JP2022059378A - Thermosetting resin based composition - Google Patents

Abstract

To provide a thermosetting resin based composition with fast curability and good storage stability, and a thermosetting resin based cured product.MEANS: The thermosetting resin based composition comprises a thermosetting resin, dicyandiamide, and a thermosetting resin curing accelerator. The thermosetting resin curing accelerator is a phosphonium salt comprising an anion residue of an organic acid and a phosphonium cation represented by the general formula (5) in the figure or the like. The thermosetting resin based cured product is obtained by curing the thermosetting resin based composition.SELECTED DRAWING: None

Description

The present invention relates to a thermosetting resin-based composition having fast-curing properties and good storage stability.

Conventionally, a thermosetting resin-based composition typified by an epoxy resin or the like can be used as a molded body having excellent mechanical, chemical and electrical properties, and thus can be used as an insulating sealing material for a semiconductor element or a printed circuit board material. Widely used in paints, composite materials for aircraft and automobiles, etc.

For example, in the production of fiber-reinforced composite materials, a sheet-shaped intermediate base material (prepreg) in which reinforcing fibers are impregnated with a thermosetting resin-based composition is widely used, and a molded body is formed by laminating the prepreg and heating it to cure it. can get. In particular, the thermosetting resin-based composition for prepreg is preferably easy to handle because it can be stored at room temperature. Therefore, the storage stability of the thermosetting resin-based composition is important.

In the thermosetting resin-based composition, a thermosetting resin-based composition using an epoxy resin as a thermosetting resin and dicyandiamide as a curing agent is preferably used because it is easy to handle. However, it is known that the thermosetting resin-based composition requires a long time to cure.

The curing accelerator contained as a component in the thermosetting resin-based composition accelerates the curing of the thermosetting resin-based composition by adding it, and also has adhesiveness and heat resistance of the cured product which is a molded product thereof. It is extremely important to select a suitable curing accelerator because it affects various properties such as.

Under such circumstances, there is a demand for a curing accelerator for a thermosetting resin that provides a thermosetting resin-based composition having an excellent balance between curing promoting ability and storage stability. However, the ability to accelerate curing and storage stability tend to be in a trade-off relationship, and it is difficult to satisfy these at the same time.

Triphenylphosphine is used as a curing accelerator in order to shorten the curing time (see Patent Document 1), but the curing promoting ability is insufficient. Further, imidazoles are also used as a curing accelerator having a strong curing accelerating ability (see Patent Documents 2 and 3), but there is a problem that the storage stability of the thermosetting resin-based composition at room temperature is poor. Further, a technique of microencapsulating and using imidazoles for the purpose of improving the storage stability is also known (see Patent Document 4), but an encapsulation processing step is required, and the capsule component is a foreign substance. There was a problem of remaining. Examples of the curing accelerator having a good balance between the curing accelerating ability and the storage stability include TPP-SCN (see Patent Document 5) and TPTP (see Patent Document 6), but they are not satisfactory.

Japanese Unexamined Patent Publication No. 08-012858 Japanese Unexamined Patent Publication No. 2005-255793 Japanese Unexamined Patent Publication No. 2005-281488 Japanese Unexamined Patent Publication No. 2000-323193 Japanese Unexamined Patent Publication No. 2010-083941 Japanese Unexamined Patent Publication No. 2011-07942

The present invention is intended to solve the problems associated with the above-mentioned prior art. That is, it is to provide a thermosetting resin-based composition having fast-curing property and good storage stability.

In view of such a situation, the present inventors have diligently studied. As a result, they have found that a thermosetting resin-based composition having fast-curing property and good storage stability can be obtained when a specific phosphonium compound is blended as a curing accelerator, and the present invention has been completed. rice field.

（式中、Ｒ^１～Ｒ^４は、同一または異なって、炭素数１～１６の置換もしくは非置換の炭化水素基を示す。）で表されるホスホニウムカチオンと、
下記の一般式（２）から一般式（４）で表される有機酸からなる群から選ばれる少なくとも１種の有機酸のアニオン残基からなるホスホニウム塩を含むことを特徴とするを含むことを特徴とする熱硬化性樹脂系組成物。

（式中、Ｒ^５は、炭素数１～１６の置換もしくは非置換の炭化水素基を示す。）

（式中、Ｘ、Ｙは、同一または異なって、それぞれメチレン基、イミノ基、酸素原子を示し、Ｚはジメチルメチレン基、カルボニル基を示す。）

（式中、Ａは、カルボニル基、スルホニル基を示す。）
〔２〕前記一般式（１）において、Ｒ^１～Ｒ^４が、同一または異なって、ブチル基、フェニル基、４－メチルフェニル基、４－メトキシフェニル基、ベンジル基、メトキシメチル基、および、カルボキシエチル基から選ばれる置換基である〔１〕に記載の熱硬化性樹脂系組成物。
〔３〕前記一般式（１）において、Ｒ^１～Ｒ^４が全てフェニル基である〔１〕に記載の熱硬化性樹脂系組成物。
〔４〕前記一般式（１）において、Ｒ^１～Ｒ^４が全てブチル基である〔１〕に記載の熱硬化性樹脂系組成物。
〔５〕前記一般式（２）が酢酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ステアリン酸、コハク酸、クエン酸、マレイン酸、１，２－シクロヘキサンジカルボン酸、１，４－シクロヘキサンジカルボン酸、安息香酸、フタル酸、トリメリット酸、ピロメリット酸からなる群から選ばれる１種の有機酸であることを特徴とする〔１〕～〔４〕のいずれかに記載の熱硬化性樹脂系組成物。
〔６〕前記一般式（３）がメルドラム酸、ジメドン、バルビツール酸からなる群から選ばれる１種の有機酸であることを特徴とする〔１〕～〔４〕のいずれかに記載の熱硬化性樹脂系組成物。
〔７〕前記一般式（４）がフタルイミド、サッカリンからなる群から選ばれる１種の有機酸であることを特徴とする〔１〕～〔４〕のいずれかに記載の熱硬化性樹脂系組成物。
〔８〕前記熱硬化性樹脂が、エポキシ樹脂、マレイミド樹脂、シアネート樹脂、および、イソシアネート樹脂から選ばれる１種または２種以上の熱硬化性樹脂である、〔１〕～〔７〕のいずれかに記載の熱硬化性樹脂系組成物。
〔９〕〔１〕～〔８〕のいずれかに記載の熱硬化性樹脂系組成物を硬化して得られる熱硬化性樹脂系硬化物。 That is, the gist of the present invention is as follows.
[1] A thermosetting resin-based composition comprising a thermosetting resin, dicyandiamide, and a curing accelerator for a thermosetting resin, which has the following general formula (1) as a curing accelerator for a thermosetting resin.

(In the formula, R ¹ to R ⁴ represent substituted or unsubstituted hydrocarbon groups having 1 to 16 carbon atoms, which are the same or different.) And the phosphonium cation.
It is characterized by containing a phosphonium salt consisting of an anion residue of at least one organic acid selected from the group consisting of organic acids represented by the following general formulas (2) to (4). A characteristic thermosetting resin-based composition.

(In the formula, R ⁵ indicates a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms.)

(In the formula, X and Y are the same or different and represent a methylene group, an imino group and an oxygen atom, respectively, and Z represents a dimethylmethylene group and a carbonyl group.)

(In the formula, A represents a carbonyl group and a sulfonyl group.)
[2] In the general formula (1), R ¹ to R ⁴ are the same or different, and have a butyl group, a phenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a benzyl group, a methoxymethyl group, and a group. The thermosetting resin-based composition according to [1], which is a substituent selected from a carboxyethyl group.
[3] The thermosetting resin-based composition according to [1], wherein in the general formula (1), R ¹ to R ⁴ are all phenyl groups.
[4] The thermosetting resin-based composition according to [1], wherein in the general formula (1), R ¹ to R ⁴ are all butyl groups.
[5] The general formula (2) is acetic acid, caproic acid, capric acid, capric acid, lauric acid, stearic acid, succinic acid, citric acid, maleic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid. The thermosetting resin according to any one of [1] to [4], which is one kind of organic acid selected from the group consisting of acid, benzoic acid, phthalic acid, trimellitic acid and pyromellitic acid. System composition.
[6] The heat according to any one of [1] to [4], wherein the general formula (3) is one organic acid selected from the group consisting of meldrum's acid, dimedone, and barbituric acid. Curable resin-based composition.
[7] The thermosetting resin composition according to any one of [1] to [4], wherein the general formula (4) is one organic acid selected from the group consisting of phthalimide and saccharin. thing.
[8] Any one of [1] to [7], wherein the thermosetting resin is one or more thermosetting resins selected from epoxy resins, maleimide resins, cyanate resins, and isocyanate resins. The thermosetting resin-based composition according to.
[9] A thermosetting resin-based cured product obtained by curing the thermosetting resin-based composition according to any one of [1] to [8].

The thermosetting resin-based composition containing the phosphonium salt of the present invention is useful because it has fast-curing properties and good storage stability as compared with the case where a conventional curing accelerator is used.

Hereinafter, the present invention will be described in detail.
In the present invention, the substituted or unsubstituted hydrocarbon group is a hydrocarbon group having 1 to 16 carbon atoms, and has an aliphatic hydrocarbon group which may have a substituent and a substituent. Also contains good aromatic hydrocarbon groups. When the hydrocarbon group has a substituent, the number of carbon atoms of the hydrocarbon group does not include the number of carbon atoms contained in the substituent.

In the present invention, the aliphatic hydrocarbon group which may have a substituent may be a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic group. It may be a hydrocarbon group. Specific examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group and 1-ethylpropyl group as alkyl groups. n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group , 2,2-Dimethylbutyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethyl-2-methylbutyl group, n-pentyl group, neopentyl group, 2-Pentyl group, 3-Pentyl group, tert-Pentyl group, 1-Methylpentyl group, 2-Methylpentyl group, 3-Methylpentyl group, 4-Methylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group , N-hexyl group, isohexyl group, 2-hexyl group, 3-hexyl group, 1-methylhexyl group, 2-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group , N-Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group and other saturated aliphatic hydrocarbon groups. Examples of the alkenyl group include an allyl group and a vinyl group, and examples of the alkynyl group include an unsaturated aliphatic hydrocarbon group such as an ethynyl group and a butyl group.

In the present invention, the aliphatic hydrocarbon group which may have a substituent may be an alicyclic hydrocarbon group. Further, the alicyclic hydrocarbon group may be an alicyclic saturated hydrocarbon group or an alicyclic unsaturated hydrocarbon group. Specifically, as the alicyclic hydrocarbon group, as the cycloalkyl group, an alicyclic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an adamantyl group, etc. Examples of the cycloalkenyl group include an alicyclic unsaturated hydrocarbon group such as a cyclobutenyl group, a cyclopentenyl group and a cyclohexenyl group.

In the present invention, the aromatic hydrocarbon group which may have a substituent may be a monocyclic or polycyclic aromatic hydrocarbon group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthrasenyl group and the like as an aryl group.

In the present invention, the substituent which may be substituted with the aliphatic hydrocarbon group includes an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aryloxy group, a hydroxyl group, a carboxy group, an acyl group, an amino group, a halogen atom and the like. Can be mentioned. Specific examples of the aliphatic hydrocarbon group having a substituent include a methoxymethyl group, an ethoxymethyl group and the like as an alkoxy-substituted alkyl group, and a benzyl group and the like as an aryl-substituted alkyl group.

In the present invention, the substituents that may be substituted with the aromatic hydrocarbon group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aryloxy group, a hydroxyl group, and a carboxy group. Examples thereof include an acyl group, an amino group and a halogen atom. Specific examples of the aromatic hydrocarbon group having a substituent include a trill group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group, an n-butylphenyl group, a t-butylphenyl group and the like as an alkyl group substituted aryl group. Examples of the alkoxy group-substituted aryl group include a methoxyphenyl group, an ethoxyphenyl group, an n-butoxyphenyl group, a t-butoxyphenyl group and the like.

When the aliphatic hydrocarbon group or the aromatic hydrocarbon group has a substituent, the position of the substituent and the number of substituents are not particularly limited. Also, if they have two or more substituents, they may be the same or different.

The present invention is a thermosetting resin-based composition containing at least a thermosetting resin, dicyandiamide, and a curing accelerator for a thermosetting resin.
Further the present invention is a thermosetting resin-based composition further containing a curing agent for a thermosetting resin. Hereinafter, these may be referred to as "thermosetting resin-based compositions of the present invention".

The thermosetting resin, dicyandiamide, the curing agent for the thermosetting resin, and the curing accelerator for the thermosetting resin, which are the components of the thermosetting resin-based composition of the present invention, will be described below.

（式中、Ｒ^１～Ｒ^４は、同一または異なって、炭素数１～１６の置換もしくは非置換の炭化水素基を示す。）で表されるホスホニウムカチオンと、
下記の一般式（２）から一般式（４）で表される有機酸からなる群から選ばれる少なくとも１種の有機酸のアニオン残基からなるホスホニウム塩が挙げられる。

（式中、Ｒ^５は、炭素数１～１６の置換もしくは非置換の炭化水素基を示す。）

（式中、Ｘ、Ｙは、同一または異なって、それぞれメチレン基、イミノ基、酸素原子を示し、Ｚはジメチルメチレン基、カルボニル基を示す。）

（式中、Ａは、カルボニル基、スルホニル基を示す。） <Curing accelerator for thermosetting resin>
The phosphonium salt used as a curing accelerator for a thermosetting resin in the thermosetting resin-based composition of the present invention has the following general formula (1).

(In the formula, R ¹ to R ⁴ represent substituted or unsubstituted hydrocarbon groups having 1 to 16 carbon atoms, which are the same or different.) And the phosphonium cation.
Examples thereof include a phosphonium salt consisting of an anion residue of at least one organic acid selected from the group consisting of organic acids represented by the following general formulas (2) to (4).

(In the formula, R ⁵ indicates a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms.)

(In the formula, X and Y are the same or different and represent a methylene group, an imino group and an oxygen atom, respectively, and Z represents a dimethylmethylene group and a carbonyl group.)

(In the formula, A represents a carbonyl group and a sulfonyl group.)

《Phosphonium cation》
R ¹ to R ⁴ in the phosphonium cation of the general formula (1) represent the same or different substituted or unsubstituted hydrocarbon groups having 1 to 16 carbon atoms.

In the phosphonium cation represented by the general formula (1), the substituents represented by R ¹ to R ⁴ are substituted or unsubstituted hydrocarbon groups having 1 to 16 carbon atoms, and the number of carbon atoms is from the viewpoint of curability. 1 to 12 is preferable, and 1 to 6 carbon atoms are more preferable. Examples of the hydrocarbon group include the above-mentioned substituents, specifically, an ethyl group, a propyl group, an n-butyl group, an octyl group, a dodecyl group, an allyl group, a cyclohexyl group, a methoxymethyl group, a benzyl group and a carboxyethyl group. A phenyl group, a 4-methylphenyl group and a 4-methoxyphenyl group are preferable, and an n-butyl group, a benzyl group, a methoxymethyl group, a carboxyethyl group and a phenyl group are particularly preferable.

Examples of the phosphonium cation of the general formula (1) include tetraphenylphosphonium cation, tetrakis (4-methylphenyl) phosphonium cation, tetrakis (4-methoxyphenyl) phosphonium cation, tetrabutylphosphonium cation, tetrakis (methoxymethyl) phosphonium cation, and tetrakis. (Carboxyethyl) phosphonium cation, tetrabenzylphosphonium cation, phenyltris (4-methylphenyl) phosphonium cation, phenyltris (4-methoxyphenyl) phosphonium cation, phenyltributylphosphonium cation, phenyltris (methoxymethyl) phosphonium cation, phenyltris (Carboxyethyl) phosphonium cation, phenyltribenzylphosphonium cation, (4-methylphenyl) triphenylphosphonium cation, (4-methoxyphenyl) triphenylphosphonium cation, butyltriphenylphosphonium cation, (methoxymethyl) triphenylphosphonium cation, (Carboxyethyl) Triphenylphosphonium cation, benzyltriphenylphosphonium cation and the like can be mentioned.

Specifically, tetraphenylphosphonium cation, tetrabutylphosphonium cation, (4-methylphenyl) triphenylphosphonium cation, (4-methoxyphenyl) triphenylphosphonium cation, butyltriphenylphosphonium cation, (methoxymethyl) triphenylphosphonium cation. , (Carboxyethyl) triphenylphosphonium cations, benzyltriphenylphosphonium cations are preferred.

In particular, tetraphenylphosphonium cations, tetrabutylphosphonium cations, butyltriphenylphosphonium cations, (methoxymethyl) triphenylphosphonium cations, (carboxyethyl) triphenylphosphonium cations, and benzyltriphenylphosphonium cations are more preferable.

<< Anion residue of organic acid (conjugated base) >>
As the location of the proton that deviates from the organic acid, it is presumed that the obtained anion residue (conjugated base) can exist most stably. It is difficult to estimate which proton is released because it may form an intramolecular hydrogen bond, but it may be estimated by NMR measurement.

In the organic acid represented by the general formula (2), R ⁵ represents a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms.

Examples of the aliphatic hydrocarbon group which may have a substituent having ¹ to 16 carbon atoms as R5 in the organic acid represented by the general formula (2) include the above-mentioned examples, and specific examples thereof include carbon atoms. Preferred are 1 to 16 linear alkyl groups, cyclohexyl groups and the like, and examples of the substituents which may be substituted with an aliphatic hydrocarbon group include the above-mentioned examples, specifically, an aryl group, a hydroxyl group and a carboxy group. Etc. are preferable.

Examples of the aromatic hydrocarbon group which may have a substituent having ¹ to 16 carbon atoms as R5 in the organic acid represented by the general formula (2) include the above-mentioned examples, and specifically, a phenyl group. Etc. are preferable, and examples of the substituent which may be substituted with an aromatic hydrocarbon group include the above-mentioned examples. Specifically, an alkyl group having 1 to 4 carbon atoms, an aryl group, a hydroxyl group, a carboxy group and the like are preferable. ..

Specific examples of the organic acid represented by the general formula (2) include acetic acid, capric acid, capric acid, lauric acid, stearic acid, succinic acid, citric acid, maleic acid, 1,2-cyclohexanedicarboxylic acid, 1, Examples thereof include 4-cyclohexanedicarboxylic acid, benzoic acid, phthalic acid, trimellitic acid and pyromellitic acid.

In the organic acid represented by the general formula (3), X and Y represent the same or different methylene group, imino group and oxygen atom, respectively, and Z represents a dimethylmethylene group and a carbonyl group.

Specific examples of the organic acid represented by the general formula (3) include meldrum's acid, dimedone, barbituric acid and the like.

In the organic acid represented by the general formula (4), A represents a carbonyl group and a sulfonyl group.

Specific examples of the organic acid represented by the general formula (4) include phthalimide and saccharin.

The salt of the above-mentioned phosphonium cation and the anion residue of the organic acid can be easily produced by a known method based on the description of the present specification.

For example, an alkali metal salt of an organic acid is synthesized by a conventional method (the solvent is water, methanol, etc.), and then 1 mol of a tetra-substituted phosphonium halide is charged to 1 mol of the alkali metal salt of the organic acid and reacted. The method of forming and the like can be mentioned. In this case, the tetra-substituted phosphonium halide and the alkali metal salt of the organic acid may be used alone or in combination of two or more to form the salt. When two or more kinds are mixed, two or more kinds of tetra-substituted phosphonium halides and alkali metal salts of organic acids may be mixed first, and then a tetra-substituted phosphonium salt may be formed, or two or more kinds of tetra-substituted phosphonium salts may be formed. Phosphonium salts may be mixed.

Alternatively, a salt may be formed by neutralizing 1 mol of tetra-substituted phosphonium hydroxide with 1 mol of an organic acid.

For the purpose of precipitating high-purity crystals from the obtained reaction product and removing unreacted raw materials and by-produced inorganic salts, the obtained reaction product is subjected to water, an alcohol-based organic solvent (methanol, ethanol, etc.). Propanol, butanol, etc.), ketone-based organic solvents (acetone, methylethylketone, methylisobutylketone, diethylketone, etc.), ether-based organic solvents (tetrachloride, diethyl ether, dibutyl ether, 2-methyltetrachloride, cyclopentylmethyl ether, dioxane, etc.), It may be washed and recrystallized with a non-polar solvent (benzene, toluene, xylene, hexane, heptane, etc.) and a mixed solvent thereof.

As the tetra-substituted phosphonium halide, the tetra-substituted phosphonium hydroxide, the organic acid, and the solvent, commercially available ones may be used.

（式中、Ｒ^１～Ｒ^５は、前記と同意である。）

（式中、Ｒ^１～Ｒ^４、Ｘ、Ｙ、Ｚは、前記と同意である。）

（式中、Ｒ^１～Ｒ^４、Ａは、前記と同意である。） The phosphonium salt obtained by these methods is usually mainly composed of a 1: 1 (molar ratio) salt of a phosphonium cation and an anion residue of an organic acid, and is represented by the general formulas (5) to (7). ..

(In the formula, R ¹ to R ⁵ agree with the above.)

(In the formula, R ¹ to R ⁴ , X, Y, Z agree with the above.)

(In the formula, R ¹ to R ⁴ , A agree with the above.)

The thermosetting resin-based composition containing a curing accelerator for a thermosetting resin containing a phosphonium salt of the present invention as a component has fast-curing property and good storage stability.

Further, when it is difficult to homogenize the phosphonium salt with the curing agent for thermosetting resin, a master obtained by reacting the phosphonium salt with the curing agent for thermosetting resin in advance for the purpose of facilitating homogenization. The batch may be used as a curing accelerator for thermosetting resins.

In addition to the above phosphonium salt, the curing accelerator for thermosetting resin of the present invention further contains solvents, fillers, additives and the like usually used for curing accelerator for thermosetting resin as long as the effect is not affected. But it may be.

In addition to the above-mentioned phosphonium salt, the curing accelerator for thermosetting resin of the present invention may be used in combination with a curing accelerator for thermosetting resin as appropriate.

Typical examples of the phosphonium salt represented by the general formula (5) are shown in Table 1, and typical examples of the phosphonium salt represented by the general formula (6) are shown in Table 2 by the general formula (7). Typical examples of phosphonium salts are summarized in Table 3, but are not limited thereto.

The following description in the table indicates the following functional groups. Me: Methyl group, Bu: Butyl group, CH ₃ (CH ₂ ) ₆ : Heptyl group, CH ₃ (CH ₂ ) ₈ : Nonyl group, CH ₃ (CH ₂ ) ₁₀ : Undecyl group, CH ₃ (CH ₂ ) ₁₆ : Heptadecyl group, MeOCH ₂ : methoxymethyl group, HOOC (CH ₂ ) ₂ : carboxyethyl group, Bn: benzyl group, HOOCCH = CH: carboxyethenyl group, 2- _HOOC6 H ₁₀ : 2-carboxycyclohexyl group, Ph : Phenyl group, 4-MeC ₆ H ₄ : 4-methylphenyl group, 4-MeOC ₆ H ₄ : 4-methoxyphenyl group, 2- _HOOC6 H ₄ : 2-carboxyphenyl group, 2,4- (HOOC) ₂ C ₆ H ₃ : 2,4-dicarboxyphenyl group, 2,4,5- (HOOC) ₃ C ₆ H ₂ : 2,4,5-tricarboxyphenyl group, CH ₂ : Methylene group, CMe ₂ : Dimethylmethylene group, NH: imino group, C = O: carbonyl group, S (= O) ₂ : sulfonyl group, O: oxygen atom

<Thermosetting resin>
Examples of the thermosetting resin include epoxy resin, maleimide resin, cyanate resin, isocyanate resin and the like.

The epoxy resin is not particularly limited, and a general-purpose epoxy resin having two or more epoxy groups in one molecule can be used. For example, phenol, cresol, xylenol, catechol, resorcin, bisphenol A, etc. Phenols such as bisphenol F and / or naphthols such as naphthol and dihydroxynaphthalene and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are condensed or co-condensed in the presence of an acidic catalyst. Phenol novolak type epoxy resin obtained by epoxidizing the obtained novolak resin, orthocresol novolak type epoxy resin; bisphenol type epoxy obtained by epoxidizing bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, stilben-based phenols, etc. Resin, biphenyl type epoxy resin, stilben type epoxy resin; phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin, etc. synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl are epoxidized. Phenolic aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin; glycidyl ether type epoxy resin of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester type epoxide resin; glycidyl type or methyl glycidyl type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline or isocyanuric acid is replaced with a glycidyl group; vinylcyclohexene epoxide obtained by epoxidizing an olefin bond in the molecule. , 3,4-Epoxide cyclohexylmethyl-3,4-epoxide cyclohexanecarboxylate, 2- (3,4-epoxide) cyclohexyl-5,5-spiro (3,4-epoxide) cyclohexane-m-dioxane and other aliquots Epoxide resin; glycidyl ether of paraxylylene and / or metaxylylene-modified phenolic resin; glycidyl ether of terpene-modified phenolic resin; dicyclopentadiene-modified phenolic resin synthesized from phenols and / or naphthols and dicyclopentadiene , Dicyclopentadiene type naphthol resin glycidyl ether; cyclopentadiene modified phenol resin glycidyl ether; polycyclic aromatic ring-modified phenol resin glycidyl ether; naphthalene ring-containing phenol resin glycidyl ether; halogenated phenol novolac type epoxy resin; hydroquinone type Epoxy resin; Trimethylol propane type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Diphenylmethane type epoxy resin; Sulfur atom-containing epoxy resin and the like can be mentioned.

These epoxy resins may be used alone or in admixture of two or more, may be used as they are, may be appropriately added with a solvent, an additive, or the like, or may be a commercially available product. good.

The maleimide resin is not particularly limited, and a general-purpose maleimide resin having two or more maleimide groups in one molecule can be used, for example, 4,4'-bismaleimide diphenylmethane, N, N'. -1,3-Phenylimide maleimide, 2,2'-bis [4- (4-maleimide phenoxy) phenyl] propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide , 4-Methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, polyphenylmethanemaleimide and the like.

These maleimide resins may be used alone or in admixture of two or more, may be used as they are, may be appropriately added with a solvent, an additive, or the like, or may be a commercially available product. good.

The cyanate resin is not particularly limited, and a general-purpose cyanate resin having two or more cyanate groups in one molecule can be used, for example, 1,3-disyanatobenzene and 1,4-disi. Anatobenzene, 1,3,5-trisianatobenzene, bis (3,5-dimethyl-4-cyanatophenyl) methane, 1,3-disianatonaphthalene, 1,4-disyanatonaphthalene, 1,6-disi Anatonaphthalene, 1,8-disianatonaphthalene, 2,6-disianatonaphthalene, 2,7-disianatonaphthalene, 1,3,6-tricianatonaphthalene, 4,4'-disyanatobiphenyl, bis (4) -Cyanatophenyl) methane, 2,2'-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) Examples thereof include sulfone, 2,2'-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, and phenol novolak-type cyanate resin obtained by cyanating a novolak resin.

These cyanate resins may be used alone or in admixture of two or more, may be used as they are, may be appropriately added with a solvent, an additive, or the like, or may be a commercially available product. good.

The isocyanate resin is not particularly limited, and a general-purpose isocyanate resin having two or more isocyanate groups in one molecule can be used, for example, polyisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and polypropylene. Examples thereof include isocyanate resins in which the terminal isocyanate group of the terminal isocyanate group oligomer obtained by reaction with a polyol such as glycol and polytetramethylene glycol is blocked with phenols, alcohols and the like.

These isocyanate resins may be used alone or in admixture of two or more, may be used as they are, may be appropriately added with a solvent, an additive, or the like, or may be a commercially available product. good.

<Cyanoguanidine>
A dicyandiamide is a curing agent for a latent thermosetting resin that is solid at room temperature, disperses in a thermosetting resin-based composition without being dissolved, and dissolves when a temperature near the melting point is reached to rapidly start a reaction. It is a kind.

As the dicyandiamide in the present invention, one pulverized into granules or powder is used. It is desirable to use granular or powdery dicyandiamide uniformly dispersed in the thermosetting resin-based composition. If granular or powdery dicyandiamide is not uniformly dispersed and aggregates are present, the curing reaction is biased and a uniform cured resin product cannot be obtained.

Commercially available dicyandiamide is in the form of granules or powder and can be used as it is in the present invention.

In the present invention, dicyandiamide is distinguished from other thermosetting resin curing agents, so that the thermosetting resin curing agent described in the present invention does not contain dicyandiamide.

<Curing agent for thermosetting resin>
Examples of the curing agent for thermosetting resin (hereinafter, also referred to as “curing agent”) include a phenol resin-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, a benzoxazine-based curing agent, and the like. Further, a thermosetting resin other than the thermosetting resin used as the main agent of the thermosetting resin-based composition may be used as the curing agent for the thermosetting resin.

The phenolic resin-based curing agent is not particularly limited, and a general-purpose phenolic resin having two or more phenolic hydroxyl groups in one molecule generally used as a curing agent can be used, for example, catechol. Compounds having two or more phenolic hydroxyl groups in one molecule, such as resorcin, hydroquinone, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F , Phenols such as phenylphenol and aminophenol and / or naphthols such as naphthol and dihydroxynaphthalene and novolak type phenol resin synthesized from formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like; phenols and / or naphthols Phenolic aralkyl resins synthesized from dimethoxyparaxylene and bis (methoxymethyl) biphenyl, naphthol aralkyl resins, biphenyl aralkyl resins and other aralkyl-type phenolic resins; paraxylylene and / or metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenols. Resin; dicyclopentadiene-type phenol resin, dicyclopentadiene-type naphthol resin synthesized from phenols and / or naphthols and dicyclopentadiene; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin ; Triphenylmethane type phenol resin and the like can be mentioned.

The amine-based curing agent is not particularly limited, and general-purpose aromatic amines, aliphatic amines and the like can be used. For example, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexa and the like can be used. Alicyclics such as aliphatic polyamines such as methylenediamine and 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine and 1,2-diaminocyclohexane. Piperazine-type polyamines such as formula polyamines, N-aminoethylpiperazines, 1,4-bis (2-amino-2-methylpropyl) piperazines, diethyltoluenediamines, dimethylthiotoluenediamines, 4,4'-diamino-3, 3'-diethyldiphenylmethane, bis (methylthio) toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, polyoxytetra Methylenebis (p-aminobenzoate) and the like can be mentioned.

The acid anhydride-based curing agent is not particularly limited, and a general-purpose acid anhydride can be used, for example, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methyl. Hexahydrophthalic anhydride, 1-methylnorbornan-2,3-dicarboxylic acid anhydride, 5-methylnorbornan-2,3-dicarboxylic acid anhydride, norbornan-2,3-dicarboxylic acid anhydride, 1-methylnagic Acid anhydride, 5-methylnadic acid anhydride, nagic acid anhydride, phthalic acid anhydride, tetrahydrophthalic acid anhydride, 3-methyltetrahydrophthalic acid anhydride, 4-methyltetrahydrophthalic acid anhydride, and dodecenyl succinic acid anhydride. Things etc. can be mentioned.

The benzoxazine-based curing agent is not particularly limited, and a general-purpose benzoxazine resin can be used. For example, a Fa-type benzoxazine resin obtained by reacting bisphenol F with formaldehyde and aniline, diaminodiphenylmethane. And P-d type benzoxazine resin obtained by reacting formaldehyde with phenol and the like can be mentioned.

These curing agents can be used alone or in combination of two or more, and may be used as they are as they are, or a solvent, an additive, etc. may be added as appropriate and used as a curing agent composition. It is also possible to use a commercially available product.

<Thermosetting resin-based composition>
The thermosetting resin-based composition of the present invention comprises a thermosetting resin, dicyandiamide, and a curing accelerator for a thermosetting resin, and may further contain a curing agent for a thermosetting resin. Further, a solvent, a filler, an additive and the like usually used in a thermosetting resin-based composition may be further contained as long as the effect is not affected.

The thermosetting resin-based composition can contain various known inorganic fillers in order to reduce the coefficient of linear expansion. Examples of the inorganic filler include fused silica, crystalline silica, alumina, aluminum nitride and the like. These inorganic fillers may be surface-treated with a coupling agent such as a silane coupling agent.

In addition, a pigment such as an ion trap agent, a mold release agent, and carbon black may be added to the thermosetting resin-based composition, and a resin other than the thermosetting resin may be contained.

If the content of dicyandiamide in the thermosetting resin-based composition of the present invention is less than 0.5 parts by weight, the curing reaction time may become longer and the glass transition temperature Tg may decrease, and if it is more than 20 parts by weight. Since the curing reaction time may be shortened and the dissolution of dicyandiamide during the curing reaction may be insufficient, it is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the thermosetting resin, and the cured physical properties are improved. More strictly, it is more preferable that the content is 5 to 10 parts by weight.

If the content of the phosphonium salt in the thermosetting resin-based composition of the present invention is less than 0.5 parts by weight, the curing power of the composition may not be sufficiently exerted, and if it is more than 10 parts by weight, the composition. Since the storage stability of the product may deteriorate, it is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin, and if the curability is more strictly considered, such a content may be determined. It is more preferably 0.7 to 5 parts by weight. Further, when a curing agent for a thermosetting resin is used, the content of the curing agent is the reactive group equivalent in the thermosetting resin (for example, in the case of an epoxy resin, the epoxy equivalent in the resin) and the dicyandiamide + curing agent. In general, the equivalent ratio between the reactive group equivalent and the equivalent of dicyandiamide + curing agent is 1.0: 0.9 to 1.0: 1.2 in consideration of the equivalent ratio with the equivalent of. To do so.

When the thermosetting resin-based composition of the present invention is used for a prepreg, it is preferable that each component is in the state of a varnish dissolved or dispersed in an organic solvent.

Examples of the organic solvent used for producing the varnish include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvents, ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethylsulfoxide. And the like, an aprotonic polar solvent and the like can be mentioned. These organic solvents may be used alone or in admixture of two or more, or commercially available products may be used.

The method for preparing the thermosetting resin-based composition is not particularly limited, and the thermosetting resin-based composition can be prepared by uniformly mixing the above components. As a preferable preparation method, a method of uniformly stirring and mixing the thermosetting resin, didiandiamid, and the curing accelerator for the thermosetting resin at a temperature of about 20 to 150 ° C. can be mentioned, and in some cases, the above-mentioned varnish is produced. The solvent exemplified as the solvent used in the above may be used. When a curing agent for a thermosetting resin is added, it is preferable that the mixture of the curing agent and the curing accelerator is heated and then cooled, then mixed with dicyandiamide and the thermosetting resin, heated and then cooled.

By heating the mixture of the curing agent and the curing accelerator, the viscosity of the curing agent is lowered, stirring and mixing are facilitated, and the curing agent and the curing accelerator are uniformly dispersed.

The mixture of the curing agent and the curing accelerator can be accurately weighed and handled easily by pre-cooling the mixture before mixing with the thermosetting resin and dicyandiamide.

If it is difficult to homogenize the curing accelerator into a curing agent, a masterbatch obtained by heating and dissolving the curing accelerator in a part of the curing agent at a high concentration and then cooling may be used as the curing accelerator. This masterbatch has relatively good solubility in a curing agent. In addition, dicyandiamide is not usually used for a masterbatch.

Further, each component of the thermosetting resin, dicyandiamide, curing agent, and curing accelerator may be mixed at once in each mixing step, or may be mixed little by little in a plurality of times. Further, when the above solvent, additive, inorganic filler and the like are mixed, the mixture can be similarly mixed once or in a plurality of times at an arbitrary time.

When mixing the curing agent and the curing accelerator, or when mixing the thermosetting resin and dicyandiamide, in order to facilitate uniform stirring and mixing, a kneader such as a roll, kneader, bead mill, mixer, etc. May be used.

The thermosetting resin-based composition of the present invention exhibits high catalytic activity, can be cured in a short time, and has good storage stability.

<Thermosetting resin-based cured product>
In the present invention, the thermosetting resin-based cured product loses the fluidity of the thermosetting resin by heating the thermosetting resin-based composition under specific conditions according to the thermosetting resin-based composition. , A hardened solid substance. Hereinafter, the solid substance obtained by curing the thermosetting resin-based composition of the present invention may be referred to as "the thermosetting resin-based cured product of the present invention".

The thermosetting resin-based cured product of the present invention can be obtained by heating the above-mentioned thermosetting resin-based composition of the present invention under normal conditions for curing the thermosetting resin-based composition. It can be obtained by heating at a normal curing temperature of about 100 to 250 ° C. and a curing time of 30 seconds to 15 hours, and the conditions can be changed as appropriate.

Hereinafter, the thermosetting resin-based composition of the present invention will be described in detail with reference to Examples and Test Examples, but the present invention is not limited thereto.

<Example 1>
100 parts by weight of liquid bisphenol A type epoxy resin jER828EL (epoxy equivalent 186, manufactured by Mitsubishi Chemical Co., Ltd.), dicyandiamide (Tokyo Kasei Kogyo) in a plastic cup dedicated to the rotating / revolving mixer (Awatori Rentaro ARE-310 manufactured by Shinky Co., Ltd.) (Manufactured) 8 parts by weight and 2 parts by weight of tetrabutylphosphonium laurate (Compound No. 5-43) (hereinafter referred to as "TBPLA") were added and heated to 40 ° C. in an oven. This was set in ARE-310, stirred at 2000 rpm for 1 minute, and defoamed for another 1 minute to obtain a thermosetting resin-based composition.

<Example 2>
Thermosetting as in Example 1 except that 2 parts by weight of tetrabutylphosphonium hydroxyhexahydrophthalate (Compound No. 5-95) (hereinafter referred to as "TBP-3S") was used instead of 2 parts by weight of TBPLA. A resin-based composition was obtained.

<Example 3>
Thermosetting resin-based composition in the same manner as in Example 1 except that 2 parts by weight of tetrabutylphosphonium phthalimide (Compound No. 7-4) (hereinafter referred to as “TBP-phthalimide”) was used instead of 2 parts by weight of TBPLA. Got

<Example 4>
Thermosetting resin-based as in Example 1 except that 2 parts by weight of tetrabutylphosphonium dimedone salt (Compound No. 6-17) (hereinafter referred to as “TBP-dimedone”) was used instead of 2 parts by weight of TBPLA. The composition was obtained.

<Example 5>
Thermosetting resin-based composition as in Example 1 except that 2 parts by weight of tetrabutylphosphonium saccharide (Compound No. 7-17) (hereinafter referred to as "TBP-saccharide") was used instead of 2 parts by weight of TBPLA. Got

<Comparative Example 1>
A thermosetting resin-based composition was obtained in the same manner as in Example 1 except that 2 parts by weight of tetraphenylphosphonium thiocyanate (hereinafter referred to as “TPP-SCN”) was used instead of 2 parts by weight of TBPLA.

<Comparative Example 2>
A thermosetting resin-based composition was obtained in the same manner as in Example 1 except that 4 parts by weight of tri-p-tolylphosphine (hereinafter referred to as "TPTP") was used instead of 2 parts by weight of TBPLA.

<Comparative Example 3>
A thermosetting resin-based composition was obtained in the same manner as in Example 1 except that 4 parts by weight of triphenylphosphine (hereinafter referred to as “TPP”) was used instead of 2 parts by weight of TBPLA.

<Comparative Example 4>
A thermosetting resin-based composition was obtained in the same manner as in Example 1 except that 0.8 parts by weight of 2-ethyl-4-methylimidazole (hereinafter referred to as "2E4MZ") was used instead of 2 parts by weight of TBPLA. ..

<Comparative Example 5>
A thermosetting resin-based composition was obtained in the same manner as in Example 1 except that 2 parts by weight of TBPLA was omitted.

[Curability test]
As a conventional method for evaluating the curability of a thermosetting resin-based composition, a gelation time measurement method based on EIMS T-901, a differential scanning calorimetry method based on JIS K 6910, and JIS K 6300-2 are based. Although a torque measurement method can be mentioned, the thermosetting resin-based composition of the present invention was evaluated for curability by a differential scanning calorimetry method based on JIS K 6910. In the differential scanning calorimetry method, a sample is heated using a differential scanning calorimeter (DSC), and the superiority or inferiority of the curability is evaluated by the calorific value calculated by the measurement. The curing reaction of the thermosetting resin-based composition is an exothermic reaction, and it can be said that the larger the calorific value, the more the crosslink formation by addition polymerization progresses and the better the curability.

The test and evaluation methods are described below.
The obtained thermosetting resin-based composition was subjected to a measurement temperature range of 30 ° C. to 200 ° C. and a temperature rise rate of 10 ° C./under under a nitrogen stream using a differential scanning calorimeter (DSC7020 manufactured by SII Nanotechnology Co., Ltd.). It was measured under the condition of min. The larger the calorific value, the better the curability, and if the calorific value measured using DSC is 150 J / g or more, it can be said that the curability is good, but preferably 175 J / g or more, more. It is preferably 200 J / g or more.

[Storage stability test]
The storage stability of the thermosetting resin-based composition can be measured and evaluated by a conventional storage stability evaluation method, but in the present invention, the calorific value calculated by the differential scanning calorimetry method is thermally cured. The storage stability was evaluated based on the calorific value retention rate by comparing immediately after the preparation of the sex resin-based composition and after storage at 25 ° C. for 7 days.

The test and evaluation methods are described below.
The obtained thermosetting resin-based composition was stored at 25 ° C. for 7 days, and DSC measurement was performed again. A thermosetting resin-based composition having poor storage stability tends to undergo a curing reaction (exothermic reaction) during storage at 25 ° C., and the DSC calorific value after storage for a certain period of time tends to be small. Therefore, in the thermosetting resin-based composition described in this example, if the DSC calorific value retention rate after storage at 25 ° C. for 7 days is 80% or more, the storage stability is good, but preferably 85. % Or more, more preferably 90% or more.
Therefore, the calorific value immediately after the preparation and after 7 days at 25 ° C. were compared, and those having a DSC calorimetry retention rate of 90% or more were marked with ◯, those with a DSC calorimeter retention rate of 80 to 90% were marked with Δ, and those with a DSC calorific value of 80% or less were marked with x.
The results are shown in Tables 4 and 5.

As shown in Tables 4 and 5, the thermosetting resin-based composition according to the present invention has a large DSC calorific value and a high calorific value retention rate after 7 days at 25 ° C.

That is, the thermosetting resin-based composition containing the phosphonium salt of the present invention is useful because it has fast curing property and good storage stability as compared with the case where a conventional curing accelerator is used.

Since the thermosetting resin-based composition of the present invention is excellent in quick-curing property and storage stability, for example, resin encapsulation of various small electric / electronic parts and semiconductor parts, fiber-reinforced composite materials, and lamination are performed. It is also extremely useful in the fields of films and sheets for applications such as boards.

Claims (9)

A thermosetting resin-based composition comprising a thermosetting resin, dicyandiamide, and a curing accelerator for a thermosetting resin, wherein the curing accelerator for a thermosetting resin has the following general formula (1).

(In the formula, R ¹ to R ⁴ represent substituted or unsubstituted hydrocarbon groups having 1 to 16 carbon atoms, which are the same or different.) And the phosphonium cation.
It is characterized by containing a phosphonium salt consisting of an anion residue of at least one organic acid selected from the group consisting of organic acids represented by the following general formulas (2) to (4). A characteristic thermosetting resin-based composition.

(In the formula, R ⁵ indicates a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms.)

(In the formula, X and Y are the same or different and represent a methylene group, an imino group and an oxygen atom, respectively, and Z represents a dimethylmethylene group and a carbonyl group.)

(In the formula, A represents a carbonyl group and a sulfonyl group.) In the general formula (1), R ¹ to R ⁴ are the same or different, and have a butyl group, a phenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a benzyl group, a methoxymethyl group, and a carboxyethyl group. The thermosetting resin-based composition according to claim 1, which is a substituent selected from the above. The thermosetting resin-based composition according to claim 1, wherein in the general formula (1), R ¹ to R ⁴ are all phenyl groups. The thermosetting resin-based composition according to claim 1, wherein in the general formula (1), R ¹ to R ⁴ are all butyl groups. The general formula (2) is acetic acid, caproic acid, capric acid, capric acid, lauric acid, stearic acid, succinic acid, citric acid, maleic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, benzoic acid. The thermosetting resin-based composition according to any one of claims 1 to 4, wherein it is one kind of organic acid selected from the group consisting of an acid, a phthalic acid, a trimellitic acid, and a pyromellitic acid. The thermosetting resin-based composition according to any one of claims 1 to 4, wherein the general formula (3) is one organic acid selected from the group consisting of meldrum's acid, dimedone, and barbituric acid. thing. The thermosetting resin-based composition according to any one of claims 1 to 4, wherein the general formula (4) is one kind of organic acid selected from the group consisting of phthalimide and saccharin. The thermosetting according to any one of claims 1 to 7, wherein the thermosetting resin is one or more thermosetting resins selected from an epoxy resin, a maleimide resin, a cyanate resin, and an isocyanate resin. Sex resin-based composition. A thermosetting resin-based cured product obtained by curing the thermosetting resin-based composition according to any one of claims 1 to 8.