JP2016089053A - Salt of epoxy-amine adduct, resin composition, and fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound that can improve adhesion between a resin and an addition material in a polymer composite, and has excellent water-solubility.SOLUTION: A salt of epoxy-amine adduct is salt of an amine compound [I] having two or more amino groups in a molecule and a phosphoric acid [II], where the amine compound [I] is an epoxy-amine adduct obtained by the reaction between an epoxy compound (A) having two or more alicyclic epoxy groups in a molecule and an amine compound (B) having two or more amino groups in a molecule.SELECTED DRAWING: None

Description

  The present invention relates to a salt (phosphate) of an epoxy-amine adduct, a resin composition containing the salt, and a fiber-reinforced composite formed from a prepreg obtained by impregnating or coating the resin composition on a reinforcing fiber. Regarding materials.

  Conventionally, epoxy-amine adducts (sometimes referred to as “amine adducts”) produced by reacting an amine compound with an epoxy compound are known. Examples of the amine adduct include, for example, Patent Document 1 and Patent Document 2, an addition compound obtained by reacting an epoxy resin having a glycidyl group with a dialkylamine, and neutralization treatment with an acidic substance on the surface of the addition compound powder. Things are disclosed. In Patent Document 3, for example, an amino compound having an amino group and an N, N-dialkylamino group is reacted with an epoxy resin having an average of more than one glycidyl group in a molecule at a specific ratio. The resulting epoxy-amine adduct is disclosed.

JP 56-155222 A Japanese Unexamined Patent Publication No. 57-1000012 JP 61-228018 A

  Patent Documents 1 to 3 describe that the amine adduct is used as an epoxy resin curing agent (latent curing agent). However, since the amine adduct may be able to exert various properties by selecting the amine compound and epoxy compound as raw materials, it is expected to be applied not only to the above-mentioned curing agent but also to various other uses. Is done. Specifically, taking advantage of the reactivity of the amine adduct, for example, composite materials (fiber reinforced composite materials) of reinforcing fibers such as carbon fibers and resins (fiber reinforced composite materials), nano-sized materials such as talc, kaolin, and layered silicates. In polymer composites such as nanocomposites in which a filler is dispersed in a resin, it is expected to be used as an adhesion improver that improves the adhesion between the reinforcing fibers and fillers and the resin and the resin. Moreover, the use as an adhesive or a paint, and the use as an adhesion improver for improving the adhesion to an adherend in these adhesive or paint are also expected.

  The amine adduct is easily blended with other materials when it is assumed to be used as an additive to other materials (for example, curable resins such as thermoplastic resins and epoxy compounds). We need to be able to do it. Particularly in recent years, from the viewpoints of environmental protection and safety of the working environment, in order to be able to be used in the form of an aqueous solution or aqueous dispersion, it is required to have excellent solubility in water (water solubility). ing. However, for example, an adduct of an epoxy compound having a glycidyl group such as an amine adduct disclosed in Patent Documents 1 to 3 or a bisphenol A diglycidyl ether conventionally known as an amine adduct and a polyamine compound has a crosslinked structure. Since it is formed, it does not soften or melt even when heated, and it does not dissolve in solvents such as water, so that it is difficult to uniformly mix with other materials.

  Furthermore, the amine adduct has, for example, excellent heat resistance that can withstand even when the above polymer composite is processed at high temperature, and to prevent contamination due to adhesion to a processing machine or the like. It may be required to have a glass transition temperature that is somewhat high (for example, a glass transition temperature of room temperature or higher).

Accordingly, an object of the present invention is to provide a compound that can improve the adhesion between a resin and an additive in a polymer composite and is excellent in water solubility.
Moreover, the other object of this invention is to provide the said compound which was further excellent in heat resistance.
Furthermore, the other object of this invention is to provide the resin composition which can form the polymer type composite excellent in the adhesiveness of resin and an additive.
Furthermore, another object of the present invention is to provide a fiber-reinforced composite material having excellent adhesion between a resin and reinforcing fibers and having high mechanical properties (for example, toughness).

  As a result of intensive studies to solve the above problems, the present inventors have found that the phosphate of a specific epoxy-amine adduct can improve the adhesion between the resin and the additive in the polymer composite, and is water-soluble. The present invention was completed.

［式中、Ｘは単結合、又は１以上の原子を有する二価の基を示す。］
（３）アミン化合物（Ｂ）が、下記式（ｂ−１）

［式（ｂ−１）中、Ｒ²及びＲ³は、同一又は異なって、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが直接又はヘテロ原子を含む連結基を介して連結した二価の基を示す。ｑは、０又は１以上の整数を示す。］
で表されるアミン化合物（Ｂ１）、下記式（ｂ−２）

［式（ｂ−２）中、Ｒ⁴及びＲ⁵は、同一又は異なって、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが連結して形成される二価の基を示す。ｒは、１以上の整数を示す。］
で表されるアミン化合物（Ｂ２）、及び下記式（ｂ−３）

［式（ｂ−３）中、Ｒ⁶及びＲ⁸は、同一又は異なって、炭素数１〜４のアルキレン基、又は炭素数６〜１２のアリーレン基を示す。ｓは、０又は１を示す。Ｒ⁷は、一価の有機基、酸素原子含有基、硫黄原子含有基、窒素原子含有基、又はハロゲン原子を示す。ｔは、０〜１０の整数を示す。］
で表されるアミン化合物（Ｂ３）からなる群より選択される少なくとも一種の化合物である（１）又は（２）に記載のエポキシ−アミン付加物の塩。
（４）（１）〜（３）のいずれか１つに記載のエポキシ−アミン付加物の塩と、熱可塑性樹脂とを含む樹脂組成物。
（５）繊維強化複合材料用樹脂組成物である（４）に記載の樹脂組成物。
（６）（５）に記載の樹脂組成物を強化繊維に含浸又は塗工して得られるプリプレグ。
（７）（６）に記載のプリプレグより形成される繊維強化複合材料。
（８）（１）〜（３）のいずれか１つに記載のエポキシ−アミン付加物の塩を含むサイジング剤。
（９）（８）に記載のサイジング剤を炭素繊維に塗布して得られるサイジング剤塗布炭素繊維。
（１０）（９）に記載のサイジング剤塗布炭素繊維と、熱可塑性樹脂又は硬化性化合物を硬化させて得られる硬化物とを含む繊維強化複合材料。
（１１）（１）〜（３）のいずれか１つに記載のエポキシ−アミン付加物の塩を含む水溶液。 That is, the present invention relates to the following.
(1) A salt of an amine compound [I] having two or more amino groups in the molecule and phosphoric acid [II],
The amine compound [I] is obtained by a reaction between an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule. A salt of an epoxy-amine adduct, which is an epoxy-amine adduct.
(2) The salt of the epoxy-amine adduct according to (1), wherein the epoxy compound (A) is a compound represented by the following formula (a).

[Wherein, X represents a single bond or a divalent group having one or more atoms. ]
(3) The amine compound (B) is represented by the following formula (b-1)

[In the formula (b-1), R ² and R ³ are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic group. A divalent group in which one or more hydrocarbon groups and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. q represents 0 or an integer of 1 or more. ]
An amine compound (B1) represented by the following formula (b-2):

[In formula (b-2), R ⁴ and R ⁵ are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic group. A divalent group formed by linking one or more hydrocarbon groups and one or more cyclic aliphatic hydrocarbon groups. r represents an integer of 1 or more. ]
And an amine compound (B2) represented by the following formula (b-3):

[In Formula (b-3), R ⁶ and R ⁸ are the same or different and each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. s represents 0 or 1. R ⁷ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. t shows the integer of 0-10. ]
The salt of the epoxy-amine adduct according to (1) or (2), which is at least one compound selected from the group consisting of amine compounds (B3) represented by:
(4) A resin composition comprising a salt of an epoxy-amine adduct according to any one of (1) to (3) and a thermoplastic resin.
(5) The resin composition according to (4), which is a resin composition for fiber-reinforced composite materials.
(6) A prepreg obtained by impregnating or coating a reinforcing fiber with the resin composition according to (5).
(7) A fiber-reinforced composite material formed from the prepreg according to (6).
(8) A sizing agent comprising a salt of the epoxy-amine adduct according to any one of (1) to (3).
(9) Sizing agent application | coating carbon fiber obtained by apply | coating the sizing agent as described in (8) to carbon fiber.
(10) A fiber-reinforced composite material comprising the sizing agent-coated carbon fiber according to (9) and a cured product obtained by curing a thermoplastic resin or a curable compound.
(11) An aqueous solution containing a salt of the epoxy-amine adduct according to any one of (1) to (3).

Since the salt of the epoxy-amine adduct of the present invention has the above-described structure, it has excellent water solubility and can be easily blended with other components, and in particular, it can satisfy demands such as environmental protection and safety of work environment. Is. In addition, reactive functionalities such as hydroxy groups, carboxy groups, and epoxy groups (particularly glycidyl groups) present on the surface of additives such as reinforcing fibers and fillers by pyrolysis and other treatments (for example, treatment with a strong base). Since it can be converted into an epoxy-amine adduct having a high reactivity to the group, the adhesion between the resin and the additive in the polymer composite such as a fiber reinforced composite material or a nanocomposite can be effectively improved.
Further, the salt of the epoxy-amine adduct of the present invention can have a high thermal decomposition temperature and excellent heat resistance by using a specific compound as a raw material, and in this case, it can be applied to processing at a high temperature. It is possible and can contribute to the improvement of the productivity of the polymer composite. Moreover, it can be set to have a somewhat high glass transition temperature. In this case, contamination of a processing machine (roll or the like) is prevented, and the handleability is also excellent.
Accordingly, by using the salt of the epoxy-amine adduct of the present invention, a resin composition capable of forming a polymer composite (fiber reinforced composite material, etc.) having excellent adhesion between the resin and the additive (reinforced fiber, etc.) is obtained. It is done. In addition, a fiber-reinforced composite material having excellent adhesion between the resin and the reinforcing fiber and having high mechanical properties (particularly toughness) can be obtained with high productivity.

¹ is a chart of ¹ H-NMR spectrum (solvent: DMSO-d6) of an epoxy compound (Celoxide 2021P) used as a raw material for an epoxy-amine adduct in Examples. ¹ is a chart of ¹ H-NMR spectrum (solvent: DMSO-d6) of triethylenetetramine used as a raw material for an epoxy-amine adduct in Examples. ¹ is a chart of ¹ H-NMR spectrum (solvent: DMSO-d6) of isophoronediamine used as a raw material for an epoxy-amine adduct in Examples. ¹ is a chart of ¹ H-NMR spectrum (solvent: DMSO-d6) of an epoxy-amine adduct produced in an example. 1 is a chart of ¹ H-NMR spectrum (solvent: DMSO-d6) of phosphoric acid (85% aqueous solution) used in Example 1. 1 is a chart of ¹ H-NMR spectrum (solvent: DMSO-d6) of a salt (phosphate; 40% aqueous solution) of an epoxy-amine adduct produced in Example 1.

<Salt of epoxy-amine adduct>
The salt of the epoxy-amine adduct of the present invention is a salt of an amine compound [I] having two or more amino groups in the molecule and phosphoric acid (sometimes referred to as “phosphoric acid [II]”). Compound phosphate). In the present specification, the term “amino group” simply means —NH ₂ (unsubstituted amino group), and “—NH— group” refers to the unsubstituted amino group (—NH ₂ ). Shall not be included.

  Among them, the salt of the epoxy-amine adduct of the present invention is a compound in which the amine compound [I] has two or more amino groups in the molecule, and has two or more alicyclic epoxy groups in the molecule. The epoxy compound (A) having (sometimes simply referred to as “epoxy compound (A)”) and the amine compound (B) having two or more amino groups in the molecule (simply referred to as “amine compound (B)”) It is an epoxy-amine adduct obtained by reaction with

[Epoxy-amine adduct]
As described above, the epoxy-amine adduct as a raw material of the salt of the epoxy-amine adduct of the present invention (sometimes simply referred to as “epoxy-amine adduct salt”) has two or more in the molecule. A compound having an amino group (—NH ₂ ), which is an epoxy-amine adduct obtained by a reaction between an epoxy compound (A) and an amine compound (B). More specifically, the epoxy-amine adduct is one or more epoxy compounds produced by reacting the alicyclic epoxy group of the epoxy compound (A) with the amino group of the amine compound (B). It is an adduct of (A) and one or more molecules of amine compound (B).

1. Epoxy compound (A)
The epoxy compound (A) as a raw material of the epoxy-amine adduct is a polyepoxy compound (alicyclic epoxy compound) having two or more alicyclic epoxy groups in the molecule. The “alicyclic epoxy group” in the present specification means an epoxy group composed of two adjacent carbon atoms constituting an alicyclic ring (aliphatic ring) and an oxygen atom.

  Although the alicyclic epoxy group which an epoxy compound (A) has is not specifically limited, For example, C4-C16 aliphatic rings (aliphatic hydrocarbon), such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring And an epoxy group composed of two adjacent carbon atoms constituting a ring) and an oxygen atom. Especially, as said alicyclic epoxy group, the epoxy group (cyclohexene oxide group) comprised by two adjacent carbon atoms which comprise a cyclohexane ring, and an oxygen atom is preferable.

  The number of alicyclic epoxy groups in the molecule of the epoxy compound (A) is not particularly limited as long as it is 2 or more, but 2 to 6 is preferable, 2 to 5 is more preferable, and 2 is more preferable. Or three. By setting the number of alicyclic epoxy groups to 6 or less, the water-solubility of the salt of the epoxy-amine adduct tends to be further improved.

As the epoxy compound (A), a compound (epoxy compound) represented by the following formula (a) is particularly preferable.

  X in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include divalent hydrocarbon groups, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which two or more of the groups are linked.

  Examples of the epoxy compound (A) in which X in the formula (a) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

  The linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —CO—O—, —O—, —CO—NH. -, An epoxidized alkenylene group; a group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, and the like. Examples of the divalent hydrocarbon group include those exemplified above.

As a typical example of the alicyclic epoxy compound represented by the above formula (a), compounds represented by the following formulas (a-1) to (a-10), 2,2-bis (3,4) -Epoxycyclohexane-1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1- Yl) ethane, bis (3,4-epoxycyclohexylmethyl) ether, and the like. In the following formulas (a-5) and (a-7), l and m each represent an integer of 1 to 30. R ′ in the following formula (a-5) represents an alkylene group having 1 to 8 carbon atoms. For example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene. And straight-chain or branched alkylene groups such as a hexylene group, a heptylene group, and an octylene group. Among these, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group is preferable. N1 to n6 in the following formulas (a-9) and (a-10) each represent an integer of 1 to 30.

  As the epoxy compound (A), a compound represented by the above formula (a) is preferable. In particular, from the viewpoint of heat resistance and handleability, the compound represented by the above formula (a-1) [3,4-epoxy Preferred is cyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; trade name “Celoxide 2021P” (manufactured by Daicel Corporation).

2. Amine compound (B)
The amine compound (B) as a raw material of the epoxy-amine adduct is a polyamine compound having two or more amino groups (—NH ₂ ; unsubstituted amino group) in the molecule. The number of amino groups in the molecule of the amine compound (B) may be two or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, still more preferably 2 or 3 It is a piece. By setting the number of amino groups to 6 or less, the water solubility of the salt of the epoxy-amine adduct tends to be further improved.

Examples of the amine compound (B) include p-valent amine compounds represented by the following formula (b).

  P in the above formula (b) represents an integer of 2 or more. Although p should just be an integer greater than or equal to 2, it is not specifically limited, 2-6 are preferable, More preferably, it is 2-5, More preferably, it is 2 or 3.

R ¹ in the above formula (b) represents a p-valent organic group (organic residue) having a carbon atom at the binding site with the nitrogen atom shown in the formula. Examples of R ¹ include a linear or branched p-valent aliphatic hydrocarbon group; a cyclic p-valent aliphatic hydrocarbon group; a p-valent aromatic hydrocarbon group; and two or more of these groups Or a p-valent group bonded directly or via a linking group (a divalent group) containing a hetero atom.

Examples of the linear or branched p-valent aliphatic hydrocarbon group include a linear or branched divalent aliphatic hydrocarbon group, a linear or branched trivalent aliphatic hydrocarbon group, and the like. Examples include a hydrogen group, a linear or branched tetravalent aliphatic hydrocarbon group, and the like. Examples of the linear or branched divalent aliphatic hydrocarbon group include an alkylene group [eg, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, A linear or branched chain having 1 to 30 carbon atoms (C _1-30 ) such as nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, etc. Alkylene group (preferably C _1-18 alkylene group)], alkenylene group [alkenylene group corresponding to the above alkylene group, for example, a linear or branched alkenylene group having 2 to 30 carbon atoms such as vinylene group, arylene group, etc. (Preferably a C _2-18 alkenylene group) and the like]. Examples of the linear or branched trivalent aliphatic hydrocarbon group include, for example, alkane-triyl group [for example, propane-triyl group, 1,1,1-trimethylpropane-triyl group, etc. 30 linear or branched alkane-triyl groups (preferably C _3-18 alkane-triyl groups) and the like. Examples of the linear or branched tetravalent aliphatic hydrocarbon group include, for example, alkane-tetrayl groups [for example, butane-tetrayl groups, 2,2-dimethylpropane-tetrayl groups and the like having 4 to 30 carbon atoms. Straight chain or branched chain alkane-tetrayl group (preferably C _4-18 alkane-tetrayl group) and the like].

  The linear or branched p-valent aliphatic hydrocarbon group may have various substituents (that is, the linear or branched p-valent aliphatic hydrocarbon group is And at least one of the hydrogen atoms it has may be substituted with various substituents). Examples of the substituent include a halogen atom, an oxo group, a hydroxy group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, and an acyloxy group), a carboxy group, and a substituted oxycarbonyl group (alkoxycarbonyl group). Aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group and the like. The hydroxy group and carboxy group may be protected with a protective group commonly used in the field of organic synthesis (for example, acyl group, alkoxycarbonyl group, organic silyl group, alkoxyalkyl group, oxacycloalkyl group, etc.).

  Examples of the substituted or unsubstituted carbamoyl group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group, or an acetyl group and a benzoyl group. And a carbamoyl group having an acyl group or the like, or an unsubstituted carbamoyl group. Examples of the substituted or unsubstituted amino group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, and t-butyl group, acetyl group, and benzoyl group. An amino group having an acyl group such as a group, or an unsubstituted amino group.

The heterocyclic ring constituting the heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocyclic ring include a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a 3-membered ring such as an oxirane ring, a 4-membered ring such as an oxetane ring, a furan ring, a tetrahydrofuran ring, an oxazole ring, and γ-butyrolactone. 5-membered ring such as a ring, 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring and morpholine ring, benzofuran ring, 4-oxo-4H-chromene ring, condensed ring such as chroman ring, 3-oxa Bridged ring such as tricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring ), Hetero rings containing a sulfur atom as a hetero atom (for example, a 5-membered ring such as a thiophene ring, a thiazole ring or a thiadiazole ring, a 6-membered ring such as a 4-oxo-4H-thiopyran ring, a condensed ring such as a benzothiophene ring) , Hetero rings containing a nitrogen atom as a hetero atom (for example, pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole ring, triazole ring, etc. 5-membered ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring And 6-membered rings such as indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring, and purine ring). The heterocyclic group may be a heterocyclic group having a substituent, and the substituent may be, for example, the linear or branched p-valent aliphatic hydrocarbon group. In addition to good substituents, alkyl groups (eg, C _1-4 alkyl groups such as methyl and ethyl groups), alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups (eg, phenyl groups, naphthyl groups, etc.) And monovalent hydrocarbon groups. Further, the nitrogen atom constituting the heterocyclic ring in the heterocyclic group is a conventional protective group (for example, an alkoxy group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group, an aralkyl group, an acyl group, an arylsulfonyl group). , An alkylsulfonyl group, etc.).

Examples of the cyclic p-valent aliphatic hydrocarbon group include a cyclic divalent aliphatic hydrocarbon group, a cyclic trivalent aliphatic hydrocarbon group, and a cyclic tetravalent aliphatic hydrocarbon group. . Examples of the cyclic divalent aliphatic hydrocarbon group include a cycloalkylene group [for example, a cycloalkylene group having 3 to 20 carbon atoms such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group ( Preferably a C _3-15 cycloalkylene group)], cycloalkenylene group [cycloalkenylene group corresponding to the above cycloalkylene group, for example, a cycloalkenylene group having 3 to 20 carbon atoms such as a cyclohexenylene group (preferably C _{3 -15} cycloalkenylene group), etc.], cycloalkylidene group [cycloalkylidene group corresponding to the above cycloalkylene group, for example, cyclopentylidene group, cyclohexylidene group, etc., having 3 to 20 carbon atoms (preferably C _3-15 cycloalkylidene group), etc.], cycloalkadienyl Eni alkylene group [the Cycloalkadienyl Eni alkylene groups corresponding to Kuroarukiren group, for example, cyclopentadienylide cycloalkadienyl Eni alkylene group (preferably a C _4-15 cycloalkadienyl Eni alkylene group) having 4 to 20 carbon atoms such as alkylene group or the like], divalent A polycyclic hydrocarbon group [e.g., a spiro hydrocarbon (e.g., spiro [4.4] nonane, spiro [4.5] decane, etc.)-a divalent spiro hydrocarbon group such as a diyl group; (For example, bicyclopropyl and the like) -divalent ring assembly hydrocarbon group such as diyl group; bridged ring hydrocarbon (for example, bicyclo [2.1.0] pentane, bicyclo [3.2.1] octane, norbornane , Norbornene, adamantane and the like) -divalent bridged ring hydrocarbon groups such as diyl group] and the like. Examples of the cyclic trivalent aliphatic hydrocarbon group include a cycloalkane-triyl group and a polycyclic hydrocarbon-triyl group. Examples of the cyclic tetravalent aliphatic hydrocarbon group include a cycloalkane-tetrayl group and a polycyclic hydrocarbon-tetrayl group. The cyclic p-valent aliphatic hydrocarbon group may have a substituent. Examples of the substituent include the linear or branched p-valent aliphatic hydrocarbon group. In addition to the substituents that may be present, monovalents such as alkyl groups (eg, C _1-4 alkyl groups such as methyl and ethyl groups), alkenyl groups, and aryl groups (eg, phenyl and naphthyl groups) And the like.

Examples of the p-valent aromatic hydrocarbon group include groups obtained by removing p hydrogen atoms from an aromatic hydrocarbon in terms of the structural formula. Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, naphthacene, pyrene, perylene, biphenyl, binaphthyl, and bianthryl. The p-valent aromatic hydrocarbon group may have a substituent. Examples of the substituent include the linear or branched p-valent aliphatic hydrocarbon group. In addition to the substituents that may be used, alkyl groups (for example, C _1-4 alkyl groups such as methyl and ethyl groups), monovalent hydrocarbon groups such as alkenyl groups, cycloalkyl groups, and cycloalkenyl groups are exemplified. It is done.

Examples of the linking group containing a hetero atom (divalent group) include -CO-, -O-, -CO-O-, -O-CO-O-, -CO-NH-, and -CO-NR. ^a- (substituted amide group; R ^a represents an alkyl group), —NH—, —NR ^b — (R ^b represents an alkyl group), —SO—, —SO ₂ — and the like heteroatom (oxygen atom, A divalent group containing a nitrogen atom, a sulfur atom, etc.), a divalent group in which a plurality of these are connected, and the like.

More specifically, as the amine compound (B), an amine compound (B1) represented by the following formula (b-1), a compound (B2) represented by the following formula (b-2), and the following formula ( a compound (B3) represented by b-3), a compound (B4) represented by the following formula (b-4), and the like.

In the above formula (b-1), R ² and R ³ are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic group. A divalent group in which one or more of the hydrocarbon groups and one or more of the cyclic aliphatic hydrocarbon groups are bonded directly or via a linking group (a divalent group) containing a hetero atom. Examples of the linear, branched, or cyclic divalent aliphatic hydrocarbon group include, for example, a substituted or unsubstituted linear, branched, or cyclic divalent aliphatic hydrocarbon group exemplified as R ^1. Is mentioned. Examples of the divalent group in which one or more of the above-described linear or branched aliphatic hydrocarbon groups and one or more of the cyclic aliphatic hydrocarbon groups are directly bonded include, for example, the following formula (b- Examples include groups exemplified as groups formed by removing two amino groups at both ends from the structural formula represented by 3). Furthermore, as a coupling group containing a hetero atom, the group illustrated as a coupling group containing the hetero atom in R < ¹ > is mentioned, for example.

Among these, R ² is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. -4 linear or branched alkylene groups (especially ethylene group, trimethylene group, propylene group).

Among them, R ³ is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. -4 linear or branched alkylene groups (especially ethylene group, trimethylene group, propylene group). In the case of q is 2 or more integer, R ³ each in brackets (multiple R ³⁾ may be the same or different. Moreover, when it has 2 or more types of R < ³ >, the addition form (polymerization form) of the structure in the parenthesis which attached | subjected q may be a random type, and may be a block type.

  In the above formula (b-1), q represents 0 or an integer of 1 or more. As q, for example, 0 to 100 is preferable, more preferably 0 to 70, still more preferably 1 to 30, and particularly preferably 1 to 8. By setting q to 100 or less, the water-solubility of the salt of the epoxy-amine adduct is improved, and depending on the application, the heat resistance of the epoxy-amine adduct and the salt thereof, a polymer-based composite (particularly a fiber reinforced composite) There is a tendency that the heat resistance and mechanical properties (toughness, etc.) of the material) are further improved. On the other hand, by setting q to 1 or more, there is a tendency that the adhesion between the resin and the additive in the polymer composite using the salt of the epoxy-amine adduct is improved.

Note that R ² and R ³ in the above formula (b-1) may be the same or different.

  Among these, as the compound represented by the above formula (b-1), water-solubility of the salt of the epoxy-amine adduct, adhesion to the additive (particularly reinforcing fiber) of the epoxy-amine adduct, wettability, heat resistance In view of the above, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) are preferable, and triethylenetetramine is more preferable. Moreover, a commercial item can also be used as a compound represented by the said Formula (b-1).

R ⁴ in the above formula (b-2) is a linear, branched or cyclic divalent aliphatic hydrocarbon group or one or more linear or branched aliphatic hydrocarbon groups and a cyclic group. A divalent group formed by linking one or more aliphatic hydrocarbon groups. Examples of R ⁴ include the divalent groups exemplified as the above R ² and R ³ .

Among them, R ⁴ is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. -4 linear or branched alkylene groups (especially ethylene group, trimethylene group, propylene group).

R ⁵ in the above formula (b-2) is a linear, branched or cyclic divalent aliphatic hydrocarbon group or one or more linear or branched aliphatic hydrocarbon groups and a cyclic group. A divalent group formed by linking one or more aliphatic hydrocarbon groups. Examples of R ⁵ include the divalent groups exemplified as the above R ² and R ³ .

Among them, R ⁵ is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. -4 linear or branched alkylene groups (especially ethylene group, trimethylene group, propylene group). In the case of r is 2 or more integer, R ⁵ each in parentheses (multiple R ⁵⁾ may be the same or different. Moreover, when it has 2 or more types of R < ⁵ >, the addition form (polymerization form) of the structure in the parenthesis to which r is attached may be a random type or a block type.

  In the above formula (b-2), r (the number of repeating structural units in parentheses to which r is attached) represents an integer of 1 or more. As r, for example, 1 to 100 is preferable, more preferably 1 to 70, and still more preferably 1 to 30. By setting r to 100 or less, the water solubility of the salt of the epoxy-amine adduct is improved, and depending on the application, the heat resistance of the epoxy-amine adduct and the salt thereof, a polymer-based composite (particularly, fiber reinforced composite) There is a tendency that the heat resistance and mechanical properties (toughness, etc.) of the material) are further improved. On the other hand, when r is 1 or more, the adhesion between the resin and the additive in the polymer composite using the salt of the epoxy-amine adduct tends to be improved.

Note that R ⁴ and R ⁵ in the above formula (b-2) may be the same or different.

  Among them, the compound represented by the above formula (b-2) includes an amine terminal (both terminal amino groups) from the viewpoint of adhesion to an additive (particularly reinforcing fiber) of an epoxy-amine adduct and wettability with a resin. ) Polyethylene glycol, amine-terminated polypropylene glycol, and amine-terminated polybutylene glycol are preferred, and amine-terminated polypropylene glycol is more preferred. Moreover, as a compound represented by the said formula (b-2), a commercial item (For example, the product name "JEFFAMINE" series by the HUNTSMAN company etc.) can also be used.

R ⁶ and R ⁸ in the above formula (b-3) are the same or different and represent an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. Specific examples of R ⁶ and R ⁸ include an alkylene group having 1 to 4 carbon atoms and an arylene group having 6 to 12 carbon atoms exemplified as R ¹ in the formula (b) (from an aromatic hydrocarbon to two hydrogen atoms. And the like).

  S in the above formula (b-3) represents 0 or 1.

R ⁷ in the above formula (b-3) represents a substituent on the cyclohexane ring represented by the formula, and is the same or different and is a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom. A containing group, a monovalent nitrogen atom-containing group, or a halogen atom. Specific examples of R ⁷ include alkyl groups, halogen atoms (fluorine atoms, chlorine atoms, etc.), hydroxy groups, carboxy groups, alkoxy groups, alkenyloxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, Mercapto group, alkylthio group, alkenylthio group, arylthio group, aralkylthio group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group, nitro group, mono- or dialkylamino group, acylamino group, epoxy group, glycidyl Group, acyl group, cyano group, isocyanate group, isothiocyanate group, carbamoyl group, sulfo group and the like. Also, t in the above formula (b-3) is the number of substituents on the cyclohexane ring shown in formula (R ^7), an integer of 0. When t in the formula (b-3) is an integer of 2 or more, each R ⁷ may be the same or different.

  More specifically, examples of the group formed by removing the two amino groups at both ends from the structural formula represented by the above formula (b-3) include 1,2-cyclohexylene-methylene group, 1, 3-cyclohexylene-methylene, 1,4-cyclohexylene-methylene, cyclohexylidene-methylene, 1,2-cyclohexylene-ethylene, 1,3-cyclohexylene-ethylene, 1,4-cyclohexyl Silene-ethylene group, cyclohexylidene-ethylene group, methylene-1,5,5-trimethyl-1,3-cyclohexylene group (a divalent group formed by removing two amino groups from isophoronediamine), etc. Cyclohexylene-alkylene group; 1,2-cyclohexylene-phenylene group, 1,3-cyclohexylene-phenylene group, 1,4-cyclohexylene -Cyclohexylene-arylene group such as phenylene group; alkylene such as methylene-1,2-cyclohexylene-methylene group, methylene-1,3-cyclohexylene-methylene group, methylene-1,4-cyclohexylene-methylene group- Cyclohexylene-alkylene group; alkylene-cyclohexylene-phenylene group such as methylene-1,2-cyclohexylene-phenylene group, methylene-1,3-cyclohexylene-phenylene group, methylene-1,4-cyclohexylene-phenylene group, etc. An arylene-cyclohexylene-arylene group such as a phenylene-1,2-cyclohexylene-phenylene group, a phenylene-1,3-cyclohexylene-phenylene group, a phenylene-1,4-cyclohexylene-phenylene group, and the like.

  Especially, as a compound represented by the said formula (b-3), isophorone diamine is preferable from a heat resistant viewpoint of an epoxy-amine adduct and its salt. Moreover, as a compound represented by the said Formula (b-3), a commercial item (For example, Evonik Degussa Japan Co., Ltd. make, brand name "Vestamine IPD") can also be used.

In the above formula (b-4), u (the number of repeating structural units in parentheses to which u is attached) represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 70, and even more preferably 1. ~ 30. In the above formula (b-4), v (the number of structures in parentheses to which v bonded to R ⁹ is attached) represents an integer of 3 or more, preferably 3-6, more preferably 3-5. More preferably, it is 3 or 4.

R ¹⁰ in the above formula (b-4) is a linear, branched or cyclic divalent aliphatic hydrocarbon group or one or more linear or branched aliphatic hydrocarbon groups and a cyclic group. A divalent group formed by linking with one or more aliphatic hydrocarbon groups is exemplified, and examples thereof include the divalent groups exemplified as R ² and R ³ described above. R ⁹ represents a v-valent organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula, and is the same as R ¹ (for example, a linear or branched p-valence). Aliphatic hydrocarbon groups, cyclic p-valent aliphatic hydrocarbon groups, etc.).

  As the compound represented by the above formula (b-4), commercially available products (for example, product name “JEFFAMINE” series, manufactured by HUNTSMAN Co., Ltd.) can be used.

  As the amine compound (B), the compound represented by the formula (b-1), the formula (b-2), particularly from the viewpoint of improving the adhesion between the resin of the epoxy-amine adduct and the additive, heat resistance, and the like. ) And a compound represented by formula (b-3) are preferred, and a compound represented by formula (b-1) and a compound represented by formula (b-3) are more preferred.

3. Production method of epoxy-amine adduct; reaction of epoxy compound (A) and amine compound (B) The epoxy-amine adduct can be produced by reacting an epoxy compound (A) with an amine compound (B). More specifically, the epoxy-amine adduct is produced by reacting the alicyclic epoxy group of the epoxy compound (A) with the amino group of the amine compound (B).

  The epoxy compound (A) and the amine compound (B) as raw materials for the epoxy-amine adduct can be appropriately selected according to the properties to be imparted to the epoxy-amine adduct and its salt. The above-mentioned epoxy-amine adduct is, for example, particularly water-soluble epoxy-amine adduct salts, adhesion to additives (reinforced fibers, etc.) of epoxy-amine adducts, wettability with resin, heat resistance, and handling properties. When emphasis is placed on the epoxy-amine obtained by reacting the compound represented by the formula (a) with the amine compound (B1) (more preferably both of the amine compounds (B1) and (B3)) It is preferably an adduct (referred to as “epoxy-amine adduct (i)”). For example, when heat resistance is particularly important, an epoxy-amine adduct obtained by reacting the compound represented by the formula (a) with the amine compound (B2) and the amine compound (B3). (Referred to as “epoxy-amine adduct (ii)”). In the epoxy-amine adducts (i) and (ii), an epoxy compound other than the essential epoxy compound (A) and the amine compound (B) or an amine compound can be used in combination. For example, an amine compound other than the amine compound (B1) (for example, an amine compound (B2), an amine compound (B3), an amine compound (B4), etc.) can be used in combination as a raw material for the epoxy-amine adduct (i). In addition, amine compounds other than the amine compound (B2) and the amine compound (B3) (for example, the amine compound (B1), the amine compound (B4), etc.) can be used in combination as a raw material for the epoxy-amine adduct (ii). .

  When the above-mentioned epoxy-amine adduct (i) or epoxy-amine adduct (ii) is used as the epoxy-amine adduct which is a raw material of the salt of the epoxy-amine adduct of the present invention, the epoxy-amine adduct Since it has a high thermal decomposition temperature and excellent heat resistance, it can be applied to processing at a high temperature and can contribute to the improvement of the productivity of the polymer composite. Moreover, since it has a glass transition temperature that is somewhat high, contamination of a processing machine (such as a roll) is prevented, and the handleability is excellent.

  Of the compound represented by the formula (a) in the total amount (100% by weight) of the epoxy compound (A) which is a raw material of the epoxy-amine adduct (for example, epoxy-amine adduct (i), (ii)) The ratio is not particularly limited, but is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 98 to 100% by weight. By setting the ratio of the compound represented by the formula (a) to 80% by weight or more, adhesion to an additive of an epoxy-amine adduct (especially a reinforcing fiber such as carbon fiber), a polymer composite (particularly a fiber reinforced composite) There is a tendency that the adhesion between the resin and the additive (particularly reinforcing fiber) in the material) is improved efficiently.

  The proportion of the amine compound (B1) in the total amount (100% by weight) of the amine compound (B) that is a raw material of the epoxy-amine adduct (i) is not particularly limited, but is 10% by weight or more (for example, 10 to 100). % By weight) is preferable, more preferably 20 to 90% by weight, and still more preferably 50 to 80% by weight. By controlling the ratio of the amine compound (B1) within the above range, the water solubility of the epoxy-amine adduct, the adhesiveness to the additive of the epoxy-amine adduct (especially reinforcing fibers such as carbon fibers), wettability, polymer There is a tendency that the adhesiveness between the additive (particularly the reinforcing fiber) and the resin in the base composite (particularly the fiber-reinforced composite material) and the solubility in a solvent such as water solubility are further improved.

  The ratio of the amine compound (B3) in the total amount (100% by weight) of the amine compound (B) as the raw material of the epoxy-amine adduct (i) is not particularly limited, but is preferably 10 to 70% by weight, more preferably Is 20 to 60% by weight, more preferably 30 to 50% by weight. By controlling the ratio of the amine compound (B3) within the above range, the adhesiveness to the additive (especially reinforcing fiber) of the epoxy-amine adduct, wettability, and the additive in the polymer composite (especially fiber reinforced composite material) ( In particular, the heat resistance tends to be further improved while the adhesion between the reinforcing fiber) and the resin is ensured.

  The ratio of the amine compound (B2) in the total amount (100% by weight) of the amine compound (B) that is a raw material of the epoxy-amine adduct (ii) is not particularly limited, but is preferably 10 to 90% by weight, more preferably Is 20 to 80% by weight, more preferably 30 to 70% by weight. By controlling the ratio of the amine compound (B2) within the above range, the adhesiveness and wettability of the epoxy-amine adduct to the additive (especially reinforcing fiber), the additive in the polymer composite (especially fiber reinforced composite material) ( In particular, the adhesion between the reinforcing fiber) and the resin tends to be further improved.

  The ratio of the amine compound (B3) in the total amount (100% by weight) of the amine compound (B) as a raw material of the epoxy-amine adduct (ii) is not particularly limited, but is preferably 10 to 90% by weight, more preferably Is 20 to 80% by weight, more preferably 30 to 70% by weight. By controlling the ratio of the amine compound (B3) within the above range, the adhesiveness to the additive (especially reinforcing fiber) of the epoxy-amine adduct, wettability, and the additive in the polymer composite (especially fiber reinforced composite material) ( In particular, the heat resistance tends to be further improved while the adhesion between the reinforcing fiber) and the resin is ensured.

  The above reaction (reaction of epoxy compound (A) and amine compound (B)) can be allowed to proceed in the presence of a solvent, or can be allowed to proceed in the absence of a solvent (that is, without solvent). Although it does not specifically limit as said solvent, The thing which can melt | dissolve or disperse | distribute an epoxy compound (A) and an amine compound (B) uniformly is preferable. More specifically, examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, Halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate Esters of amides; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Methanol, ethanol, isopropyl alcohol, butanol and the like Alcohols; dimethyl sulfoxide and the like. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The amount of solvent used in the above reaction is not particularly limited and can be set as appropriate.

  The ratio of the epoxy compound (A) to the reaction and the amine compound (B) is not particularly limited, but the alicyclic epoxy group of the epoxy compound (A) in the reaction and the amino group of the amine compound (B) The ratio [alicyclic epoxy group / amino group] (equivalent ratio) is 0.05 to 1.00 (more preferably 0.10 to 0.95, still more preferably 0.15 to 0.90). It is preferable to control as described above. By setting the ratio [alicyclic epoxy group / amino group] to 0.05 (particularly 0.5) or more, the unreacted amine compound (B) tends not to remain in the product. On the other hand, when the ratio [alicyclic epoxy group / amino group] is 1.00 or less, the unreacted epoxy compound (A) tends not to remain in the product.

The reaction of the epoxy compound (A) and the amine compound (B) can be caused to proceed by, for example, the following method [1], the following [2], or the following [3]. However, the method for causing the reaction to proceed is not limited to the following methods [1] to [3].
[1] A method in which the epoxy compound (A) and the amine compound (B) are charged all at once in a reaction vessel, and heated to the reaction temperature as necessary to react both.
[2] A method in which the amine compound (B) is sequentially added to a reaction vessel in which the epoxy compound (A) is charged and heated to the reaction temperature as necessary, and both are reacted.
[3] A method in which the epoxy compound (A) is sequentially added to a reaction vessel in which the amine compound (B) is charged and heated to the reaction temperature as necessary, and both are reacted.

  The “sequential addition” means continuous addition (a mode of adding over a certain period of time) or intermittent addition (a mode of split addition in multiple times).

  Among the above methods [1] to [3], the reaction heat can be easily controlled, and the method of the above [2] or the point of being easy to produce an epoxy-amine adduct having a high molecular weight and a high glass transition temperature. The method [3] is preferred. On the other hand, the epoxy-amine adduct may have a lower molecular weight depending on the application, but in such a case, the reaction is preferably carried out by the method [1] above.

  The rate of adding the amine compound (B) in the method [2] is not particularly limited. For example, when the total amount of the amine compound (B) to be added is 100 parts by weight, 0.1 to 20 parts by weight / It can set suitably from the range of minutes. Moreover, the speed | rate which adds an epoxy compound (A) in the method of said [3] is not specifically limited, For example, when the total amount of the epoxy compound (A) to add is 100 weight part, it is 0.1-20 weight. It can set suitably from the range of a part / minute. The amine compound (B) or epoxy compound (A) to be added can be added as it is, or can be added in the state of a solution or dispersion dissolved or dispersed in a solvent.

  In addition, when using 2 or more types of amine compounds (B), in the method of said [2], it may be dripped in the state which mixed each amine compound (B), and it is dripped in the state (each) which is not mixed. May be. In the latter case, each amine compound (B) can be dropped simultaneously or sequentially. The same applies to the dropping in the case of using two or more epoxy compounds (A) in the method [3].

  Although the temperature (reaction temperature) in the said reaction is not specifically limited, 30-280 degreeC is preferable, More preferably, it is 80-260 degreeC, More preferably, it is 120-250 degreeC. By setting the reaction temperature to 30 ° C. or higher, the reaction rate is increased and the productivity of the epoxy-amine adduct tends to be further improved. On the other hand, by making reaction temperature 280 degrees C or less, there exists a tendency for the thermal decomposition of an epoxy compound (A) or an amine compound (B) to be suppressed, and the yield of an epoxy-amine adduct to improve more. During the reaction, the reaction temperature can be controlled to be always constant (substantially constant), or can be controlled to change stepwise or continuously.

  Although the time (reaction time) which implements the said reaction is not specifically limited, 0.2-20 hours are preferable, More preferably, it is 0.5-10 hours, More preferably, it is 2-8 hours. By making reaction time 0.2 hours or more, there exists a tendency for the yield of an epoxy-amine adduct to improve more. On the other hand, when the reaction time is 20 hours or less, the productivity of the epoxy-amine adduct tends to be improved.

  The above reaction can be carried out under normal pressure, under pressure or under reduced pressure. In addition, the atmosphere in which the above reaction is performed is not particularly limited, and the reaction can be performed in any atmosphere such as an inert gas (for example, nitrogen, argon, or the like) or air.

  The said reaction is not specifically limited, It can implement by any system of a batch system (batch system), a semibatch system, and a continuous distribution system.

  An epoxy-amine adduct is obtained by the above reaction (reaction between the epoxy compound (A) and the amine compound (B)). After the above reaction, the resulting epoxy-amine adduct is obtained by, for example, known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination means combining these. It is possible to separate and purify by, for example.

The number of amino groups (—NH ₂ ; unsubstituted amino group) possessed by the epoxy-amine adduct is 2 or more, preferably 2 to 10, more preferably 2 to 4, and even more preferably 2. Or three. Moreover, the said epoxy-amine adduct does not have an epoxy group (especially alicyclic epoxy group derived from an epoxy compound (A)) substantially.

The amino group (—NH ₂ ; unsubstituted amino group) in the epoxy-amine adduct is not particularly limited, but is usually a molecular chain terminal of the epoxy-amine adduct (in particular, a linear epoxy-amine adduct). In some cases, it is located at both ends of the molecular chain of the epoxy-amine adduct. However, it is not limited to this.

As described above, the epoxy-amine adduct is produced by the reaction of the alicyclic epoxy group of the epoxy compound (A) and the amino group (—NH ₂ ; unsubstituted amino group) of the amine compound (B). . The epoxy-amine adduct is an -NH- group (substituted amino group) generated by the reaction of the alicyclic epoxy group and an amino group (in addition, when an amine compound (B1) is used, an amine compound (B1 ) -NH-group (when m is 1 or more)) and the alicyclic epoxy group of the epoxy compound (A), it is presumed that the reactivity is low. The group remains unreacted. The number of —NH— groups in the molecule of the epoxy-amine adduct is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, and still more preferably 2 to 100. When the epoxy-amine adduct does not have an -NH- group, the reactivity of the epoxy-amine adduct is lowered, or depending on the use, the effect of improving the adhesion between the resin and the reinforced fiber in the fiber reinforced composite material is sufficient. It may not be obtained. In addition, water solubility decreases. The number of —NH— groups in the epoxy-amine adduct is, for example, the epoxy constituting the epoxy-amine adduct using the molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). It is possible to calculate by obtaining the number of the compound (A) and the amine compound (B).

  In contrast to the above, for example, a compound (epoxy-amine adduct) obtained by a reaction between an epoxy compound having a glycidyl group and an amine compound (B) is obtained by a reaction between a glycidyl group and an amino group (unsubstituted amino group). Since the -NH- group to be generated and the glycidyl group are very reactive, usually the -NH- group does not substantially remain.

  Although the number average molecular weight of the said epoxy-amine adduct is not specifically limited, 200-40000 are preferable, More preferably, it is 300-30000, More preferably, it is 400-20000. By setting the number average molecular weight to 200 or more, the glass transition temperature of the epoxy-amine adduct is increased to some extent, and contamination of the processing machine (roll or the like) tends to be suppressed. Moreover, there exists a tendency which can provide the outstanding texture and handleability with respect to the reinforced fiber (for example, sizing agent application | coating carbon fiber) which apply | coated the epoxy-amine adduct or its salt. On the other hand, when the number average molecular weight is 40,000 or less, the water-solubility of the salt of the epoxy-amine adduct tends to be further improved. In addition, the number average molecular weight of an epoxy-amine adduct can be calculated using a molecular weight in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.

  Although the glass transition temperature (Tg) of the said epoxy-amine adduct is not specifically limited, -50-200 degreeC is preferable, More preferably, it is -40-190 degreeC, More preferably, it is -30-180 degreeC, Most preferably, it is 20 ~ 180 ° C. By setting the Tg of the epoxy-amine adduct to −50 ° C. or more (particularly 20 ° C. or more), the heat resistance and mechanical properties (toughness, etc.) of the polymer composite (particularly fiber-reinforced composite material) tend to be further improved. is there. Further, contamination of the processing machine (roll or the like) is suppressed, and excellent texture and handling properties can be imparted to reinforcing fibers (for example, sizing agent-coated carbon fibers) coated with an epoxy-amine adduct or a salt thereof. Tend. On the other hand, by setting the Tg of the epoxy-amine adduct to 200 ° C. or less, blending with other components of the epoxy-amine adduct or a salt thereof may be facilitated. The Tg of the epoxy-amine adduct can be measured, for example, by differential scanning calorimetry (DSC), dynamic viscoelasticity measurement, or the like. More specifically, it can be measured by the method disclosed in the examples.

The 5% weight loss temperature (Td ₅ ) of the epoxy-amine adduct is not particularly limited, but is preferably 280 ° C. or higher, more preferably 300 ° C. or higher. By setting the 5% weight loss temperature of the epoxy-amine adduct to 280 ° C. or higher (particularly 300 ° C. or higher), the epoxy-amine adduct or its salt is processed at a higher temperature (for example, production of sizing agent-coated carbon fiber) ) Tend to be applicable. The 5% weight loss temperature of the epoxy-amine adduct can be measured by TG / DTA. More specifically, it can be measured by the method disclosed in the examples.

［式（I）中、Ｘは、上記式（ａ）におけるものと同じ。］

［式（II）中、Ｒ²、Ｒ³、及びｑは、上記式（ｂ−１）におけるものと同じ。］

［式（III）中、Ｒ⁶、Ｒ⁷、Ｒ⁸、ｓ、及びｔは、上記式（ｂ−３）におけるものと同じ。］ The above-mentioned epoxy-amine adduct (i) includes a structural unit represented by the following formula (I) (structural unit; a structural unit derived from the compound represented by the formula (a)) and the following formula (II). It is an epoxy-amine adduct having an amino group at both ends including a structural unit represented (a structural unit derived from an amine compound (B1)). It is preferable that the epoxy-amine adduct (i) further contains a structural unit represented by the following formula (III).

[In the formula (I), X is the same as in the above formula (a). ]

[In formula (II), R ² , R ³ and q are the same as those in formula (b-1) above. ]

[In formula (III), R ⁶ , R ⁷ , R ⁸ , s, and t are the same as those in formula (b-3) above. ]

The epoxy-amine adduct (i) includes a structural unit derived from the epoxy compound (A) (for example, a structural unit represented by the formula (I)) and a structural unit derived from the amine compound (B) (for example, the formula (II) and a structural unit represented by formula (III) are alternately arranged, and have amino groups (—NH ₂ ) at both ends of the molecular chain ( That is, it is an epoxy-amine adduct having a structural unit derived from the amine compound (B) at both ends. The addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be a random type or a block type.

In the above formula (I), assuming that the carbon atom to which X is bonded among the carbon atoms constituting the cyclohexane ring is the “position 1” carbon atom, each cyclohexane ring of the structural unit represented by formula (I) The bonding position of the nitrogen atom (—NH—) of the structural unit derived from the amine compound (B) bonded to is the carbon atom at the 3-position or the carbon atom at the 4-position of the cyclohexane ring. When the bonding position of the nitrogen atom is the carbon atom at the 3-position, the bonding position of the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is the carbon atom at the 4-position. Moreover, when the bonding position of the nitrogen atom is the 4-position carbon atom of the cyclohexane ring, the bonding position of the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is the 3-position carbon atom. The bonding positions of the nitrogen atoms (or the bonding positions of hydroxy groups) in a plurality of (two or more) cyclohexane rings in the formula (I) may be the same or different. In addition, when the above-mentioned position number is attached | subjected to the carbon atom which comprises the cyclohexane ring in Formula (I), it will become like a following formula. The same applies to the epoxy-amine adduct (ii).

［式（IV）中、Ｒ⁴、Ｒ⁵、及びｒは、上記式（ｂ−２）におけるものと同じ。］ The epoxy-amine adduct (ii) includes a structural unit represented by the above formula (I) (a structural unit derived from the compound represented by the formula (a)) and a structural unit represented by the following formula (IV): Epoxy having an amino group at both ends, including (a structural unit derived from the amine compound (B2)) and a structural unit represented by the above formula (III) (a structural unit derived from the amine compound (B3)). It is an amine adduct.

[In the formula (IV), R ⁴ , R ⁵ and r are the same as those in the formula (b-2). ]

The epoxy-amine adduct (ii) includes a structural unit derived from the epoxy compound (A) (for example, a structural unit represented by the formula (I)) and a structural unit derived from the amine compound (B) (for example, the formula (III) and a structural unit represented by the formula (IV) are alternately arranged, and have amino groups (—NH ₂ ) at both ends of the molecular chain ( That is, it is an epoxy-amine adduct having a structural unit derived from the amine compound (B) at both ends. The addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be a random type or a block type.

[Phosphoric acid [II]]
The phosphoric acid [II] constituting the salt of the epoxy-amine adduct of the present invention is a component that reacts with a basic group such as an amino group of the epoxy-amine adduct to form a phosphate. In producing the salt of the epoxy-amine adduct of the present invention, phosphoric acid [II] can be used as it is or in the form of a solution (for example, an aqueous solution) or a dispersion. You can also.

  In the salt of the epoxy-amine adduct of the present invention, a part of the basic group such as an amino group of the epoxy-amine adduct has an acid other than phosphoric acid [II] (sometimes referred to as “other acid”). It may have a structure converted into a salt. The other acid is not particularly limited as long as it is capable of forming an acid-base reaction with the basic group to form a salt, and examples thereof include hydrochloric acid, carbonic acid, sulfuric acid, nitric acid, hydrobromic acid and the like. Inorganic acids; organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, malic acid, lactic acid, maleic acid, and fumaric acid. Other acids can be used alone or in combination of two or more. Among these, as the other acid, carbonic acid and organic acid are preferable, and carbonic acid and acetic acid (particularly carbonic acid (especially carbonic acid) are more preferable because they can be easily converted into an epoxy-amine adduct by handling, thermal decomposition of a salt, and the like. ). In producing the salt of the epoxy-amine adduct of the present invention, other acids can be used as they are, or can be used in the form of a solution (for example, an aqueous solution) or a dispersion. . In addition, the salt of the epoxy-amine adduct of the present invention may not have a structure converted to a salt by other acid.

[Method for producing salt of epoxy-amine adduct]
The salt of the epoxy-amine adduct of the present invention can be produced by a known or conventional method for producing a salt. Specifically, for example, by a method in which the epoxy-amine adduct (specifically, a basic group such as an amino group contained in the epoxy-amine adduct) is reacted with phosphoric acid [II] (acid-base reaction). The salt of the epoxy-amine adduct of the present invention can be obtained.

  The above reaction can be allowed to proceed in the presence of a solvent, or can be allowed to proceed in the absence of a solvent (that is, without solvent). The solvent is not particularly limited, and for example, those exemplified in the reaction of the epoxy compound (A) and the amine compound (B) can be used, but it is particularly preferable to use at least water. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type. Moreover, the usage-amount of the solvent in the said reaction is not specifically limited, It can set suitably.

  The ratio of the epoxy-amine adduct and phosphoric acid [II] to be subjected to the reaction (reaction between the epoxy-amine adduct and phosphoric acid [II]) is not particularly limited, and the base which the epoxy-amine adduct has Can be selected as appropriate according to the ratio (for example, it can be determined according to the desired water-solubility, etc.) to be converted to a salt among the functional groups (for example, amino group, —NH— group, etc.) It is.

  The operation for carrying out the reaction is not particularly limited. For example, the epoxy-amine adduct and phosphoric acid [II] can be charged into a reaction vessel in a batch and reacted, or the epoxy-amine adduct can be reacted. Either phosphoric acid [II] or phosphoric acid [II] is charged in a reaction vessel, and the other is added (for example, the above-described sequential addition) to cause the reaction.

  The temperature (reaction temperature) and time (reaction time) in the above reaction are not particularly limited and can be appropriately set. For example, the reaction can proceed at room temperature.

  The above reaction can be carried out under normal pressure, under pressure or under reduced pressure. In addition, the atmosphere in which the above reaction is performed is not particularly limited, and the reaction can be performed in any atmosphere such as an inert gas (for example, nitrogen, argon, or the like) or air.

  The said reaction is not specifically limited, It can implement by any system of a batch system (batch system), a semibatch system, and a continuous distribution system.

  When other acids are used in combination with phosphoric acid [II], the other acids can be reacted with the above epoxy-amine adduct in the same manner as phosphoric acid [II]. Phosphoric acid [II] and other acids can be reacted simultaneously or sequentially with the epoxy-amine adduct. When the phosphoric acid [II] and other acids are sequentially reacted with the epoxy-amine adduct, the order of the reaction of these is not particularly limited.

  By the above reaction, the salt (phosphate) of the epoxy-amine adduct of the present invention is formed. After the above reaction, the epoxy-amine salt of the present invention is a known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination means combining these. It is possible to separate and purify by, for example. The epoxy-amine salt of the present invention is particularly excellent in water solubility, and therefore can be preferably used in the state of an aqueous solution.

  The salt of the epoxy-amine adduct of the present invention is obtained by an acid-base reaction in which a part or all of the basic group (especially amino group, —NH-group) of the epoxy-amine adduct is at least with phosphoric acid [II]. Since it has the structure which became a phosphate, it has excellent water solubility, and can be preferably used particularly in the state of an aqueous solution. An epoxy-amine having an amino group or —NH— group can be easily converted into a basic group (particularly an amino group or —NH— group) by thermal decomposition or other treatment (eg, treatment with a strong base). Since it can be converted into an adduct, the effect of improving the adhesion between the resin and the additive in the polymer composite produced by the epoxy-amine adduct can be exhibited. Needless to say, the salt of the epoxy-amine adduct of the present invention has a structure in which only a part of the basic group of the epoxy-amine adduct is a salt (that is, an amino group). And -NH- groups) improve the adhesion between the resin and additives in polymer composites such as fiber reinforced composites and nanocomposites, even if they are not converted to epoxy-amine adducts. Has an effect.

  The use of the salt of the epoxy-amine adduct of the present invention is not particularly limited. For example, the salt of the epoxy-amine adduct of the present invention improves the adhesion to the adherend and an adhesion improver (adhesion improver) for improving the adhesion between the resin and the additive in the polymer composite. Adhesive improver (adhesive improver), compatibility improver (compatibilizer) to improve the solubility of two or more different components (especially polymers), dispersibility of additives in polymer composites Various additives such as dispersibility improvers, fluidity improvers, fluidity suppressors, plasticizers, crosslinkers such as epoxy resins, etc .; adhesives; paints (especially aqueous paints); sealants; sizing It can be used for various applications such as agents. In particular, since the salt of the epoxy-amine adduct of the present invention has high water solubility, it can be preferably used for applications of products using water or a solvent containing water as a main component (for example, aqueous paint).

  The salt of the epoxy-amine adduct of the present invention can be used as it is, or as a solution or dispersion. In particular, since the salt of the epoxy-amine adduct of the present invention is excellent in water solubility, it can be preferably used in the form of an aqueous solution (the aqueous solution containing the epoxy-amine adduct of the present invention as an essential component is referred to as “aqueous solution of the present invention”). ). The salt of the epoxy-amine adduct of the present invention can be used in various modes because precipitation of the dissolved matter is unlikely to occur even when the concentration of the aqueous solution (the aqueous solution of the present invention) is low. It is. The aqueous solution of the present invention can be used for the various applications described above (for example, water-based paints, sizing agents, etc.).

<Resin composition>
A resin composition (sometimes referred to as “resin composition of the present invention”) is obtained by blending (mixing) a salt of the epoxy-amine adduct of the present invention with a known or conventional resin. Although it does not specifically limit as said resin, For example, polyolefin (for example, polyethylene, polypropylene, polybutadiene, etc.), vinyl polymer (for example, acrylic resin, polystyrene, etc.), polyamide (for example, nylon 6, nylon 66, nylon 11). , Nylon 12, nylon 610, nylon 612, nylon 61, nylon 6T, nylon 9T, etc.), polyester (eg, polyethylene terephthalate, polybutylene terephthalate), polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide , Polyether sulfone, polyether ether ketone and other thermoplastic resins; epoxy resins, unsaturated polyesters, vinyl ester resins, allyl resins (eg Curable resins (curable compounds) such as diallyl phthalate resins), phenol resins, polyimides, cyanate resins, maleimide resins, urea resins, melamine resins, silicone resins (for example, thermosetting resins (thermosetting compounds)) And photocurable resins (photocurable compounds) and the like). However, the “resin” does not include the salt of the epoxy-amine adduct of the present invention. In addition, in the resin composition of this invention, the said resin can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Among these, a resin composition using a thermoplastic resin as the resin, that is, a resin composition (thermoplastic resin composition) containing at least a salt of the epoxy-amine adduct of the present invention and a thermoplastic resin is particularly cured. Compared to a curable resin composition (for example, a thermosetting resin composition, a photocurable resin composition, etc.), it has an advantage that it can be molded in a short time. For this reason, the resin composition containing at least the salt of the epoxy-amine adduct of the present invention and a thermoplastic resin can be particularly preferably used for applications that require a reduction in molding time (for example, automotive parts applications).

  The content (blending amount) of the resin in the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 99.9% by weight with respect to the total amount (100% by weight) of the resin composition. Preferably it is 1-99 weight%, More preferably, it is 2-98 weight%. When the content is 0.1% by weight or more, the heat resistance and mechanical properties (toughness, etc.) of the polymer composite (particularly fiber reinforced composite material) tend to be further improved. On the other hand, by setting the content to 99.9% by weight or less, the adhesion between the resin and the additive (particularly reinforcing fiber) in the polymer composite (particularly fiber-reinforced composite material) tends to be further improved.

  In the resin composition of the present invention, the epoxy-amine adduct salt of the present invention can be used singly or in combination of two or more.

  The content (blending amount) of the salt of the epoxy-amine adduct of the present invention in the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the resin, More preferably, it is 1-100 weight part, More preferably, it is 2-50 weight part. By setting the content of the salt of the epoxy-amine adduct of the present invention to 0.1 parts by weight or more, the adhesion between the resin and the additive (particularly reinforcing fiber) in the polymer composite (particularly fiber-reinforced composite material) is further improved. There is a tendency to improve. On the other hand, when the content of the salt of the epoxy-amine adduct of the present invention is 200 parts by weight or less, the heat resistance and mechanical properties (toughness, etc.) of the polymer composite (particularly fiber-reinforced composite material) are further improved. Tend.

  The resin composition of the present invention includes, for example, the above-described epoxy-amine adduct, polymerization initiator (thermal polymerization initiator, photopolymerization initiator, etc.) in addition to the above-described resin and the salt of the epoxy-amine adduct of the present invention. , Curing agent, curing accelerator, antifoaming agent, leveling agent, coupling agent (silane coupling agent etc.), surfactant, inorganic filler (silica, alumina etc.), flame retardant, colorant, antioxidant, Conventional additives such as an ultraviolet absorber, an ion adsorbent, a pigment, a phosphor, and a release agent may be contained.

  The resin composition of this invention should just contain the salt and resin of the epoxy-amine adduct of this invention at least, and the manufacturing method (preparation method) is not specifically limited. Specifically, for example, it can be prepared by stirring and mixing each component constituting the resin composition at a predetermined ratio. In addition, a known apparatus, for example, a rotation / revolution mixer, a planetary mixer, a kneader, a dissolver, or the like can be used for stirring and mixing the components.

  The salt of the epoxy-amine adduct of the present invention in the resin composition of the present invention is particularly in a composite material (fiber reinforced composite material) of a reinforced fiber such as carbon fiber and a resin by being converted into an epoxy-amine adduct. Since the adhesion between the resin and the reinforcing fiber can be improved, it can be preferably used as a resin composition (resin composition for fiber-reinforced composite material) for forming a fiber-reinforced composite material. Specifically, the fiber-reinforced composite material is formed from a prepreg obtained by impregnating or coating the reinforcing fiber with the resin composition of the present invention. More specifically, for example, when the resin composition of the present invention is a resin composition containing at least the salt of the epoxy-amine adduct of the present invention and a thermoplastic resin, the resin composition is in a molten state. Alternatively, a reinforced fiber is impregnated or coated in a state dissolved in a suitable solvent to obtain a prepreg (thermoplastic prepreg), and further, the fiber-reinforced composite material is obtained by molding the prepreg. On the other hand, for example, when the resin composition of the present invention is a resin composition containing at least the salt of the epoxy-amine adduct of the present invention and a curable resin, the reinforcing fiber is impregnated or coated with the resin composition. Thus, a prepreg (curable prepreg) is obtained, and a fiber-reinforced composite material is obtained by further curing and molding the curable resin in the prepreg. In particular, the thermoplastic prepreg can be preferably used in applications that require a reduction in molding time (for example, automotive parts applications).

  As the reinforcing fiber, known or commonly used reinforcing fiber can be used, and is not particularly limited. For example, carbon fiber, glass fiber, aramid fiber, boron fiber, graphite fiber, silicon carbide fiber, high-strength polyethylene fiber, Examples thereof include tungsten carbide fibers and polyparaphenylene benzoxazole fibers (PBO fibers). Examples of the carbon fiber include polyacrylonitrile (PAN) -based carbon fiber, pitch-based carbon fiber, and vapor-grown carbon fiber. Among these, carbon fiber, glass fiber, and aramid fiber are preferable from the viewpoint of mechanical properties (toughness and the like). In addition, the said reinforced fiber can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The reinforcing fiber may be subjected to a known or conventional surface treatment such as a coupling treatment, an oxidation treatment, or a coating treatment.

  The form of the reinforcing fiber is not particularly limited, and examples thereof include a filament (long fiber) form, a tow form, a unidirectional material form in which tows are arranged in one direction, a woven form, and a non-woven form. It is done. Examples of reinforcing fiber woven fabrics include stitches that prevent unraveling sheets that are aligned in one direction, such as plain weave, twill weave, satin weave, or non-crimp fabric, or sheets that are laminated at different angles. Stitched sheets and the like.

  The content of the reinforcing fiber in the prepreg (thermoplastic prepreg, curable prepreg) of the present invention is not particularly limited and can be appropriately adjusted.

  In addition, when the prepreg of the present invention is a curable prepreg, the prepreg is impregnated or coated on the reinforcing fiber with the resin composition of the present invention, and further subjected to heating, active energy ray irradiation, etc. A part of the curable resin in the resin composition may be cured (that is, semi-cured).

  The method for impregnating or coating the reinforcing fiber with the resin composition of the present invention is not particularly limited, and can be carried out by a method of impregnation or coating in a known or conventional prepreg manufacturing method.

  As described above, the fiber-reinforced composite material of the present invention is formed from the prepreg of the present invention, and the production method thereof is not particularly limited, but known or conventional methods such as hand layup method, prepreg method, RTM method, It can be produced by pultrusion method, filament winding method, spray-up method, pultrusion method, melt impregnation method, powder method and the like.

  The fiber-reinforced composite material of the present invention can be used as a material for various structures, and is not particularly limited. For example, an aircraft fuselage, main wing, tail wing, moving wing, fairing, cowl, door, etc .; spacecraft Motor case, main wing, etc .; Artificial satellite structure; Automobile parts such as automobile chassis; Railcar structure; Bicycle structure; Ship structure; Wind power blade; Pressure vessel; Fishing rod; Tennis racket; Arm: It can be preferably used as a material for a structure such as a cable (for example, a cable core).

[Sizing agent]
As described above, the salt of the epoxy-amine adduct of the present invention is particularly excellent in water solubility, and is converted to an epoxy-amine adduct, whereby a hydroxy group, a carboxy group, and an epoxy group are present on the surface of the reinforcing fiber. It can be used preferably as a sizing agent (especially a sizing agent for carbon fiber) because it has a high reactivity to functional groups such as, and can effectively improve the adhesion between the resin and the reinforcing fiber in the fiber-reinforced composite material. Can do. A sizing agent is a process applied (coated) to reinforcing fibers to improve handling in the reinforcing fiber manufacturing process and higher-order processing processes (textile process, prepreg process, and other molding processes). Agent, sometimes referred to as sizing agent. In the present specification, the sizing agent containing the salt of the epoxy-amine adduct of the present invention may be referred to as “the sizing agent of the present invention”.

  The sizing agent of the present invention only needs to contain the salt of the epoxy-amine adduct of the present invention as an essential component, and in addition to the salt of the epoxy-amine adduct of the present invention, a solvent, other additives, etc. It may be included, or may be composed only of the salt of the epoxy-amine adduct of the present invention (the salt of the epoxy-amine adduct of the present invention itself).

  The solvent that the sizing agent of the present invention may contain is not particularly limited, but water; aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; benzene, toluene, xylene, and ethylbenzene Aromatic hydrocarbons such as: halogenated hydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Esters such as ethyl acetate, isopropyl acetate and butyl acetate; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Methanol, ethanol and isopropyl Alcohol, alcohols such as butanol; dimethyl sulfoxide and the like. Especially, water and alcohol (especially water) are preferable at the point with a small load with respect to an environment or a working environment. That is, the sizing agent of the present invention comprises a salt solution (particularly an aqueous solution) or a dispersion (particularly an aqueous solution) of the epoxy-amine adduct of the present invention containing water and / or alcohol (one or both of water and alcohol). Water dispersion). The sizing agent of the present invention is particularly advantageous in that it can be easily prepared as a low-concentration aqueous solution. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

  In addition, the sizing agent of the present invention may contain various additives such as lubricants such as fatty acids, amides and esters; coupling agents such as silane coupling agents and titanium coupling agents.

[Carbon fiber coated with sizing agent]
By applying (coating) the sizing agent of the present invention to carbon fibers, sizing agent-coated carbon fibers (sometimes referred to as “sizing agent-coated carbon fibers of the present invention”) are obtained.

  The method for applying the sizing agent of the present invention to the carbon fiber is not particularly limited. For example, the method of immersing the carbon fiber in the sizing agent of the present invention, or the method of bringing the carbon fiber into contact with the roller to which the sizing agent of the present invention is attached. Well-known or conventional methods such as a method of spraying the sizing agent of the present invention on a carbon fiber in the form of a mist are exemplified. In addition, application | coating of the sizing agent of this invention may be performed with respect to the whole surface of carbon fiber, and may be performed with respect to one part surface. Also, the coating thickness and the coating amount can be adjusted as appropriate, and are not particularly limited.

  After applying the sizing agent of the present invention, heat treatment may be performed as necessary. Although the conditions of the said heat processing are not specifically limited, 40-300 degreeC is preferable for heating temperature, More preferably, it is 60-250 degreeC. The heating time can be appropriately adjusted according to the heating temperature and is not particularly limited, but is preferably 1 second to 60 minutes, more preferably 5 seconds to 10 minutes. In the heat treatment, the heating temperature can be constant, or can be changed continuously or stepwise. Further, the heat treatment may be performed continuously in one step, or may be performed intermittently in two or more steps. The heat treatment is generally performed to accelerate the impregnation of the sizing agent and dry the solvent. The heat treatment can be performed by a known or conventional method (for example, heating using a hot air oven).

  The sizing agent-coated carbon fiber of the present invention may be one obtained by applying the sizing agent of the present invention and heat-treating, and further applying the above-described thermoplastic resin, the above-described curable compound (curable resin), or the like. Good. Thereby, depending on the kind of the thermoplastic resin or the curable resin, tack of the sizing agent-coated carbon fiber may be reduced, and handling (handling) may be improved. The method of application is not particularly limited, and can be performed, for example, in the same manner as the application of the sizing agent of the present invention to carbon fibers. In addition, the said application | coating may be performed with respect to the whole surface of sizing agent application | coating carbon fiber, and may be performed with respect to one part surface. Also, the coating thickness and the coating amount can be adjusted as appropriate, and are not particularly limited.

  Since the sizing agent-coated carbon fiber of the present invention is coated with the salt of the epoxy-amine adduct of the present invention in the sizing agent of the present invention, it has excellent adhesion to the resin. Further, when an epoxy-amine adduct excellent in heat resistance is used as a raw material of the salt of the epoxy-amine adduct of the present invention in the sizing agent of the present invention, processing at a high temperature (for example, sizing agent-coated carbon fiber And can contribute to the improvement of the productivity of the fiber-reinforced composite material. Further, when an epoxy-amine adduct having a somewhat high glass transition temperature is used as a raw material for the salt of the epoxy-amine adduct of the present invention in the sizing agent of the present invention, contamination of the processing machine (roll, etc.) is prevented. Moreover, it is also possible to impart excellent texture and handleability to the reinforcing fiber (for example, sizing agent-coated carbon fiber) coated with a sizing agent. Furthermore, since the sizing agent of the present invention has excellent functions as a general sizing agent such as a function of converging carbon fibers and a function of imparting flexibility to the carbon fibers, the sizing agent-coated carbon of the present invention The fiber has good handleability and excellent high-order processability.

  Since the sizing agent-coated carbon fiber of the present invention has the above characteristics, it is obtained by curing the sizing agent-coated carbon fiber and various matrix resins (for example, the above-described thermoplastic resin and the above-described curable compound (curable resin)). The fiber reinforced composite material including a cured product (cured resin, etc.) obtained has excellent heat resistance and mechanical strength, and has high productivity. In addition, the said fiber reinforced composite material can be manufactured by well-known thru | or usual methods, such as the manufacturing method of the above-mentioned fiber reinforced composite material. Moreover, the said fiber reinforced composite material can be preferably used as a material of the above-mentioned various structures.

  The salt of the epoxy-amine adduct of the present invention is not particularly limited to the above-mentioned uses. For example, paper and paper processing field; adhesion industry field; ink, photographic industry field; textile industry field; flocculant, clarifier, As floating agent; as chelate resin, ion exchange resin, separation membrane, adsorbent; cosmetics, toiletry field; as lubricant, rust inhibitor, dispersant; as plating agent; biological, medical enzyme field; cement additive, petroleum mining It can be widely used in various fields such as a pharmaceutical agent.

  The salt of the epoxy-amine adduct of the present invention is used, for example, as a wet paper strength enhancer in papermaking and paper processing fields; promotes water drainage and improves drainage in the papermaking process; fine fibers, sizing agents, various fillers, pigments, dyes As a yield improver, etc .; it can be used for purposes such as clarification of white water and paper wastewater treatment. More specifically, the salt of the epoxy-amine adduct of the present invention utilizes the reactivity of the salt of the epoxy-amine adduct of the present invention with an acid dye, for example, by treatment of the salt of the epoxy-amine adduct of the present invention. Inkjet recording paper by improving the water resistance of the prepared water-based ink; oil-resistant paper treated with a reaction product of a phosphate ester and a salt of the epoxy-amine adduct of the present invention; quaternized or ethoxylated epoxy-amine addition of the present invention Dyed paper using a salt of the product; an alkali or neutral sizing agent using an anionic sizing agent and a salt of the epoxy-amine adduct of the present invention (yield agent); a salt of the epoxy-amine adduct of the present invention and a fatty acid Softening, size and wet strength improvement of paper using reaction product of chloroquine and epichlorohydrin; heat-resistant paper using salt of polyphosphoric acid flame retardant and epoxy-amine adduct of the present invention; Kokishiru of epoxy of the present invention - can be used in the manner and application of the deinking agent of wastepaper using the salt of the amine adduct.

  The salt of the epoxy-amine adduct of the present invention can be used in the field of the adhesive industry, for example, as a water-soluble adhesion promoter (laminate anchor agent). More specifically, the salt of the epoxy-amine adduct of the present invention is, for example, an FRP product treated with the salt of the epoxy-amine adduct of the present invention; the salt of the epoxy-amine adduct of the present invention and a polyepoxy compound. Water dispersible adhesive composition comprising a reactant; Packaging and masking tape pressure-sensitive adhesive composition comprising a diene polymer and the salt of the epoxy-amine adduct of the present invention; Salt of the epoxy-amine adduct of the present invention and nickel Or a rubber / metal adhesion promoter containing a metal complex comprising a cobalt salt; a water-soluble vinyl acetate copolymer emulsion adhesive modified with a salt of the epoxy-amine adduct of the present invention; Two-component fast-curing water-based adhesive for wood, tile, etc. composed of salt and acetoacetylated polyvinyl alcohol; epoxy-amine of the present invention It can be used in the manner and application of the moisture actuated heat melting adhesive consisting of a salt of the pressurized product and a hydroxy substituted organic compound and compatibility adhesive.

  The salt of the epoxy-amine adduct of the present invention is used in the ink and photographic industry fields, for example, to improve the storage stability and color contamination of a color developing solution; to impart antistatic properties to a silver halide photographic light-sensitive material; It can be used for purposes such as improving the water fastness characteristics of products. More specifically, the salt of the epoxy-amine adduct of the present invention is, for example, a color developing solution containing diethylhydroxyamine and the salt of the epoxy-amine adduct of the present invention; the salt of the epoxy-amine adduct of the present invention. Silver halide photographic light-sensitive material using an ion conductive polymer complex composed of an acid and a metal salt; Aspect and use of an inkjet composition comprising a hydroxyethylated epoxy-amine adduct salt of the present invention and a water-soluble dye Can be used in

  The salt of the epoxy-amine adduct of the present invention can be used in the textile industry, for example, for applications such as improving the dyeability of various fibers including cellulose fibers, shrinkage prevention, flameproofing treatment, and antistatic treatment. More particularly, the salt of the epoxy-amine adduct of the present invention is, for example, an antistatic polyamide composition treated with an acylate of the salt of the epoxy-amine adduct of the present invention; Antistatic agent for synthetic fiber using amphoteric polymer obtained by adding alkylene oxide and ethylenically unsaturated monomer to salt; fiber in which salt of epoxy-amine adduct of the present invention and anionic latex are internally added to fiber slurry Sheet: Functional fiber obtained by mixing the salt of the epoxy-amine adduct of the present invention and polyvinyl alcohol, dry spinning and crosslinking with glutaraldehyde, etc .; treated with the salt of the epoxy-amine adduct of the present invention and halophosphite It can be used in modes and applications such as fire retardant fibers.

  As described above, the salt of the epoxy-amine adduct of the present invention can be used as a flocculant, a clarifying agent, a flotation agent, for example, an exchange agent for purifying wastewater; a flocculant for activated sludge; Agent; Water treatment agent to remove organic and inorganic substances dispersed and emulsified in water; Treatment of water containing waste paint in wet paint booth circulating water; Agglomeration and recovery of silica dissolved in geothermal water; Coal and minerals It can be used for purposes such as collection of harmful heavy metals contained in wastewater; oil recovery from wastewater in oil recovery. More specifically, the salt of the epoxy-amine adduct of the present invention is, for example, an exchange agent for wastewater purification using a modified product of cellulose or a derivative thereof with the salt of the epoxy-amine adduct of the present invention; Flocculant for pulp wastewater comprising salt of epoxy-amine adduct and inorganic salt; porous water treatment material comprising salt of polyethylene, silica and epoxy-amine adduct of the present invention; starch xanthate and epoxy of the present invention Aggregation of coal and mineral by adduct with amine adduct salt; recovery of oil from waste water in oil recovery by reaction product of epoxy-amine adduct salt and epichlorohydrin of the present invention, etc. Can be used for various purposes.

  As described above, the salt of the epoxy-amine adduct of the present invention can be used as a chelate resin, ion exchange resin, separation membrane, adsorbent, anion exchange resin; heavy metal adsorbent; chelate resin; uranium adsorbent; Metal chelate adsorbent; Composite membrane for high performance reverse osmosis; Control release by microcapsule separation membrane of high electrolyte; Ion selective electrode; Acid gas adsorbent; Separation membrane for production of high-concentration sugar liquid. More specifically, the salt of the epoxy-amine adduct of the present invention includes, for example, an anion exchange resin formed from the salt of the epoxy-amine adduct of the present invention and epihalohydrin; Heavy metal adsorbent with a reaction product of a salt and carbon disulfide; Chelate resin in which a salt of the epoxy-amine adduct of the present invention and epichlorohydrin is grafted on a chloromethylated crosslinked polystyrene; Carboxy group-containing polymer Adsorption of low molecular metal chelate using an ion exchanger having an active group derived from the salt of the epoxy-amine adduct of the present invention; An ion-selective electrode using a membrane containing a salt of an epoxy-amine adduct of the present invention or a derivative thereof; porous An acid gas adsorbent obtained by adhering or reacting a salt of the epoxy-amine adduct of the present invention to the surface of the product; Separation of production of high-concentration sugar liquor by a reaction product of the salt of the epoxy-amine adduct of the present invention and a dialdehyde It can be used in forms and applications such as membranes.

  The salt of the epoxy-amine adduct of the present invention is used in the cosmetics and toiletries fields, for example, bar soap for washing skin; cosmetics for hair (shampoos, rinses, treatments, etc.); nail enamel compositions; It can be used for purposes such as prevention. More specifically, the salt of the epoxy-amine adduct of the present invention is a soap for washing skin containing the salt of the epoxy-amine adduct of the present invention or a modified product thereof; the salt of the epoxy-amine adduct of the present invention or Cosmetics for hair blended with the derivative; Neel enamel composition blended with a polyion complex synthesized by the reaction of the anionic polymer salt with the salt of the epoxy-amine adduct of the present invention; It can be used in aspects and applications such as removal of mud soil and prevention of recontamination using a salt of an epoxy-amine adduct.

  As described above, the salt of the epoxy-amine adduct of the present invention can be used as a lubricant, a rust inhibitor, and a dispersant. For example, a metal processing oil composition; a metal rolling lubricant; a ceramic dispersant; Dispersant in magnetic layer of recording medium; dispersant for coal-water slurry; prevention of adhesion of ash to metal etc. in pulverized coal-oil mixture; high-concentration low-viscosity water slurry of fine silica powder. In more detail, the salt of the epoxy-amine adduct of the present invention is, for example, a metalworking oil composition comprising a condensate of a carboxylic acid and a salt of the epoxy-amine adduct of the present invention as an active ingredient; A metal rolling lubricant containing an epoxy adduct dispersant of an epoxy-amine adduct salt of the present invention; a reaction product of the epoxy-amine adduct salt of the present invention and a carboxy group-containing polyester dispersed in a magnetic layer A magnetic recording medium containing as an agent; a dispersant for a coal-water slurry comprising a formalin condensate of a polyoxyalkylene ether of an epoxy-amine adduct of the present invention and an aromatic sulfonate; and a pulverized coal-oil mixture according to the present invention. By adding an alkylene oxide adduct of a salt of the epoxy-amine adduct, it can be used in an aspect or application such as prevention of adhesion of ash to a metal or the like.

  As described above, the epoxy-amine adduct salt of the present invention can be used as a plating agent, for example, improving glossiness; electrodeposition of bright copper on printed circuit boards; acid zinc plating; high-speed copper electroplating; It can be used for applications such as forming an electroless plating film. More particularly, the salt of the epoxy-amine adduct of the present invention improves glossiness by adding it to, for example, a plating bath (for example, a black rhodium plating bath); It can be used in forms and applications such as formation of an electroless plating film activated with a salt of.

  The salt of the epoxy-amine adduct of the present invention is used in the biological, medical and enzymatic fields, for example, comprehensive immobilization of enzymes (for example, production of palatinose by α-glucosyl transferase, immobilization of sucrose mutase, alcohol oxidase, glucose Immobilization of oxidase, cholesterol oxidase, etc., immobilization of Bacillus subtilis using 3-acetoxy group elimination product from 7-β-acylamide cephalosporanic acid, transcinnamic acid by immobilized Sporoboromyces roseus cells Production of L-phenylalanine from E. coli; purification of DNA polymerase III from cell-free extract of E. coli; detection of analyte by antibody immunofluorescence; purification of human interferon-β; purification of monoclonal and monoclonal antibodies; anti-blood Coagulant synthesis; use of enzyme-immobilized membranes, etc. It can be used in the Application. More specifically, the salt of the epoxy-amine adduct of the present invention includes, for example, the comprehensive immobilization of an enzyme with the salt of the epoxy-amine adduct of the present invention or a derivative thereof and glutaraldehyde, alginic acid, tannic acid, etc .; Detection of analyte by antibody immunofluorescence using a reaction product of a salt of an epoxy-amine adduct and a functional fluorescent dye molecule; monoclonal and monoclonal antibody using silica gel carrying a salt of the epoxy-amine adduct of the present invention Purification of an anticoagulant using a sulfonated salt of the epoxy-amine adduct of the present invention; an embodiment of an enzyme-immobilized membrane by cross-linking of the salt of the epoxy-amine adduct of the present invention and a dialdehyde Can be used for various purposes.

  As described above, the salt of the epoxy-amine adduct of the present invention can be used as a cement additive and an oil mining agent, such as a cement water reducing agent; a fluid loss agent in oil mining cementing; a concrete admixture, and the like. Can be used for More particularly, the use of the epoxy-amine adduct salts of the present invention, for example, cement water reducing agents using the hydroxy-alkylated epoxy-amine adduct salts of the present invention; carboxyethylated present invention. It can be used in embodiments and applications such as a concrete admixture using a salt of an epoxy-amine adduct.

  The salt of the epoxy-amine adduct of the present invention includes, for example, a solid electrolyte composition; binding of metal ions; accumulation of monomolecular films (cumulative method); production of sustained-release microcapsules; It can be used for such applications. More specifically, the salt of the epoxy-amine adduct of the present invention includes, for example, a solid electrolyte composition using a cross-linked product of the salt of the epoxy-amine adduct of the present invention and a polyfunctional epoxy compound; Metal ion binding by amine adduct salts or derivatives thereof; monolayer film accumulation by previously treating the surface of a solid substrate with the epoxy-amine adduct salt of the present invention (cumulative method); Production of sustained-release microcapsules by interfacial polymerization of amine adduct salt and diisocyanate compound; for aspects such as antibacterial and sterilization in water using polystyrene grafted with the epoxy-amine adduct salt of the present invention Can be used.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
[Production of salt of epoxy-amine adduct]
As the epoxy compound (A), 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate [manufactured by Daicel Corporation, trade name “Celoxide 2021P”] was used. Ethylenetetramine [manufactured by HUNTSMAN, trade name “TETA”] and isophoronediamine [manufactured by Evonik Degussa Japan Co., Ltd., trade name “Vestamine IPD”] were used.
A 1 L stainless steel reaction vessel was charged with a mixture of 228.0 g of triethylenetetramine and 171.0 g of isophoronediamine, and 632.5 g of epoxy compound (A) was added at 160 ° C. for 60 minutes in a nitrogen atmosphere. It was dripped over. Then, the epoxy-amine adduct (amine adduct) was obtained by making it react by stirring at 200 degreeC for 3 hours, and also at 220 degreeC for 2 hours.
After allowing to cool, the content of the content is flowable (130 to 150 ° C.), and then poured onto a release paper from the reaction vessel, further cooled and solidified, and then pulverized to give an epoxy-amine 1000 g of adduct was obtained.
Then, 100 g of 40% aqueous solution of the epoxy-amine adduct obtained above is put into a 300 mL flask (reaction vessel), and 9.4 g of 85% aqueous phosphoric acid solution is added to this aqueous solution and stirred for 30 minutes to react. Gave the phosphate salt of the epoxy-amine adduct (as 40% aqueous solution).

Comparative Example 1
30.0 g of bisphenol A type epoxy resin [manufactured by Nippon Steel Chemical Co., Ltd., trade name “Epototo YD128”] and 41.3 g of amine-terminated polypropylene glycol [manufactured by HUNTSMAN, trade name “JEFFAMINE D-230”] Then, both components were reacted by stirring at 160 ° C. for 2 hours. As a result, a resin having no thermoplasticity was obtained.

[Evaluation]
The following evaluation was implemented about the phosphate of the epoxy-amine adduct obtained in the Example.

(1) Evaluation of water solubility First, a 40% aqueous solution of the epoxy-amine adduct synthesized in Example 1 (before reaction with phosphoric acid) was prepared. This aqueous solution was transparent, and the epoxy-amine adduct was dissolved in the aqueous solution. Thereafter, water was added to the aqueous solution to dilute the concentration to 2%. As a result, an epoxy-amine adduct was precipitated and the solution became cloudy.
On the other hand, when the concentration of the 40% aqueous solution of the epoxy-amine adduct phosphate obtained in Example 1 was diluted by adding water to 2%, this 2% aqueous solution remained transparent. It was. Thus, it was confirmed that the water solubility is remarkably improved by using a salt.
The resin obtained in Comparative Example 1 did not dissolve in water at all.

  Moreover, the following evaluation was implemented about the epoxy-amine adduct (before making it react with phosphoric acid) obtained in Example 1. FIG.

(2) Glass transition temperature The glass transition temperature (Tg) of the epoxy-amine adduct was measured with a differential scanning calorimeter (DSC) [manufactured by Seiko Instruments Inc.]. In the measurement, the temperature was raised from 25 ° C. to 200-230 ° C. at a rate of temperature increase of 20 ° C./min under nitrogen flow, and then cooled to −100 ° C. at a cooling rate of 20 ° C./min. Next, the temperature is raised to 350 ° C. at a rate of 10 ° C./min, and then cooled to 25 ° C. at a rate of 20 ° C./min (from the end of the first scan to here) For the second scan). The glass transition temperature was determined from the DSC curve at the time of temperature increase in the second scan. As a result, the measured glass transition temperature was 79.9 ° C.

(3) 5% weight loss temperature (Td ₅ )
The thermal decomposition temperature (5% weight loss temperature (Td ₅ )) of the epoxy-amine adduct was measured with a differential thermothermal gravimetric simultaneous measurement device (TG / DTA) [manufactured by Seiko Instruments Inc.]. The measurement was performed by raising the temperature from 25 ° C. to 400 ° C. at a rate of 10 ° C./min under a nitrogen flow. As a result, the measured 5% weight loss temperature was 317.6 ° C.

Claims (6)

A salt of an amine compound [I] having two or more amino groups in the molecule and phosphoric acid [II],
The amine compound [I] is obtained by a reaction between an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule. A salt of an epoxy-amine adduct, which is an epoxy-amine adduct. The epoxy-amine adduct salt according to claim 1, wherein the epoxy compound (A) is a compound represented by the following formula (a).

[Wherein, X represents a single bond or a divalent group having one or more atoms. ] The amine compound (B) is represented by the following formula (b-1)

[In the formula (b-1), R ² and R ³ are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic group. A divalent group in which one or more hydrocarbon groups and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. q represents 0 or an integer of 1 or more. ]
An amine compound (B1) represented by the following formula (b-2):

[In formula (b-2), R ⁴ and R ⁵ are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic group. A divalent group formed by linking one or more hydrocarbon groups and one or more cyclic aliphatic hydrocarbon groups. r represents an integer of 1 or more. ]
And an amine compound (B2) represented by the following formula (b-3):

[In Formula (b-3), R ⁶ and R ⁸ are the same or different and each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. s represents 0 or 1. R ⁷ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. t shows the integer of 0-10. ]
The salt of an epoxy-amine adduct according to claim 1 or 2, which is at least one compound selected from the group consisting of amine compounds (B3) represented by formula (1).   The resin composition containing the salt of the epoxy-amine adduct as described in any one of Claims 1-3, and a thermoplastic resin.   The resin composition according to claim 4, which is a resin composition for fiber-reinforced composite materials.   The aqueous solution containing the salt of the epoxy-amine adduct as described in any one of Claims 1-3.

Images