Okisadodeshiren group _{(-n-C 8 H 16 -CO} -O-C 2 H 4 -), 10- oxo-11-Okisadodeshiren group (- _{n-C 9 H 18 -CO-} O-CH 2 -), 2- oxa-3 Okisododeshire Down group _{(-CH 2 -O-CO-n} -C 9 H 18 -), 3- oxa-4 Okisododeshiren group _{(-C 2 H 4 -O-CO} -n-C 8 H 16 -), 4- oxa-5 Okisododeshiren group _{(-n-C 3 H 6 -O} -CO-n-C 7 H 14 -), 5- oxa-6-Okisododeshiren group _{(--n C 4 H 8 -O} -CO-n -C ₆ H ₁₂ -), 6- oxa-7- Okisododeshiren group _{(-n-C 5 H 10 -O} -CO-n-C 5 H 10 -), 7- oxa-8-Okisododeshiren group (-n- _{C 6 H 12 -O-CO-} n-C 4 H 8 -), 8- oxa-9 Okisododeshiren group _{(-n-C 7 H 14 -O} -CO-n-C 3 H 6 -), 9- oxa-10-Okisododeshiren group _{(-n-C 8 H 16 -O} -CO-C 2 H 4 -) and 10 Kisa -11- Okisododeshiren group _{(-n-C 9 H 18 -O} -CO-CH 2 -) and the like.

As a C2-C12 linear alkylene group containing an ester bond, 2-oxa- 3-oxo pentylene group, 3-oxa- 4-oxo pentylene group, 2-oxa- 3-oxo hexylene group, 3-oxa-4-oxohexylene, 2-oxa-3-oxoheptylene, 3-oxa-4-oxoheptylene, 2-oxa-3-oxooctylene or 3-oxa-4-oxooctylene Preferably, a 3-oxa-4-oxohexylene group or a 3-oxa-4-oxoheptylene group is more preferable from the viewpoint of easy availability of production raw materials.

As a C2-C12 linear alkylene group containing an ether bond, it corresponds to what changed the carbonyl group in the C2-C12 linear alkylene group containing the said ester bond to the methylene group,
2-oxapropylene group, 2-oxabutylene group, 3-oxabutylene group, 2-oxapentylene group, 3-oxapentylene group, 4-oxapentylene group,
2-oxahexylene group, 3-oxahexylene group, 4-oxahexylene group, 5-oxahexylene group, 2-oxaheptylene group, 3-oxaheptylene group, 4-oxaheptylene group, 5-oxaheptylene group, 6- Oxaheptylene group, 2-oxaoctylene group, 3-oxaoctylene group, 4-oxaoctylene group, 5-oxaoctylene group, 6-oxaoctylene group, 7-oxaoctylene group, 2-oxanonylene group, 3-oxanonylene group, 4-oxanonylene group, 5- Oxanononylene group, 6-oxanonylene group, 7-oxanonylene group, 8-oxanonylene group, 2-oxadecylene group, 2-oxadecylene group, 3-oxadecylene group, 4-oxadecylene group, 5-oxadecylene group, 6-oxadecylene group, 7-oxadecylene group, 8- Oxadecylene group 9-oxadecylene group, 2-oxaundecylene group, 3-oxaundecylene group, 4-oxaundecylene group, 5-oxaundecylene group, 6-oxaundecylene group, 7-oxaundecylene group, 8-oxaundecylene group, 8-oxaundecylene group, 9-oxa Undecylene group, 10-oxaundecylene group, 2-oxadodecylene group, 3-oxadodecylene group, 4-oxadodecylene group, 4-oxadodecylene group, 5-oxadodecylene group, 6-oxadodecylene group, 7-oxadodecylene group, 8-oxadodecylene group, 9-oxadodecylene group, 10 -Oxadodecylene group, 11-Oxadodecylene group, etc. are mentioned.

The linear alkylene group having 2 to 12 carbon atoms containing an ether bond is preferably a 2-oxapropylene group, a 2-oxabutylene group or a 2-oxapentylene group, and in view of the availability of the raw material for production, An oxabutylene group is more preferred.

As a C2-C12 linear alkylene group containing an amide bond, the ether group ([oxa] part in the said substituent name) in the C2-C12 linear alkylene group containing the said ester bond is set to azamethylene group corresponds to a modification, 2-oxo-3-Azabuchiren group _{(-CH 2 -CO-NH-CH} 2 -), 2- aza-3-oxo-butylene _{(-CH 2 -NH-CO-CH} 2 - ), 2-oxo-3-Azapenchiren group _{(-CH 2 -CO-NH-C} 2 H 4 -), 3- oxo-4-Azapenchiren group _{(-C 2 H 4 -CO-NH} -CH 2 -), 2-aza-3-oxo-pentylene group _{(-CH 2 -NH-CO-C} 2 H 4 -), 3- aza-4-oxo-pentylene group _{(-C 2 H 4 -NH-CO} -CH 2 - ), 2-oxo-3-azahexene Len group _{(-CH 2 -CO-NH-n} -C 3 H 6 -), 3- oxo-4-Azahekishiren group _{(-C 2 H 4 -CO-NH} -C 2 H 4 -), 4- oxo - 5- Azahekishiren group _{(-n-C 3 H 6 -CO} -NH-CH 2 -), 2- aza-3-oxo-hexylene group _{(-CH 2 -NH-CO-n} -C 3 H 6 -), 3-aza-4-oxo hexylene group _{(-C 2 H 4 -NH-CO} -C 2 H 4 -), 4- aza-5-oxo-hexylene group _{(--n C 3 H 6 -NH} -CO -CH ₂ -), 2- oxo-3- Azahepuchiren group _{(-CH 2 -CO-NH-n} -C 4 H 8 -), 3- oxo-4-Azahepuchiren group _{(-C 2} H 4 -CO-NH _{-n-C 3 H 6 -)} , 4- oxo-5- Azahepuchiren group _{(-n-C 3 H 6 -CO} -NH- ₂ H ₄ -), 5- oxo-6- Azahepuchiren group _{(-n-C 4 H 8 -CO} -NH-CH 2 -), 2- aza-3 Okisohepuchiren group _(-CH 2 -NH-CO-n -C ₄ H ₈ -), 3- aza-4-Okisohepuchiren group _{(-C 2 H 4 -NH-CO} -n-C 3 H 6 -), 4- aza-5 Okisohepuchiren group _{(-n-C 3 H 6 -NH-CO-C 2} H 4 -), 5- aza-6- Okisohepuchiren group _{(-n-C 4 H 8 -NH} -CO-CH 2 -), 2- oxo-3- Azaokuchiren group (- _{CH 2 -CO-NH-n-} C 5 H 10 -), 3- oxo-4-Azaokuchiren group _{(-C 2 H 4 -CO-NH} -n-C 4 H 8 -), 4- oxo-5- Azaokuchiren group _{(-n-C 3 H 6 -CO} -NH-n-C 3 H 6 -), 5- Oki Seo 6- Azaokuchiren group _{(-n-C 4 H 8 -CO} -NH-C 2 H 4 -), 6- oxo-7 Azaokuchiren group _{(-n-C 5 H 10 -CO} -NH-CH 2 - ), 2-aza-3-oxooctylene group (-CH ₂ -NH-CO-n-C ₅ H _10- ), 3-aza-4-oxooctylene group (-C ₂ H ₄ -NH-CO-n-C) ₄ H ₈ -), 4- aza-5 Okisookuchiren group _{(-n-C 3 H 6 -NH} -CO-n-C 3 H 6 -), 5- aza-6- Okisookuchiren group _{(-n-C 4 H 8 -NH-CO-C 2} H 4 -), 6- aza-7- Okisookuchiren group _{(-n-C 5 H 10 -NH} -CO-CH 2 -), 2- oxo-3- Azanoniren group (- _{CH 2 -CO-NH-n-} C 6 H 12 -), 3- oxo-4-Azanonire Group _{(-C 2 H 4 -CO-NH} -n-C 5 H 10 -), 4- oxo-5- Azanoniren group _{(-n-C 3 H 6 -CO} -NH-n-C 4 H 8 -) , 5-oxo-6- Azanoniren group _{(-n-C 4 H 8 -CO} -NH-n-C 3 H 6 -), 6- oxo-7 Azanoniren group _(-n-C 5 H 10 -CO- _{NH-C 2 H 4 -)} , 7- oxo-8- Azanoniren group _{(-n-C 6 H 12 -CO} -NH-CH 2 -), 2- aza-3 Okisononiren group _(-CH 2 -NH- _{CO-n-C 6 H 12} -), 3- aza-4-Okisononiren group _{(-C 2 H 4 -NH-CO} -n-C 5 H 10 -), 4- aza-5 Okisononiren group (-n _{-C 3 H 6 -NH-CO-} n-C 4 H 8 -), 5- aza-6- Okisononiren group _{(-n-C 4 8 -NH-CO-n-C} 3 H 6 -), 6- aza-7- Okisononiren group _{(--n C 5 H 10 -NH} -CO-C 2 H 4 -), 7- aza-8- Okisononiren group _{(-n-C 6 H 12 -NH} -CO-CH 2 -), 2- oxo-3- Azadeshiren group _{(-CH 2 -CO-NH-n} -C 7 H 14 -), 3- oxo-4 - Azadeshiren group _{(-C 2 H 4 -CO-NH} -n-C 6 H 12 -), 4- oxo-5- Azadeshiren group _{(-n-C 3 H 6 -CO} -NH-n-C 5 H 10 -), 5-oxo-6- Azadeshiren group _{(-n-C 4 H 8 -CO} -NH-n-C 4 H 8 -), 6- oxo-7 Azadeshiren group _{(-n-C 5 H 10} - _{CO-NH-n-C 3} H 6 -), 7- oxo-8- Azadeshiren group _{(-n-C 6 H} 12 -C _{O-NH-C 2 H 4} -), 8- oxo-9- Azadeshiren group _{(-n-C 7 H 14 -CO} -NH-CH 2 -), 2- aza-3 Okisodeshiren group (-CH ₂ - _{NH-CO-n-C 7} H 14 -), 3- aza-4-Okisodeshiren group _{(-C 2 H 4 -NH-CO} -n-C 6 H 12 -), 4- aza-5 Okisodeshiren group ( _{-n-C 3 H 6 -NH-} CO-n-C 5 H 10 -), 5- aza-6- Okisodeshiren group _{(-n-C 4 H 8 -NH} -CO-n-C 4 H 8 -) , 6-aza-7-Okisodeshiren group _{(-n-C 5 H 10 -NH} -CO-n-C 3 H 6 -), 7- aza-8- Okisodeshiren group _(-n-C 6 H 12 -NH- _{CO-C 2 H 4 -)} , 8- aza-9-Okisodeshiren group _{(-n-C 7 H 14 -NH} -CO-C ₂ -), 2-oxo-3-Azaundeshiren group _{(-CH 2 -CO-NH-n} -C 8 H 16 -), 3- oxo-4-Azaundeshiren group _{(-C 2} H 4 -CO-NH _{-n-C 7 H 14 -)} , 4- oxo-5- Azaundeshiren group _{(-n-C 3 H 6 -CO} -NH-n-C 6 H 12 -), 5- oxo-6- Azaundeshiren group _{(-n-C 4 H 8 -CO} -NH-n-C 5 H 10 -), 6- oxo-7 Azaundeshiren group _{(--n C 5 H 10 -CO} -NH-n-C 4 H 8 -), 7-oxo-8-Azaundeshiren group _{(-n-C 6 H 12-} -CO-NH n-C 3 H 6 -), 8- oxo-9- Azaundeshiren group _(-n-C 7 H _{14 -CO-NH-C 2 H} 4 -), 9- oxo-10-Azaundeshiren group (-n-C _{8 H 16 -CO-NH-CH} 2 -), 2- aza-3-oxo-undecylenic group _{(-CH 2 -NH-CO-n} -C 8 H 16 -), 3- aza-4-oxo-undecylenic groups ( _{-C 2 H 4 -NH-CO-} n-C 7 H 14 -), 4- aza-5-oxo-undecylenic groups _{(-n-C 3 H 6 -NH} -CO-n-C 6 H 12 -), 5-aza-6-oxo-undecylenic groups _{(-n-C 4 H 8 -NH} -CO-n-C 5 H 10 -), 6- aza-7-oxo-undecylenic groups _{(--n C 5} H 10 -NH _{-CO-n-C 4 H 8} -), 7- aza-8-oxo-undecylenic groups _{(-n-C 6 H 12-} -NH CO-n-C 3 H 6 -), 8- aza-9-oxo undecylene _{(-n-C 7 H 14 -NH} -CO-C 2 H 4 -), 9- aza-10-O Soundeshiren group _{(-n-C 8 H 16 -NH} -CO-CH 2 -), 2- oxo-3- Azadodeshiren group _{(-CH 2 -CO-NH-n} -C 9 H 18 -), 3- oxo 4- Azadodeshiren group _{(-C 2 H 4 -CO-NH} -n-C 8 H 16 -), 4- oxo-5- Azadodeshiren group _{(-n-C 3 H 6 -CO} -NH-n-C 7 H ₁₄ -), 5- oxo-6- Azadodeshiren group _{(-n-C 4 H 8 -CO} -NH-n-C 6 H 12 -), 6- oxo-7 Azadodeshiren group _(-n-C 5 H _{10 -CO-NH-n-C} 5 H 10 -), 7- oxo-8- Azadodeshiren group _{(-n-C 6 H 12 -CO} -NH-n-C 4 H 8 -), 8- oxo -9 - Azadodeshiren group _{(-n-C 7 H 14 -CO} -NH-n-C 3 H 6 -) 9-oxo-10-Azadodeshiren group _{(-n-C 8 H 16 -CO} -NH-C 2 H 4 -), 10- oxo-11-Azadodeshiren group _{(-n-C 9 H 18 -CO} -NH-CH ₂ -), 2-aza-3 Okisododeshiren group _{(-CH 2 -NH-CO-n} -C 9 H 18 -), 3- aza-4-Okisododeshiren group _{(-C 2 H 4 -NH-CO} -n -C ₈ H ₁₆ -), 4- aza-5 Okisododeshiren group _{(-n-C 3 H 6 -NH} -CO-n-C 7 H 14 -), 5- aza-6- Okisododeshiren group (-n- _{C 4 H 8 -NH-CO-} n-C 6 H 12 -), 6- aza-7- Okisododeshiren group _{(-n-C 5 H 10 -NH} -CO-n-C 5 H 10
-), 7-aza-8- Okisododeshiren group _{(-n-C 6 H 12 -NH} -CO-n-C 4 H 8 -), 8- aza-9-Okisododeshiren group _{(-n-C 7 H 14} - _{NH-CO-n-C 3} H 6 -), 9- aza-10- Okisododeshiren group _{(-n-C 8 H 16 -NH} -CO-C 2 H 4 -) and 10-aza-11-Okisododeshiren group ( _{-n-C 9 H 18 -NH-} CO-CH 2 -) and the like.

Examples of the linear alkylene group having 2 to 12 carbon atoms containing an amide bond include 2-aza-3-oxobutylene group, 2-aza-3-oxopentylene group, 3-aza-4-oxopentylene group, 3 -Aza-4-oxohexylene group is preferable, and 3-aza-4-oxohexylene group is more preferable from the viewpoint of availability of the raw material for production.

As a C2-C12 linear alkylene group containing a urethane bond, a carbonyl group ([Oxo] moiety in the above-mentioned substituent name) may be added to the C2-C12 linear alkylene group containing an ester bond. It corresponds to what changed the adjacent methylene group to azamethylene group,
2-oxa-3-oxo-4- Azapenchiren group _{(-CH 2 -O-CO-NH} -CH 2 -), 2- aza-3-oxo-4-oxa-pentylene group _(-CH 2 -NH-CO _-O-CH 2 -),
2-oxa-3-oxo-4- Azahekishiren group _{(-CH 2 -O-CO-NH} -C 2 H 4 -), 3- oxa-4-oxo-5- Azahekishiren group _{(-C 2} H 4 -O _{-CO-NH-CH 2 -)} , 2- aza-3-oxo-4-oxa-hexylene group _{(-CH 2--NH CO-O} -C 2 H 4 -), 3- aza-4-oxo - 5-oxa-hexylene group _{(-C 2 H 4 -NH-CO} -O-CH 2 -),
2-oxa-3-oxo-4- Azahepuchiren group _{(-CH 2 -O-CO-NH} -n-C 3 H 6 -), 3- oxa-4-oxo-5- Azahepuchiren group _(-C 2 _{H 4 -O-CO-NH-C 2} H 4 -), 4- oxa-5-oxo-6- Azahepuchiren group _{(-n-C 3 H 6 -O} -CO-NH-CH 2 -), 2- aza - 3-oxo-4- Okisahepuchiren group _{(-CH 2 -NH-CO-O} -n-C 3 H 6 -), 3- aza-4-oxo-5- Okisahepuchiren group _{(-C 2} H 4 -NH-CO _{-O-C 2 H 4 -)} , 4- aza-5-oxo-6-Okisahepuchiren group _{(-n-C 3 H 6 -NH} -CO-O-CH 2 -), 2- oxa-3-oxo - 4- Azaokuchiren group _{(-CH 2 -O-CO-NH} -n-C 4 H 8 -), 3- oxa 4-oxo-5- Azaokuchiren group _{(-C 2 H 4 -O-CO} -NH-n-C 3 H 6 -), 4- oxa-5-oxo-6- Azaokuchiren group _(-n-C 3 H _{6 -O-CO-NH-C} 2 H 4 -), 5- oxa-6-oxo-7-Azaokuchiren group _{(-n-C 4 H 8 -O} -CO-NH-CH 2 -), 2- aza 3-oxo-4- Okisaokuchiren group _{(-CH 2 -NH-CO-O} -n-C 4 H 8 -), 3- aza-4-oxo-5- Okisaokuchiren group _{(-C 2} H 4 -NH- _{CO-O-n-C 3} H 6 -), 4- aza-5-oxo-6-Okisaokuchiren group _{(-n-C 3 H 6 -NH} -CO-O-C 2 H 4 -), 5- aza 6-oxo-7-Okisaokuchiren group _{(-n-C 4 H 8 -NH} -CO-O-CH 2 -), 2- Kisa 3-oxo-4- Azanoniren group _{(-CH 2 -O-CO-NH} -n-C 5 H 10 -), 3- oxa-4-oxo-5- Azanoniren group _{(-C 2} H 4 -O _{-CO-NH-n-C 4} H 8 -), 4- oxa-5-oxo-6- Azanoniren group _{(-n-C 3 H 6 -O} -CO-NH-n-C 3 H 6 -), 5-oxa-6-oxo-7-Azanoniren group _{(-n-C 4 H 8 -O} -CO-NH-C 2 H 4 -), 6- oxa-7-oxo-8- Azanoniren group (-n- _{C 5 H 10 -O-CO-} NH-CH 2 -), 2- aza-3-oxo-4- Okisanoniren group _{(-CH 2 -NH-CO-O} -n-C 5 H 10 -), 3- aza-4-oxo-5- Okisanoniren group _{(-C 2 H 4 -NH-CO} -O-n-C 4 H 8 -), 4- The 5-oxo-6- Okisanoniren group _{(-n-C 3 H 6 -NH} -CO-O-n-C 3 H 6 -), 5- aza-6-oxo-7-Okisanoniren group (-n- _{C 4 H 8 -NH-CO-} O-C 2 H 4 -), 6- aza-7-oxo-8- Okisanoniren group _{(--n C 5 H 10 -NH} -CO-O-CH 2 -), 2-oxa-3-oxo-4- Azadeshiren group _{(-CH 2 -O-CO-NH} -n-C 6 H 12 -), 3- oxa-4-oxo-5- Azadeshiren group _(-C 2 _{H 4 -O-CO-NH-n-} C 5 H 10 -), 4- oxa-5-oxo-6- Azadeshiren group _{(--n C 3 H 6 -O} -CO-NH-n-C 4 H 8 - ), 5-oxa-6-oxo-7-Azadeshiren group _{(-n-C 4 H 8 -O} -CO-NH-n-C 3 H -), 6-oxa-7-oxo-8- Azadeshiren group _{(-n-C 5 H 10 -O} -CO-NH-C 2 H 4 -), 7- oxa-8-oxo-9- Azadeshiren group ( _{-n-C 6 H 12 -O-} CO-NH-CH 2 -), 2- aza-3-oxo-4- Okisadeshiren group _{(-CH 2 -NH-CO-O} -n-C 6 H 12 -) , 3-aza-4-oxo-5- Okisadeshiren group _{(-C 2 H 4 -NH-CO} -O-n-C 5 H 10 -), 4- aza-5-oxo-6-Okisadeshiren group (-n _{-C 3 H 6 -NH-CO-} O-n-C 4 H 8 -), 5- aza-6-oxo-7-Okisadeshiren group _{(-n-C 4 H 8 -NH} -CO-O-n- C ₃ H ₆ -), 6- aza-7-oxo-8- Okisadeshiren group _{(-n-C 5 H 10 -NH} -CO- -C ₂ H ₄ -), 7- aza-8-oxo-9- Okisadeshiren group _{(-n-C 6 H 12 -NH} -CO-O-CH 2 -), 2- aza-3-oxo-4- oxa undecylenic group _{(-CH 2 -NH-CO-O} -n-C 7 H 14 -), 3- aza-4-oxo-5-oxa undecylenic group _{(-C 2 H 4 -NH-CO} -O-n -C ₆ H ₁₂ -), 4- aza-5-oxo-6-oxa-undecylenic groups _{(-n-C 3 H 6 -NH} -CO-O-n-C 5 H 10 -), 5- aza -6 - oxo-7-oxa-undecylenic groups _{(-n-C 4 H 8 -NH} -CO-O-n-C 4 H 8 -), 6- aza-7-oxo-8-oxa undecylenic groups (-n-C ₅ H ₁₀ -NH-CO-O-n-C ₃ H _6- ), 7-Aza-8-oxo-9-oxaundeci Len group _{(-n-C 6 H 12 -NH} -CO-O-C 2 H 4 -), 8- aza-9-oxo-10-oxa undecylenic groups _{(-n-C 7 H 14 -NH} -CO- _O-CH 2 -), 2- oxa-3-oxo-4- Azaundeshiren group _{(-CH 2 -O-CO-NH} -n-C 7 H 14 -), 3- oxa-4-oxo-5- Azaundeshiren group _{(-C 2 H 4 -O-CO} -NH-n-C 6 H 12 -), 4- oxa-5-oxo-6- Azaundeshiren group _{(-n-C 3 H 6 -O} -CO _{-NH-n-C 5 H 10} -), 5- oxa-6-oxo-7-Azaundeshiren group _{(--n C 4 H 8 -O} -CO-NH-n-C 4 H 8 -), 6 - oxa-7-oxo-8-Azaundeshiren group _{(-n-C 5 H 10 -O} -CO-NH-n-C 3 H -), 7-oxa-8-oxo-9- Azaundeshiren group _{(-n-C 6 H 12 -O} -CO-NH-C 2 H 4 -), 8- oxa-9-oxo-10-Azaundeshiren group _{(-n-C 7 H 14 -O} -CO-NH-CH 2 -), 2- aza-3-oxo-4- Okisadodeshiren group _{(-CH 2--NH CO-O} -n-C 8 H 16 -), 3-aza-4-oxo-5- Okisadodeshiren group _{(-C 2 H 4 -NH-CO} -O-n-C 7 H 14 -), 4- aza-5-oxo-6-Okisadodeshiren group ( _{-n-C 3 H 6 -NH-} CO-O-n-C 6 H 12 -), 5- aza-6-oxo-7-Okisadodeshiren group _{(-n-C 4 H 8 -NH} -CO-O- _{n-C 5 H 10 -)} , 6- aza-7-oxo-8- Okisadodeshiren group (-n-C _{H 10 -NH-CO-O-} n-C 4 H 8 -), 7- aza-8-oxo-9- Okisadodeshiren group _{(-n-C 6 H 12 -NH} -CO-O-n-C 3 H ₆ -), 8-aza-9-oxo-10-Okisadodeshiren group _{(-n-C 7 H 14 -NH} -CO-O-C 2 H 4 -), 9- aza-10-oxo-11-Okisadodeshiren group _{(-n-C 8 H 16 -NH} -CO-O-CH 2 -), 2- oxa-3-oxo-4- Azadodeshiren group _{(-CH 2 -O-CO-NH} -n-C 8 H 16 - ), 3-oxa-4-oxo-5- Azadodeshiren group _{(-C 2 H 4 -O-CO} -NH-n-C 7 H 14 -), 4- oxa-5-oxo-6- Azadodeshiren group (- _{n-C 3 H 6 -O-} CO-NH-n-C 6 H 12 -), 5- oxa -6 Oxo-7 Azadodeshiren group _{(-n-C 4 H 8 -O} -CO-NH-n-C 5 H 10 -), 6- oxa-7-oxo-8- Azadodeshiren group _{(-n-C 5 H 10 -O-CO-NH-n-} C 4 H 8 -), 7- oxa-8-oxo-9- Azadodeshiren group _{(-n-C 6 H 12-} -O-CO-NH n-C 3 H 6 - ), 8-oxa-9-oxo-10-Azadodeshiren group _{(-n-C 7 H 14 -O} -CO-NH-C 2 H 4 -) and 9-oxa-10-oxo-11-Azadodeshiren group (- _{n-C 8 H 16 -O-} CO-NH-CH 2 -) and the like.

In addition, R ⁵ counts carbon number 1 on the side to be bonded to Z ¹ as the number ¹ and in the description of the above-mentioned substituent, it is described to bond to Z ¹ at the end on the left side.

Examples of the compound having a structure represented by the above formula (10) include tris-[(3-mercaptopyropionyloxy) -ethyl] -isocyanurate, 1,3,5-tris (mercaptomethyl) benzene, 1 And 3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,3,4,6-tetrakis (mercaptoethyl) glycoluril and the like.

As said thiol compound (C), the compound which has a structure shown by following formula (21) other than the compound which has a structure shown by the said Formula (10) is mentioned.

o is an integer of 2 to 6, p is an integer of 0 to 4, and o + p is an integer of 2 to 6. Z ² is an organic group having 1 to 6 carbon atoms, and may contain a bond selected from the group consisting of an ester bond, an ether bond, an amide bond, and a urethane bond. o R ⁷ groups are each independently and are selected from the group consisting of a chain aliphatic group, an aliphatic group containing a cyclic structure, and an organic group selected from the group consisting of an aromatic group, or a group thereof It is an organic group consisting of a combination of a plurality of organic groups, and may contain one or more groups or bonds selected from the group consisting of a carbonyl group, an ether bond, an amide bond and a urethane bond. Each of p R ^{8 s} is independently selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a fluoro group, a chloro group, a bromo group and an iodo group.

o is an integer of 2 to 6; As the content of the thiol group increases, the heat resistance of the cured resin can be expected to be improved, but in consideration of the balance between heat resistance and mechanical properties such as bending strength and toughness, o is preferably 2 to 4.
Further, as R ⁷ , the same substituents as R ⁵ described above can be suitably used.
In addition, R ⁷ counts carbon on the side to be bonded to Z ² as No. 1.

The Z ^2, is preferably a linear alkylene group having 1 to 4 carbon atoms. Also, Z ² may contain a bond selected from the group consisting of an ester bond, an ether bond, an amide bond and a urethane bond, but among these, an ether bond is included because of the availability of the raw materials for production. Is preferred.

R ⁷ represents a 2-oxa-3-oxopentylene group, a 2-oxa-3-oxohexylene group, a 2-oxa-3-oxoheptylene group, a 2-oxa-3-oxooctylene group, a 3-oxa-4-oxo group hexylene group, other 3-oxa-4-Okisohepuchiren group or 3-oxa-4-Okisookuchiren _{group, -O- (CH 2) 2 -O} -CO- (CH 2) 2 - is a group represented by 2-oxa-3-oxopentylene group or 2-oxa-3-oxohexylene group, -O- (CH ₂ ) ₂ -O-CO- (from the viewpoint of easy availability of raw materials for production). CH _{2) 2} - and more preferably a group represented by.

When Z ² contains an ether bond, it is more preferable to have a structure obtained by removing six hydroxymethyl groups (—CH ₂ —OH) from dipentaerythritol (a structure represented by the following formula (22)).

As a compound having a structure represented by the above formula (22), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropio) And dipentaerythritol hexakis (3-mercaptopropionate).

The thermosetting resin cured product obtained by the method for producing a thermosetting resin cured product of the present invention is excellent in both toughness and flexural strength, and is fiber reinforced by making it into a prepreg in which the composition before curing is impregnated into reinforcing fibers. It can be suitably used for composite materials.

Fiber reinforced composites composed of reinforcing fibers and matrix resin are widely used in sports goods, leisure goods, aerospace and general industrial applications. In order to realize products having high mechanical properties in sporting goods applications and leisure goods applications, materials that are resistant to applied compressive stress and bending stress are required.
On the other hand, in aerospace applications and general industrial applications, in addition to the above mechanical properties, high impact resistance is required, and high toughness materials are required.
Since the cured product of the present invention is excellent in both toughness and flexural strength, it can be suitably used for a fiber reinforced composite material by making the composition before curing into a prepreg impregnated with reinforcing fibers.

Further, as another method for producing a fiber-reinforced composite material, for example, as in a resin transfer molding method, a preform made of a reinforced form such as a woven form or a knitted form is placed in a mold, It is also possible to use a method of impregnating the composition before curing with the reinforcing fiber and curing it to produce a fiber reinforced composite material.

The following examples are provided to describe the present invention in detail, but the present invention is not limited to these examples.

Materials Used in the Examples
(Allyl compound)
(A) 2,2'-diallyl bisphenol A (manufactured by Daiwa Kasei Kogyo Co., Ltd .: DABPA, molecular weight 308 calculated from structural formula)
(Maleimide compound)
(B) 4,4'-diphenylmethane bismaleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd .: BMI-1100H, molecular weight calculated from structural formula 358)
(Thiol compound)
(C-1) Tetraethylene glycol bis (3-mercaptopropionate (manufactured by SC Organic Chemical Company: EGMP-4, molecular weight 372 calculated from structural formula)
(C-2) Tris-[(3-Mercaptopropionyloxy) -ethyl] -isocyanate (manufactured by SC Organic Chemical Company: TEMPIC, molecular weight 525 calculated from structural formula)

The weight average molecular weights of the oligomers obtained in Examples and Comparative Examples were measured by the following methods.
[Measurement of weight average molecular weight of oligomer]
The weight average molecular weight (Mw) of the oligomer was converted from a calibration curve using standard polyethylene glycol and standard polyethylene oxide by gel permeation chromatography (GPC).
Device: Alliance 2695 (manufactured by Waters)
Column: KD-806M, KD-802 (Shodex)
Guard column: KD-G (manufactured by Shodex)

Example 1
In an oil-jacketed container with a stirring blade, 75.0 g of BMI-1100H and 13.0 g of EGMP-4 were added and kneaded. The temperature was raised to 80 ° C. while kneading the contents, and the reaction was carried out for 3 hours to obtain an oligomer. 21.5 g of DABPA was added to the obtained oligomer, and the mixture was kneaded again. The resulting kneaded product was transferred to an aluminum cup and heated in an oven at 160 ° C. After the contents were completely melted, the pressure was reduced until no bubbles were released from the melt. After returning to atmospheric pressure, a cured product 1 was obtained by heating at 160 ° C. for 2 hours, 180 ° C. for 2 hours, 200 ° C. for 2 hours, 220 ° C. for 2 hours, and 240 ° C. for 2 hours.

Example 2
In an oil-jacketed container with a stirring blade, 25.0 g of BMI-1100H and 13.0 g of EGMP-4 were added and kneaded. The temperature was raised to 80 ° C. while kneading the contents, and the reaction was carried out for 3 hours to obtain an oligomer. To the resulting oligomer, 21.5 g of DABPA and 50.0 g of BMI-1100H were added, and the mixture was kneaded again. The resulting kneaded product was transferred to an aluminum cup and heated in an oven at 160 ° C. After the contents were completely melted, the pressure was reduced until no bubbles were released from the melt. After returning to atmospheric pressure, a cured product 2 was obtained by heating at 160 ° C. for 2 hours, 180 ° C. for 2 hours, 200 ° C. for 2 hours, 220 ° C. for 2 hours, and 240 ° C. for 2 hours.

Examples 3 to 5
Examples 3 to 5 were carried out in the same manner as Example 2 except that the composition of the raw materials used was changed as shown in Table 1, to obtain cured products 3 to 5.

Comparative Example 1
In an oil-jacketed container equipped with a stirring blade, 21.5 g of DABPA, 75.0 g of BMI-1100H, and 13.0 g of EGMP-4 were added and kneaded. The resulting kneaded product was transferred to an aluminum cup and heated in an oven at 160 ° C. After the contents were completely melted, the pressure was reduced until no bubbles were released from the melt. After returning to atmospheric pressure, heating at 160 ° C. for 2 hours, 180 ° C. for 2 hours, 200 ° C. for 2 hours, 220 ° C. for 2 hours, and 240 ° C. for 2 hours gave Comparative Cured Product 1.

Comparative example 2
In an oil-jacketed container equipped with a stirring blade, 21.5 g of DABPA and 13.0 g of EGMP-4 were added and kneaded. The temperature was raised to 80 ° C. while kneading the contents, and the reaction was carried out for 3 hours to obtain an oligomer. To the obtained oligomer, 75.0 g of BMI-1100H was added, and the mixture was kneaded again. The resulting kneaded product was transferred to an aluminum cup and heated in an oven at 160 ° C. After the contents were completely melted, the pressure was reduced until no bubbles were released from the melt. After returning to atmospheric pressure, heating at 160 ° C. for 2 hours, 180 ° C. for 2 hours, 200 ° C. for 2 hours, 220 ° C. for 2 hours, and 240 ° C. for 2 hours gave Comparative Cured Product 2.

Comparative example 3
In an oil-jacketed container equipped with a stirring blade, 13.8 g of BMI-1100H and 13.0 g of EGMP-4 were added and kneaded. The temperature was raised to 80 ° C. while kneading the contents, and the reaction was carried out for 3 hours to obtain an oligomer. To the resulting oligomer, 21.5 g of DABPA and 61.2 g of BMI-1100H were added, and the mixture was kneaded again. The resulting kneaded product was transferred to an aluminum cup and heated in an oven at 160 ° C. After the contents were completely melted, the pressure was reduced until no bubbles were released from the melt. After returning to atmospheric pressure, heating at 160 ° C. for 2 hours, 180 ° C. for 2 hours, 200 ° C. for 2 hours, 220 ° C. for 2 hours, and 240 ° C. for 2 hours gave Comparative Cured Product 3.

Evaluation of Properties With respect to the cured products 1 to 5 and comparative cured products 1 to 3 obtained in Examples 1 to 5 and Comparative Examples 1 to 3, evaluation of various characteristics was performed by the following method. The results are shown in Table 1.
Thermal decomposition temperature
The thermosetting resin according to each example and comparative example is raised by a method according to JIS K-7120 (1987) using a differential thermal thermal gravimetry simultaneous measuring apparatus (STA 7300 manufactured by Hitachi High-Tech Science Co., Ltd.) The thermal weight loss under a nitrogen atmosphere was measured at a temperature rate of 10 ° C./min. The temperature at which the weight decreased by 5% was taken as the thermal decomposition temperature.
[Glass-transition temperature]
A test piece of 15 mm × 3 mm × 3 mm is cut out from the thermosetting resin according to each example and comparative example, and JIS K-7197 (2012) is measured using a thermomechanical property measurement apparatus (TMA 8310 manufactured by Rigaku Corporation) By the method according to it, the temperature increase rate was 2 ° C./min, the load was 50 mN, and the measurement was performed in the compression load mode. The inflection point of the obtained curve was calculated by extrapolation and used as the glass transition temperature.
[Bending strength, flexural modulus, elongation at break]
A 70 mm × 10 mm × 3 mm test piece is cut out of the thermosetting resin according to each example and comparative example, and a material universal tester (AGS-X manufactured by Shimadzu Corporation) is used according to JIS K-6911 (2006). The bending strength, the bending elastic modulus, and the elongation at break were calculated by performing a three-point bending test by setting the distance between supporting points to 48 mm, the loading speed to 1.5 mm / min, and the method according to the above.
Fracture toughness
A test piece of 60 mm × 10 mm × 3 mm is cut out from the thermosetting resin according to each example and comparative example, and it conforms to ASTM D5043-93 using a material universal tester (AGS-X manufactured by Shimadzu Corporation) A fracture toughness test was performed by a three-point bending method with a distance between supporting points of 40 mm and a loading speed of 1 mm / min by a method to calculate a critical stress intensity factor (K _IC ), which was used as a fracture toughness value.

Examples 6-8, Comparative Examples 4 and 5
Examples 6 to 8 are carried out in the same manner as Example 1 except that the thiol compound to be used is changed from EGMP-4 to TEMPIC and the composition of the raw materials is changed as described in Table 2, and cured products 6 to 8 I got
In addition, Comparative Example 4 was carried out in the same manner as Comparative Example 1 except that the thiol compound to be used was changed from EGMP-4 to TEMPIC, and the composition of the raw materials was changed as described in Table 2, Obtained. Further, Comparative Example 5 was carried out in the same manner as Comparative Example 2 except that the blending of the raw materials was changed as shown in Table 2, to obtain a comparative cured product 5.
The same various characteristics were evaluated for the cured products 6 to 8 and the comparative cured products 4 and 5 as described above. The results are shown in Table 2.

From the comparison between Examples 1 to 5 in Table 1 and Comparative Example 1, when using the production method of the present invention, bending strength and fracture toughness are improved as compared with the case where a resin cured product is produced by blending three raw materials. It has been confirmed that it can be improved. In particular, by setting the ratio of the thiol compound to the maleimide compound in the composition before curing to a predetermined range (Examples 1 to 4), the bending strength and the fracture toughness can be obtained without reducing the heat resistance and the bending elastic modulus. It has been confirmed that it can be improved.
Further, from the comparison of Examples 1 to 5 and Comparative Example 2, after the maleimide compound and the thiol compound are mixed and reacted in a predetermined ratio in advance, the allyl compound is mixed and cured to improve toughness and bending strength. It was confirmed that an excellent cured resin product was obtained.
From the results in Table 2, it was confirmed that a resin cured product having both excellent toughness and flexural strength can be obtained by using the production method of the present invention even when a trifunctional compound is used as the thiol compound.

Claims (3)

An allyl compound (A) having at least two or more allyl groups in one molecule, a maleimide compound (B) having at least two or more maleimide groups in one molecule, and at least two or more thiols in one molecule A method for producing a thermosetting resin cured product using at least a thiol compound (C) having a group,
According to the production method, the thiol compound (C) and the maleimide compound (C) such that the maleimide group equivalent in the maleimide compound (B) is 1.15 to 6 with respect to the thiol group equivalent 1 in the thiol compound (C) B) mixing and then reacting to synthesize an oligomer;
A second step of mixing an oligomer obtained in the first step and a raw material containing an allyl compound (A) to form a composition,
A third step of curing the composition obtained in the second step by heating the composition at 150 ° C. or more for 5 hours or more, and a method of producing a cured thermosetting resin product. The heat according to claim 1, wherein the maleimide compound (B) has an N-phenylmaleimide structure represented by the following formula (1), and the molecular weight of the compound is less than 1,000. The manufacturing method of curable resin cured material.

[In Formula (1), R ¹ and R ² are each independently, and are a hydrogen atom or a monovalent hydrocarbon group. X is an organic group containing a maleimide group at the end, and may contain a hydrocarbon group or an aromatic ring. The number of aromatic rings constituting X may be plural, and the plurality of aromatic rings may be bonded via an ether group, an ester group, an amide group, a carbonyl group, an azamethylene group or an alkylene group, directly It may be combined. ] The method for producing a thermosetting resin cured product according to claim 1, wherein the cured product is a cured product for a fiber-reinforced composite material.