JP2021195392A - Thermosetting composition and kit for obtaining the composition - Google Patents

Abstract

To provide a thermosetting composition capable of shortening the precuring time to improve the productivity of electric/electronic materials such as semiconductors.SOLUTION: A thermosetting composition is obtained by mixing a main agent containing a polymaleimide group-containing compound and a benzoxazine compound and a curing agent containing an aromatic polyamine compound and an alicyclic amine compound in which a primary amino group is bonded to carbon atoms at at least 1 and 3 positions of the cyclohexane ring. 4,4'-diphenylmethanebismaleimide is used as the polymaleimide group-containing compound, P-d type benzoxazine is used as the benzoxazine compound, diethyltoluenediamine is used as the aromatic polyamine compound, and 4-methyl-1,3-cyclohexanediamine is used as the alicyclic amine compound.SELECTED DRAWING: None

Description

The present invention relates to a thermosetting composition that can be used as a sealing material, an impregnating material, an adhesive, or the like for an electric / electronic material such as a semiconductor or a printed wiring substrate.

Conventionally, a cured product having excellent heat resistance has been adopted as a sealing material for electric / electronic materials such as semiconductors. As a thermosetting composition for obtaining such a cured product, a composition containing a polymaleimide group-containing compound such as 4,4'-diphenylmethane bismaleimide and an aromatic polyamine compound such as 4,4'-diaminodiphenylmethane is known. (Patent Document 1).

In order to obtain a cured product using such a thermosetting composition, a method of performing final main curing after undergoing a pre-curing step is adopted. This is because if the main curing is performed without undergoing pre-curing, curing strain will occur. However, in the case of the thermosetting composition described in Patent Document 1, it takes several hours to complete the pre-curing. If the pre-curing time is long, there is a drawback that the productivity of electric / electronic materials such as semiconductors is lowered.

Japanese Patent No. 3150366

An object of the present invention is to provide a thermosetting composition capable of shortening the pre-curing time and improving the productivity of electric / electronic materials such as semiconductors.

The present invention solves the above-mentioned problems by adding two specific kinds of compounds to a polymaleimide group-containing compound and an aromatic polyamine compound. That is, the present invention comprises a polymaleimide group-containing compound, an aromatic polyamine compound, a benzoxazine compound, and an alicyclic amine compound in which a primary amino group is bonded to at least the 1st and 3rd carbon atoms of the cyclohexane ring. Hereinafter, the present invention relates to a thermosetting composition containing simply "alicyclic amine compound"). Such a thermosetting composition is generally provided in the form of a kit (combination) of a main agent and a curing agent, the main agent containing a polymaleimide group-containing compound and a benzoxazine compound, and the curing agent is an aromatic polyamine. It contains a compound and an alicyclic amine compound.

（式中、Ｒ₁及びＲ₂は水素原子又は有機基である。）
具体的には、４，４’−ジフェニルメタンビスマレイミド、ビス−（３エチル−５メチル−４−マレイミドフェニル）メタン、ビスフェノールＡジフェニルエーテルビスマレイミド、フェニレンビスマレイミド、４−メチル−１，３−フェニレンビスマレイミド又は１，６’−ビスマレイミド−（２，２，４−トリメチル）ヘキサン等が挙げられ、これらを単独で又は混合して用いられる。また、これらを重合させたポリマー（重合物）を用いてもよい。 The polymaleimide group-containing compound used in the present invention is a compound having at least two or more maleimide groups represented by Chemical formula 1 in one molecule, and conventionally known thermosetting compounds can be adopted.

(In the formula, R ₁ and R ₂ are hydrogen atoms or organic groups.)
Specifically, 4,4'-diphenylmethane bismaleimide, bis- (3 ethyl-5 methyl-4-maleimidephenyl) methane, bisphenol A diphenyl ether bismaleimide, phenylene bismaleimide, 4-methyl-1,3-phenylene bis. Examples thereof include maleimide or 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, which may be used alone or in combination. Further, a polymer obtained by polymerizing these may be used.

The polymer comprises a polymaleimide group-containing monomer such as 4,4'-diphenylmethanebismaleimide or bis- (3 ethyl-5-methyl-4-maleimidephenyl) methane, and a compound having one or more hydroxyl groups in the molecule. It can be obtained by polymerization by mixing and heating. This polymerization reaction is preferably carried out in the presence of an epoxy compound. This is because the polymer and the epoxy compound are well compatible with each other and the polymer is less likely to settle. The heating temperature is generally about 110 to 160 ° C., and the heating time is about 1 to 24 hours. As the compound having one or more hydroxyl groups in the molecule, conventionally known compounds are used, for example, hydroquinone, phenols, cresols, xylenols, methyl hydroxybenzoate and the like are used.

The benzoxazine compound used in the present invention is a compound having one or more, preferably two or more benzoxazine rings in one molecule, and conventionally known compounds can be adopted as the thermosetting compounds. Specifically, the benzoxazine compounds described in JP-A-2014-141426 such as P-d type benzoxazine, FA type benzoxazine, ALP-d type benzoxazine manufactured by Shikoku Kasei Kogyo Co., Ltd .; Konishi BS-BX2 manufactured by Kagaku Kogyo Co., Ltd .; CR-276 manufactured by Tohoku Kako Co., Ltd., etc. may be mentioned, and these may be used alone or in combination.

A polymaleimide group-containing compound and a benzoxazine compound are mixed to form a main agent, and it is preferable to further mix an epoxy compound in the main agent. By adding the epoxy compound, the curing time and the curing temperature can be reduced, and the adhesiveness can be improved. The epoxy compound is a compound having an epoxy group, and conventionally known curable compounds can be adopted. Specifically, known epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, and biphenyl type epoxy resin are used alone or in combination.

The aromatic polyamine compound used in the present invention is one of the curing agents and has an aromatic ring such as a benzene ring or a naphthalene ring in one molecule, and has two or more primary and / or secondary amino groups. It is a compound. As the aromatic polyamine compound, conventionally known compounds can be adopted. Specifically, diethylmethylbenzenediamine (manufactured by Albemar: product name EtaCure 100), bis (methylthio) toluenediamine (manufactured by Mitsui Kagaku Fine Co., Ltd .: product name EtaCure 300), 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl sulfone or 4,4'-diaminodiphenyl ether and the like are used alone or in combination. Due to the stricter regulations on aromatic amine compounds in recent years, in the present invention, the pre-curing time can be shortened, so that the curing rate is slow but the toxicity is low, diethylmethylbenzenediamine and / or bis (methylthio) toluenediamine. It is preferable to adopt.

（式中、Ｒ₃、Ｒ₄、Ｒ₅及びＲ₆は水素原子、アミノ基又は有機基を表す。）
具体的には、１，３−シクロヘキサンジアミン、６−メチル−１，３−シクロヘキサンジアミン（１−メチル−２，４−シクロヘキサンジアミンとも称呼する。）、２−メチル−１，３−シクロヘキサンジアミン（１−メチル−２，６−シクロヘキサンジアミンとも称呼する。）、１，３，５−シクロヘキサントリアミン等を用いることができる。工業製品としては、メチル−１，３−シクロヘキサンジアミンを含有するＢａｘｘｏｄｕｒ（登録商標）ＥＣ２１０が挙げられる。 The alicyclic amine compound used in the present invention has a primary amino group bonded to at least the 1st and 3rd carbon atoms of the cyclohexane ring and is one of the curing agents. In terms of the structural formula, it is as shown in Chemical formula 2.

(In the formula, R ₃ , R ₄ , R ₅ and R ₆ represent a hydrogen atom, an amino group or an organic group.)
Specifically, 1,3-cyclohexanediamine, 6-methyl-1,3-cyclohexanediamine (also referred to as 1-methyl-2,4-cyclohexanediamine), 2-methyl-1,3-cyclohexanediamine (also referred to as 1-methyl-2,4-cyclohexanediamine). It is also called 1-methyl-2,6-cyclohexanediamine), 1,3,5-cyclohexanetriamine and the like can be used. Examples of industrial products include Baxxodor® EC210 containing methyl-1,3-cyclohexanediamine.

What is characteristic of the present invention is that the pre-curing time cannot be shortened unless it is an alicyclic amine compound in which a primary amino group is bonded to carbon atoms at at least the 1st and 3rd positions of the cyclohexane ring. Is. For example, as shown in Examples and Comparative Examples below, a compound in which a primary amino group is bonded to a carbon atom at only the 1-position of the cyclohexane ring, and a primary carbon atom at the 1-position and 2-position of the cyclohexane ring. Compounds with an amino group bonded, compounds with a primary amino group bonded to the carbon atoms at the 1st and 4th positions of the cyclohexane ring, and carbon atoms other than the carbon atoms at the 1st and 3rd positions of the cyclohexane ring. Compounds to which a primary amino group is attached and aliphatic amines having no cyclohexane ring cannot shorten the time for pre-curing.

The compounding ratio of the polymaleimide group-containing compound and the benzoxazine compound, which are the main agents, is about 0.1 to 60% by mass of the benzoxazine compound with respect to the total mass of both. When the epoxy compound is contained in the main agent, the mass of the epoxy compound is about 10 to 300% by mass with respect to the total mass of the polymaleimide group-containing compound and the benzoxazine compound. The compounding ratio of the aromatic polyamine compound and the alicyclic amine compound as the curing agent is about 0.1 to 40% by mass of the alicyclic amine compound with respect to the total mass of both.

Various additives may be added to the thermosetting composition according to the present invention as long as the effects of the present invention are not impaired. For example, fillers such as silica, alumina, aluminum hydroxide, glass, talc, clay, mica, calcium carbonate or carbon; fibrous reinforcing agents such as glass fiber or carbon fiber; colorants such as dyes and pigments; silicone and fluorine. A mold release agent such as a system compound may be added.

The method of using the thermosetting composition according to the present invention is to pre-cure at 80 to 170 ° C. for about 10 minutes to 2 hours, and then to main cure at 170 to 200 ° C. for about 2 to 7 hours. Is adopted. The cured product after the main curing has excellent heat resistance. Further, a thermosetting composition according to the present invention may be dissolved in a solvent to prepare a varnish, and the varnish may be applied to a sheet to be used. As the solvent, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, N-methyl-2-pyrrolidone and the like can be used. As the sheet-like material, a metal foil such as copper foil or aluminum foil; a synthetic resin film such as a polyimide film or a polyethylene terephthalate film; a cloth made of glass fiber, carbon fiber, polyester fiber, polyamide fiber or alumina fiber; paper or the like. Can be used.

The thermosetting composition according to the present invention is used as a sealing material for electronic parts, a casting material, a molding material for a circuit board, a laminated material, a paint, an adhesive, a resist ink and the like. Further, the above-mentioned cloth may be coated and impregnated and dried to form a prepreg. A circuit board can be obtained by laminating these prepregs and curing them by heating.

Since the thermosetting composition according to the present invention contains a polymaleimide group-containing compound, an aromatic polyamine compound, a benzoxazine compound and an alicyclic amine compound, it has an effect that the pre-curing time can be shortened. Therefore, if an electronic component or the like is produced using the thermosetting composition according to the present invention, the productivity can be improved.

Example 1
9 g of bis- (3 ethyl-5 methyl-4-maleimidephenyl) methane (manufactured by Keiai Kasei Co., Ltd.) as a polymaleimide group-containing compound, and P-d type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a benzoxazine compound. 1 g, 1.8 g of diethylmethylbenzenediamine (manufactured by Albemar: product name EtaCure 100) as an aromatic polyamine compound, and 0 of methyl-1,3-cyclohexanediamine (Baxxodur® EC210) as an alicyclic amine compound. .2 g was weighed, 10 g of acetone was added thereto, and the mixture was mixed and stirred. Then, acetone was distilled off at 90 ° C. for 2 hours to obtain a thermosetting composition.

Example 2
Thermosetting composition by the same method as in Example 1 except that 1,3-cyclohexanediamine is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. I got a thing.

Example 3
4,4'-Diphenylmethane bismaleimide (manufactured by Kaye Kasei Co., Ltd.) instead of bis- (3 ethyl-5 methyl-4-maleimidephenyl) methane (manufactured by Kaye Kasei Co., Ltd.) as a polymaleimide group-containing compound. A thermosetting composition was obtained by the same method as in Example 1 except that the above was used.

Comparative Example 1
Same as Example 1 except that the mass of diethylmethylbenzenediamine (manufactured by Albemarle Corporation: product name EtaCure 100) is changed to 2 g and methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) is not used. A thermosetting composition was obtained by the above method.

Comparative Example 2
Same as Example 1 except that the mass of bis- (3 ethyl-5 methyl-4-maleimidephenyl) methane (manufactured by Keiai Kasei Co., Ltd.) is changed to 10 g and P-d type benzoxazine is not used. A thermosetting composition was obtained by the method.

Comparative Example 3
The mass of bis- (3 ethyl-5 methyl-4-maleimidephenyl) methane (manufactured by Keiai Kasei Co., Ltd.) was changed to 10 g, and P-d type benzoxazine was not used, and diethylmethylbenzenediamine (Albemar). A thermosetting composition was obtained by the same method as in Example 1 except that the mass of EtaCure 100) manufactured by the company was changed to 2 g and methyl-1,3-cyclohexanediamine was not used.

Comparative Example 4
A thermosetting composition was obtained by the same method as in Example 1 except that 1,2-cyclohexane was used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210).

Comparative Example 5
A thermosetting composition was obtained by the same method as in Example 1 except that 1,4-cyclohexane was used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210).

The thermosetting compositions obtained in Examples 1 to 3 and the thermosetting compositions obtained in Comparative Examples 1 to 5 were exposed to an atmosphere of 150 ° C. and pre-cured to become a solid. It was measured. The results are shown in Table 1.
[Table 1]
━━━━━━━━━━━━━━━━━━━━━━
Time to pre-cure
━━━━━━━━━━━━━━━━━━━━━━
Example 1 90 minutes
Example 2 102 minutes
Example 3 5 minutes
Comparative Example 1 120 minutes or more
Comparative Example 2 120 minutes or more
Comparative Example 3 120 minutes or more
Comparative Example 4 120 minutes or more
Comparative Example 5 120 minutes or more
━━━━━━━━━━━━━━━━━━━━━━

As is clear from Table 1, it can be seen that the thermosetting composition according to the examples has a shorter pre-curing time than the thermosetting composition according to the comparative example.

Example 4
(Preparation of main agent)
25 g of 4,4'-diphenylmethane bismaleimide (manufactured by KAI Kasei Co., Ltd.) as a polymaleimide group-containing compound, and bis- (3 ethyl-5methyl-4-maleimidephenyl) methane (Kay.) As a polymaleimide group-containing compound. Ai Kasei Co., Ltd.) 5 g, P-d type benzoxazine as a benzoxazine compound (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 10 g, bisphenol F type epoxy resin (manufactured by DIC: product name Epicron 830) 30 g, and alicyclic epoxy resin (manufactured by DIC) Dycel Co., Ltd .: Product name: Serokiside 2021P) 30 g was mixed at 120 ° C. and then cooled to 23 ° C. to obtain a main agent.
(Preparation of curing agent)
18 g of diethylmethylbenzenediamine (manufactured by Albemar: product name EtaCure 100) as an aromatic polyamine compound and 2 g of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound at room temperature. Mixing gave a curing agent.
The above-mentioned main agent and curing agent were mixed at room temperature to obtain a thermosetting composition.

Example 5
(Preparation of main agent)
30 g of 4,4'-diphenylmethane bismaleimide (manufactured by Keiai Kasei Co., Ltd.) as a polymaleimide group-containing compound, 10 g of P-d type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a benzoxazine compound, and a bisphenol A type epoxy resin. (Manufactured by Mitsubishi Chemical Co., Ltd .: Product name Epicoat 828) 60 g was mixed at 120 ° C. and then cooled to 23 ° C. to obtain a main agent.
This main agent and the curing agent used in Example 4 were mixed at room temperature to obtain a thermosetting composition.

Example 6
A thermosetting composition was obtained by the same method as in Example 4 except that the mass of Pd-type benzoxazine (manufactured by Shikoku Chemicals Corporation) as a benzoxazine compound was changed to 1 g.

Example 7
A thermosetting composition was obtained by the same method as in Example 4 except that the mass of Pd-type benzoxazine (manufactured by Shikoku Chemicals Corporation) as a benzoxazine compound was changed to 3 g.

Example 8
Thermosetting composition in the same manner as in Example 4, except that 1,3-cyclohexanediamine is used in place of methyl-1,3-cyclohexanediamine (Baxxodur® EC210) as an alicyclic amine compound. I got a thing.

Example 9
(Preparation of main agent)
25 g of 4,4'-diphenylmethane bismaleimide (manufactured by KAI Kasei Co., Ltd.) as a polymaleimide group-containing compound, and bis- (3 ethyl-5methyl-4-maleimidephenyl) methane (Kay.) As a polymaleimide group-containing compound. Ai Kasei Co., Ltd.) 5 g, P-d type benzoxazine as a benzoxazine compound (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 30 g, bisphenol F type epoxy resin (manufactured by DIC: product name Epicron 830) 20 g, and alicyclic epoxy resin (manufactured by DIC) Dycel Co., Ltd .: Product name: Serokiside 2021P) 40 g was mixed at 120 ° C. and then cooled to 23 ° C. to obtain a main agent.
(Preparation of curing agent)
17 g of diethylmethylbenzenediamine (manufactured by Albemar: product name EtaCure 100) as an aromatic polyamine compound and 3 g of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound at room temperature. Mixing gave a curing agent.
The above-mentioned main agent and curing agent were mixed at room temperature to obtain a thermosetting composition.

Example 10
(Preparation of main agent)
30 g of 4,4'-diphenylmethanebismaleimide (manufactured by Keiai Kasei Co., Ltd.) as a polymaleimide group-containing compound, and bis- (3 ethyl-5methyl-4-maleimidephenyl) methane (Kay.) As a polymaleimide group-containing compound. Ai Kasei Co., Ltd.) 10 g, P-d type benzoxazine as a benzoxazine compound (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 10 g, bisphenol F type epoxy resin (manufactured by DIC: product name Epicron 830) 20 g, and alicyclic epoxy resin (manufactured by DIC) Dycel Co., Ltd .: Product name: Serokiside 2021P) 40 g was mixed at 120 ° C. and then cooled to 23 ° C. to obtain a main agent.
(Preparation of curing agent)
19 g of diethylmethylbenzenediamine (manufactured by Albemar: product name EtaCure 100) as an aromatic polyamine compound and 1 g of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound at room temperature. Mixing gave a curing agent.
The above-mentioned main agent and curing agent were mixed at room temperature to obtain a thermosetting composition.

Example 11
(Preparation of main agent)
The main agent was obtained by the same method as in Example 4 except that the mass of P-d type benzoxazine (manufactured by Shikoku Chemicals Corporation) as a benzoxazine compound was changed to 3 g.
(Preparation of curing agent)
At room temperature, 15 g of diethylmethylbenzenediamine (manufactured by Albemar: product name EtaCure 100) as an aromatic polyamine compound and 5 g of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound were added at room temperature. Mixing gave a curing agent.
The above-mentioned main agent and curing agent were mixed at room temperature to obtain a thermosetting composition.

Example 12
Same as Example 4 except that the mass of the bisphenol F type epoxy resin (manufactured by DIC: product name Epicron 830) is changed to 60 g and the alicyclic epoxy resin (manufactured by Daicel: product name Serokiside 2021P) is not used. A thermosetting composition was obtained by the above method.

Example 13
A thermosetting composition is obtained by the same method as in Example 12 except that Fa-type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is used instead of Pd type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.). rice field.

Example 14
A thermosetting composition is obtained by the same method as in Example 12 except that ALP-d type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.) is used instead of P-d type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.). rice field.

Example 15
(Preparation of main agent)
25 g of 4,4'-diphenylmethanebismaleimide (manufactured by KAI Kasei Co., Ltd.) as a polymerimide group-containing monomer, and bis- (3 ethyl-5methyl-4-maleimidephenyl) methane (Kay.) As a polymerimide group-containing monomer. After mixing 5 g of Ai Kasei), 1 g of hydroquinone, 30 g of bisphenol F type epoxy resin (DIC: product name Epicron 830) and 30 g of alicyclic epoxy resin (Dycel: product name Serokiside 2021P), 150 ° C. The mixture was mixed and stirred for 3 hours to obtain a polymer by polymerizing a polymaleimide group-containing monomer. This polymer and the epoxy resin were well compatible with each other, and the product solution did not form a precipitate. The temperature of this product is cooled to 120 ° C., 10 g of Pd-type benzoxazine (manufactured by Shikoku Chemicals Corporation) as a benzoxazine compound is added, mixed for 1 hour, and then cooled to 23 ° C. to obtain a main agent. rice field.
This main agent and the curing agent used in Example 4 were mixed at room temperature to obtain a thermosetting composition.

Example 16
A thermosetting composition was obtained by the same method as in Example 15 except that the mass of the bisphenol F type epoxy resin (manufactured by DIC: product name Epicron 830) was changed to 60 g and no alicyclic epoxy resin was used. rice field.

Comparative Example 6
A thermosetting composition was obtained by the same method as in Example 4 except that methyl-1,3-cyclohexanediamine was not used as the alicyclic amine compound.

Comparative Example 7
A thermosetting composition was obtained by the same method as in Example 4 except that Pd-type benzoxazine was not used as the benzoxazine compound.

Comparative Example 8
Thermosetting composition by the same method as in Example 4, except that 1,2-cyclohexanediamine is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. I got a thing.

Comparative Example 9
Thermosetting composition by the same method as in Example 4, except that 1,4-cyclohexanediamine is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. I got a thing.

Comparative Example 10
By the same method as in Example 4, except that 4,4'-methylenebis (cyclohexylamine) is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. A thermosetting composition was obtained.

Comparative Example 11
Example 4 except that 1,3-bisaminomethylcyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc.) is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. A thermosetting composition was obtained by the same method as above.

Comparative Example 12
A thermosetting composition is prepared by the same method as in Example 4 except that isophorophondiamine is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. Obtained.

Comparative Example 13
Thermosetting by the same method as in Example 4, except that norbornane diamine (manufactured by Mitsui Chemicals, Inc.) is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. A sex composition was obtained.

Comparative Example 14
A thermosetting composition is obtained by the same method as in Example 4 except that hexamethyldiamine is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. rice field.

Comparative Example 15
By the same method as in Example 4, except that N- (2-aminoethyl) ethanolamine is used instead of methyl-1,3-cyclohexanediamine (Baxxodur (registered trademark) EC210) as an alicyclic amine compound. A thermocurable composition was obtained.

Comparative Example 16
(Preparation of main agent)
25 g of 4,4'-diphenylmethane bismaleimide (manufactured by KAI Kasei Co., Ltd.) as a polymaleimide group-containing compound, and bis- (3 ethyl-5methyl-4-maleimidephenyl) methane (Kay.) As a polymaleimide group-containing compound. After mixing 5 g (manufactured by Ai Kasei Co., Ltd.) and 60 g of bisphenol F-type epoxy resin (manufactured by DIC: product name Epicron 830) at 120 ° C., the mixture was cooled to 23 ° C. to obtain a main agent.
A curing agent consisting of 20 g of diethylmethylbenzenediamine (manufactured by Albemarle Corporation: product name EtaCure 100) as an aromatic polyamine compound was mixed with this main agent at room temperature to obtain a thermosetting composition.

Comparative Example 17
A thermosetting composition was obtained by the same method as in Comparative Example 16 except that 10 g of Pd-type benzoxazine (manufactured by Shikoku Chemicals Corporation) as a benzoxazine compound was mixed with the main agent used in Comparative Example 16. rice field.

Comparative Example 18
The main agent used in Comparative Example 16 was 18 g of diethylmethylbenzenediamine (manufactured by Albemar: product name EtaCure 100) as an aromatic polyamine compound and methyl-1,3-cyclohexanediamine (Registered) as an alicyclic amine compound. A curing agent containing 2 g of EC210) was mixed at room temperature to obtain a thermosetting composition.

Comparative Example 19
18 g of diethylmethylbenzenediamine (manufactured by Albemar Co., Ltd .: product name EtaCure 100) as an aromatic polyamine compound and 2 g of 1,3-phenylenediamine as an aromatic polyamine compound were mixed at room temperature to obtain a curing agent. This curing agent was mixed with the main agent used in Example 4 at room temperature to obtain a thermosetting composition.

The thermosetting compositions obtained in Examples 4 to 16 and the thermosetting compositions obtained in Comparative Examples 6 to 19 were exposed to an atmosphere of 120 ° C. and pre-cured to become a solid. It was measured. The results are shown in Table 2.
[Table 2]
━━━━━━━━━━━━━━━━━━━━━━
Time to pre-cure
━━━━━━━━━━━━━━━━━━━━━━
Example 4 25 minutes
Example 5 20 minutes
Example 6 30 minutes
Example 7 25 minutes
Example 8 22 minutes
Example 9 25 minutes
Example 10 30 minutes
Example 11 23 minutes
Example 12 23 minutes
Example 13 23 minutes
Example 14 23 minutes
Example 15 20 minutes
Example 16 20 minutes
Comparative Example 6 120 minutes or more
Comparative Example 7 120 minutes or more
Comparative Example 8 120 minutes or more
Comparative Example 9 120 minutes or more
Comparative example 10 120 minutes or more
Comparative Example 11 120 minutes or more
Comparative Example 12 120 minutes or more
Comparative Example 13 120 minutes or more
Comparative example 14 120 minutes or more
Comparative example 15 120 minutes or more
Comparative Example 16 110 minutes
Comparative Example 17 90 minutes
Comparative Example 18 100 minutes
Comparative Example 19 60 minutes
━━━━━━━━━━━━━━━━━━━━━━

As is clear from Table 2, it can be seen that the thermosetting composition according to the examples has a shorter pre-curing time than the thermosetting composition according to the comparative example. When the pre-cured solid was main-cured under the condition of 200 ° C. for 2 hours, a cured product having a high glass transition point and good heat resistance was obtained.

Claims (10)

Thermocurable composition containing a polymaleimide group-containing compound, an aromatic polyamine compound, a benzoxazine compound, and an alicyclic amine compound in which a primary amino group is bonded to at least the 1st and 3rd carbon atoms of the cyclohexane ring. thing. The mass of the benzoxazine compound is 0.1 to 60% by mass with respect to the total mass of the polymaleimide group-containing compound and the benzoxazine compound, and the carbon atoms at at least the 1st and 3rd positions of the aromatic polyamine compound and the cyclohexane ring. With respect to the total mass of the alicyclic amine compound to which the primary amino group is bonded, the alicyclic type in which the primary amino group is bonded to the carbon atoms at at least the 1st and 3rd positions of the cyclohexane ring. The thermosetting composition according to claim 1, wherein the weight of the amine compound is 0.1 to 40% by mass. The thermosetting composition according to claim 1, further comprising an epoxy compound. The thermosetting composition according to claim 1, wherein the polymaleimide group-containing compound comprises a polymer. Contains a main agent containing a polymaleimide group-containing compound and a benzoxazine compound, and an alicyclic amine compound in which a primary amino group is bonded to at least the 1st and 3rd carbon atoms of an aromatic polyamine compound and a cyclohexane ring. A kit for obtaining the thermosetting composition according to claim 1, which comprises a curing agent. The mass of the benzoxazine compound is 0.1 to 60% by mass with respect to the total mass of the polymaleimide group-containing compound and the benzoxazine compound, and the carbon atoms at at least the 1st and 3rd positions of the aromatic polyamine compound and the cyclohexane ring. With respect to the total mass of the alicyclic amine compound to which the primary amino group is bonded, the alicyclic type in which the primary amino group is bonded to the carbon atoms at at least the 1st and 3rd positions of the cyclohexane ring. The kit according to claim 5, wherein the weight of the amine compound is 0.1 to 40% by mass. The kit according to claim 5, wherein an epoxy compound is further contained in the main agent. The kit according to claim 5, wherein the polymaleimide group-containing compound comprises a polymer. The method for producing a polymer according to claim 4 or 8, wherein the polymerimide group-containing monomer and a compound having one or more hydroxyl groups in the molecule are mixed and heated. The method for producing a polymer according to claim 9, wherein a polymerimide group-containing monomer, a compound having one or more hydroxyl groups in the molecule, and an epoxy compound are mixed and heated.