JP2019056043A - Water dispersion type resin composition, sizing agent, carbon fiber coated with sizing agent, and fiber-reinforced composite material - Google Patents

Abstract

To provide a water dispersion type resin composition that enhances adhesion between a resin and an additive and can form a polymer-based composite (a fiber-reinforced composite material or the like) excellent in mechanical properties (toughness in particular).SOLUTION: The water dispersion type resin composition includes: an epoxy-amine adduct being a compound [I] having two or more amino groups in the molecule or a salt thereof in which the compound [I] is an adduct of (A) an alicyclic epoxy compound and (B) an amine compound; the epoxy resin (A) includes a compound represented by formula (a) as given below; and the amine compound (B) includes a compound represented by R(NH2)P [Rrepresents a p-valent organic group having a carbon atom at a binding site to a nitrogen atom; and p represents an integer of 2 or more.] and being a compound having amino groups at both terminals; a higher fatty acid ester; and a surfactant. [In the formula, X represents a single bond or a divalent group having one or more atoms.]SELECTED DRAWING: None

Description

  The present invention relates to a water-dispersed resin composition containing an epoxy-amine adduct, and a fiber-reinforced composite material formed from a prepreg obtained by impregnating or coating a reinforcing fiber with the water-dispersed resin composition.

  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. Patent Documents 4 and 5 disclose amine adducts obtained by reacting an epoxy resin having an alicyclic epoxy group with a diamine.

JP 56-155222 A Japanese Unexamined Patent Publication No. 57-1000012 JP 61-228018 A International Publication WO2013 / 172200 International Publication No. WO2013 / 172199

  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 agent, a coating material, etc., the use as an adhesive property improving agent for improving the adhesiveness with respect to a to-be-adhered body in these adhesive agents, a coating material, etc. are anticipated.

  However, the amine adducts disclosed in Patent Documents 1 to 3 do not have an active hydrogen such as a hydrogen atom directly bonded to a nitrogen atom, or the active hydrogen may be various compounds (for example, inorganic acids, organic acids, phenols). For example, when used as an adhesion improver in a polymer composite, the effect of improving the adhesion between the resin and the additive is sufficient. It was difficult to obtain.

  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. However, for example, an adduct of an epoxy compound having a glycidyl group, such as bisphenol A diglycidyl ether, which is conventionally known as an amine adduct, and a polyamine compound is softened or melted even when heated because a crosslinked structure is formed. Therefore, uniform blending with other materials was difficult.

  The amine adducts described in Patent Documents 4 and 5 are improved in the drawbacks of the amine adducts in Patent Documents 1 to 3 described above, and have reactivity with functional groups such as hydroxyl groups, carboxyl groups, and epoxy groups present on the surface of the reinforcing fiber. High, can effectively improve the adhesion between the resin and the reinforcing fiber in the fiber-reinforced composite material, and can be softened or melted by heating, or has excellent solubility in solvents, resins, etc. It is described that it can be easily blended with these components.

However, the amine adducts described in Patent Documents 4 and 5 are brittle and have a problem of insufficient toughness.
The amine adduct is required to be tough in order to exhibit excellent adhesiveness or sufficient convergence when used as an adhesive or sizing agent. If the material itself is brittle, it may not be possible to exhibit desired properties as an adhesive or the like, and problems such as contamination due to debris generated by collapse may also occur. In addition, when used as an additive, there is a concern that the performance (for example, mechanical properties) of the polymer composite may be reduced.

  Furthermore, the amine adduct is excellent in solubility in water (water-soluble) so that it can be used in the form of an aqueous solution or aqueous dispersion from the viewpoint of environmental protection or safety of the working environment. Preferably there is. For example, it is excellent in water solubility, so that it can be applied to products (for example, water-dispersed resin compositions such as water-based paints (water-soluble paints)) using water or a solvent mainly composed of water as a medium. It becomes possible. 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 is also required to have a somewhat high glass transition temperature (for example, a glass transition temperature of room temperature or higher).

Therefore, the object of the present invention is to improve the adhesion between the resin and the additive (reinforcing fiber, etc.) in the polymer composite (fiber reinforced composite material, etc.), and further excellent in mechanical properties (particularly toughness). An object of the present invention is to provide a water-dispersed resin composition capable of forming a polymer-based composite (such as a fiber-reinforced composite material).
Another object of the present invention is to improve the high-order workability of the carbon fiber, improve the adhesion between the carbon fiber and the matrix resin, and have excellent mechanical properties (particularly toughness). An object of the present invention is to provide a carbon fiber sizing agent capable of forming a reinforced composite material.
Furthermore, another object of the present invention is to provide a sizing agent-coated carbon fiber having excellent high-order processability and excellent adhesion between carbon fiber and a matrix resin, and mechanical properties (particularly by including the sizing agent-coated carbon fiber). It is to provide a fiber-reinforced composite material having excellent toughness.
Another object of the present invention is to provide a prepreg capable of forming a fiber-reinforced composite material having excellent adhesion between a matrix resin and reinforcing fibers and mechanical properties (particularly toughness).

  As a result of intensive studies to solve the above problems, the present inventors have found that a water-dispersed resin containing a specific epoxy-amine adduct, a higher fatty acid ester, a surfactant, and, if necessary, a urethane resin. The composition can improve the adhesion between the resin and the additive (reinforced fiber, etc.) in the polymer-based composite (fiber reinforced composite material, etc.) and is excellent in mechanical properties (particularly toughness). 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。］

［式中、Ｒ¹は、式中に示される窒素原子との結合部位に炭素原子を有するｐ価の有機基を示す。ｐは２以上の整数を示す。］ That is, the present invention is a compound selected from the group consisting of a compound [I] having two or more amino groups in the molecule and a salt of the compound [I],
Compound [I] is an adduct of 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,
The epoxy compound (A) includes a compound represented by the following formula (a),
The amine compound (B) includes a compound represented by the following formula (b),
Provided is an aqueous dispersion resin composition comprising an epoxy-amine adduct, which is a compound having an amino group at both ends, a higher fatty acid ester, and a surfactant.

[Wherein, X represents a single bond or a divalent group having one or more atoms. ]

[Wherein, R ¹ represents a p-valent organic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula. p represents an integer of 2 or more. ]

  The water-dispersed resin composition may further contain a urethane resin.

  In the water-dispersed resin composition, the urethane resin may be an emulsion type urethane resin.

［式中、Ｒ^1'は、式中に示される窒素原子との結合部位に炭素原子を有する二価の有機基を示す。Ｘは単結合、又は１以上の原子を有する二価の基を示す。ｚは１以上の整数を示す。］ In the water-dispersed resin composition, the compound [I] having two or more amino groups in the molecule may be a compound having two or more amino groups in the molecule represented by the following (I): Good.

[Wherein, R ^{1 ′} represents a divalent organic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula. X represents a single bond or a divalent group having one or more atoms. z represents an integer of 1 or more. ]

  In the water-dispersed resin composition, the epoxy-amine adduct may be a carbonate or an organic acid salt of the compound [I].

  In the water-dispersed resin composition, the surfactant may be a nonionic surfactant.

  In the water-dispersed resin composition, the surfactant is at least one interface selected from the group consisting of a polyoxyalkylene alkyl ether type nonionic surfactant and a sorbitan derivative type nonionic surfactant. It may be an activator.

［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。］

［式中、Ｒ¹は、式中に示される窒素原子との結合部位に炭素原子を有するｐ価の有機基を示す。ｐは２以上の整数を示す。］ Further, the present invention is a compound selected from the group consisting of compound [I] having two or more amino groups in the molecule and a salt of compound [I],
Compound [I] is an adduct of 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,
The epoxy compound (A) includes a compound represented by the following formula (a),
The amine compound (B) includes a compound represented by the following formula (b),
Provided is a method for producing a water-dispersed resin composition, comprising mixing an aqueous dispersion containing an epoxy-amine adduct, which is a compound having an amino group at both ends, a higher fatty acid ester, and a surfactant. .

[Wherein, X represents a single bond or a divalent group having one or more atoms. ]

[Wherein, R ¹ represents a p-valent organic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula. p represents an integer of 2 or more. ]

  In the method for producing the water-dispersed resin composition, a urethane resin may be further mixed.

  In the method for producing the water-dispersed resin composition, the urethane resin may be an emulsion-type urethane resin.

  In the method for producing the water-dispersed resin composition, the surfactant may be a nonionic surfactant.

  In the method for producing the water-dispersed resin composition, the surfactant is at least selected from the group consisting of a polyoxyalkylene alkyl ether type nonionic surfactant and a sorbitan derivative type nonionic surfactant. It may be a kind of surfactant.

  The present invention also provides a carbon fiber sizing agent comprising the water-dispersed resin composition.

  The present invention also provides a carbon fiber sizing agent-coated carbon fiber coated with the carbon fiber sizing agent.

  Moreover, this invention provides the fiber reinforced composite material containing the said carbon fiber sizing agent application | coating carbon fiber.

  The present invention also provides a carbon fiber treating agent comprising the water-dispersed resin composition.

  Moreover, this invention provides the carbon fiber bundle which apply | coated the said sizing agent for carbon fibers.

  Moreover, this invention provides the prepreg by the said sizing agent application | coating carbon fiber for carbon fibers.

  Moreover, this invention provides the fiber reinforced composite material formed from a prepreg.

  Furthermore, this invention provides the fiber reinforced composite material containing the said sizing agent application | coating carbon fiber for carbon fibers, and a thermoplastic resin.

  Since the water-dispersed resin composition of the present invention contains the above-mentioned epoxy-amine adduct, for example, hydroxy groups, carboxy groups, epoxy groups (particularly glycidyl groups), etc. present on the surface of additives such as reinforcing fibers and fillers. It has high reactivity and affinity for functional groups (reactive functional groups), and can effectively improve the adhesion between matrix resin and additives in polymer composites such as fiber reinforced composite materials and nanocomposites. By including higher fatty acid esters and surfactants, the resulting fiber-reinforced composite materials and nanocomposites are excellent in mechanical properties (particularly toughness), and therefore excellent adhesion when used as an adhesive or sizing agent. , Mechanical properties, convergence, etc. can be exhibited.

  Moreover, since the sizing agent for carbon fiber of the present invention has the above-described configuration, it is possible to improve the high-order processability of the carbon fiber, and the adhesion between the carbon fiber and the matrix resin and the mechanical strength of the fiber-reinforced composite material ( In particular, the toughness can be improved. For this reason, the sizing agent-coated carbon fiber obtained by applying the sizing agent for carbon fiber of the present invention to carbon fiber is excellent in high-order processability, and adhesion, adhesion, and mechanical strength (particularly, carbon fiber and matrix resin). , Excellent toughness). Furthermore, the fiber reinforced composite material including the sizing agent-coated carbon fiber has excellent heat resistance and mechanical strength (particularly toughness) and high productivity.

  Furthermore, when the water-dispersed resin composition of the present invention contains a urethane resin, the adhesion between the matrix resin and the reinforcing fibers in the fiber-reinforced composite material can be effectively improved. In particular, the water-dispersed resin composition of the present invention is very useful in that, regardless of which matrix resin is used, the resin can widely exhibit good adhesion to reinforcing fibers. Moreover, since it takes the form of a water-dispersed resin composition, it is possible to easily impregnate or apply the reinforced resin. Furthermore, the water-dispersed resin composition of the present invention does not contain an organic solvent or can be used without selecting a working environment by making it a water-dispersed resin composition (aqueous dispersion) with a low content. It is also advantageous in terms of environmental protection. For this reason, when the water-dispersed resin composition of the present invention is used, a prepreg capable of forming a fiber-reinforced composite material having excellent productivity and excellent adhesion between the matrix resin and the reinforcing fiber is obtained. Thus, a fiber-reinforced composite material having excellent adhesion between the matrix resin and the reinforcing fibers and having high mechanical properties (particularly toughness) can be obtained.

<Water-dispersed resin composition>
The water-dispersed resin composition of the present invention comprises a water-dispersed resin composition (an epoxy-amine adduct and a higher compound) containing, as essential components, an epoxy-amine adduct described later, a higher fatty acid ester, and a surfactant. An aqueous dispersion containing a fatty acid ester and a surfactant; sometimes referred to as “water-dispersed resin composition of the present invention”. As will be described later, the water-dispersed resin composition of the present invention may further contain other components such as a urethane resin.

  In the water-dispersed resin composition of the present invention, “water-dispersed” means a state in which at least a part of the epoxy-amine adduct, the higher fatty acid ester and the surfactant is not dissolved in the aqueous medium, A suspended and dispersed state and an emulsified and dispersed state are included. In the water-dispersed resin composition of the present invention, it is preferable that at least a higher fatty acid ester is emulsified and dispersed in an aqueous medium.

<Epoxy-amine adduct>
The epoxy-amine adduct, which is an essential component of the water-dispersed resin composition of the present invention, is a compound [I] having two or more amino groups in the molecule (sometimes simply referred to as “compound [I]”). And a compound selected from the group consisting of salts of compound [I], wherein compound [I] has an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule, and A compound that is an adduct with an amine compound (B) having two or more amino groups,
The epoxy compound (A) includes a compound represented by the following formula (a),
The amine compound (B) includes a compound represented by the following formula (b),
An epoxy-amine adduct characterized by being a compound having an amino group at both ends.

［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。］

[Wherein, X represents a single bond or a divalent group having one or more atoms. ]

［式中、Ｒ¹は、式中に示される窒素原子との結合部位に炭素原子を有するｐ価の有機基を示す。ｐは２以上の整数を示す。］

[Wherein, R ¹ represents a p-valent organic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula. p represents an integer of 2 or more. ]

  In the present specification, the compound [I] may be referred to as “first embodiment of the epoxy-amine adduct of the present invention”, and the salt of compound [I] may be referred to as “second embodiment of the epoxy-amine adduct of the present invention”. is there. In addition, the first and second aspects of the epoxy-amine adduct of the present invention may be collectively referred to as “the epoxy-amine adduct of the present invention”.

  That is, the first and second embodiments of the epoxy-amine adduct of the present invention are both compound [I] [epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and 2 in the molecule. It is an adduct with an amine compound (B) having at least one amino group and has a structure derived from a compound having at least two amino groups in the molecule. Since the first and second aspects of the epoxy-amine adduct of the present invention have such a common structure, a matrix resin and an additive (for example, reinforcing fiber) in a polymer-based composite (for example, fiber-reinforced composite material) are provided. ) And a polymer composite (for example, a fiber reinforced composite material) having excellent mechanical properties (particularly toughness) and being easily compounded with other components such as a resin. There is an effect that it can be formed.

  First, the compound [I] giving the above-mentioned common structure in the epoxy-amine adduct of the present invention will be described.

[Compound [I]]
Compound [I] is a compound having two or more amino groups (—NH ₂ ) in the molecule as described above, and is an epoxy-amine adduct of an epoxy compound (A) and an amine compound (B). It is. More specifically, the compound [I] is produced by reacting an alicyclic epoxy group possessed by the epoxy compound (A) with an amino group possessed by the amine compound (B). ) And one or more (preferably two or more) amine compound (B) adduct. 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.

1. Epoxy compound (A)
The epoxy compound (A) as a raw material of the compound [I] is a polyepoxy compound (alicyclic epoxy compound) having two or more alicyclic epoxy groups in the molecule, represented by the following formula (a). It is characterized by including the compound.

  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. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring (alicyclic epoxy group) in the formula (a).

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

  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, vinylene group, propenylene group, and 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.

  When the epoxy compound (A) contains an ester bond (—CO—O—), the ester bond exchanges with the amino group of the amine compound (B) during the reaction with the amine compound (B). Thus, an amidated by-product (sometimes referred to simply as “amide by-product”) is inevitably partly formed, but the epoxy-amine adduct of the present invention impairs the effects of the present invention. Byproducts such as a decomposition product of the epoxy compound (A) and the amine compound (B) and the amide by-product may be included as long as they are not included.

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) -Epoxycyclohexyl) propane (= 2,2-bis (3,4-epoxycyclohexane-1-yl) propane), 1,2-bis (3,4-epoxycyclohexyl) ethane (= 1,2-bis (3 , 4-epoxycyclohexane-1-yl) ethane), 2,3-bis (3,4-epoxycyclohexyl) oxirane (= 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.

  The epoxy compound (A) is a compound represented by the above formula (a-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; “Celoxide 2021P” (manufactured by Daicel Corporation) and the like] are preferable.

  The epoxy compound (A) may be used alone or in combination of two or more.

2. Amine compound (B)
The amine compound (B) as a raw material of the compound [I] is a polyamine compound having two or more amino groups (—NH ₂ ; unsubstituted amino group) in the molecule and represented by the following formula (b). (Hereinafter sometimes referred to as “amine compound (b)”).

  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, blending with the other components of the epoxy-amine adduct of the present invention can be facilitated, and the solubility of the epoxy-amine adduct in a solvent, water solubility, There is a tendency that toughness and flexibility are further improved.

  Although the molecular weight of an amine compound (B) is not specifically limited, 80-10000 are preferable, More preferably, it is 100-5000, More preferably, it is 200-1000. When the molecular weight is less than 80, the amount of -NH- group (substituted amino group) described later in the epoxy-amine adduct of the present invention is excessively increased, for example, a composition with a curable resin (curable compound). In some cases, a cured product (cured resin) obtained by curing the resin becomes too brittle. On the other hand, when the molecular weight exceeds 10,000, the effect of reacting the epoxy compound (A) is reduced, or the effect obtained by blending the epoxy-amine adduct of the present invention (for example, improvement in heat resistance of a cured product (cured resin)) , Improvement in heat resistance and toughness of the fiber reinforced composite material) may be insufficient.

  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.

  Only one type of amine compound (B) may be used, or two or more types may be used in combination.

［式中、Ｒ^1aは、下記（ａ）及び（ｂ）からなる群より選択される二価の基を示す。
（ａ）二価の直鎖又は分岐鎖状の脂肪族炭化水素の２以上がヘテロ原子を含む連結基を介して結合した二価の基
（ｂ）二価の直鎖又は分岐鎖状の脂肪族炭化水素基と二価の環状の脂肪族炭化水素基とが直接結合した二価の基］ More specifically, as the amine compound (B), a compound represented by the following formula (b-I) (sometimes referred to as “amine compound (BI)”), represented by the following formula (b-II): And the like (sometimes referred to as “amine compound (BII)”).

[Wherein, R ^1a represents a divalent group selected from the group consisting of the following (a) and (b).
(A) a divalent group in which two or more divalent linear or branched aliphatic hydrocarbons are bonded via a linking group containing a heteroatom (b) a divalent linear or branched fatty acid Divalent group in which an aromatic hydrocarbon group and a divalent cyclic aliphatic hydrocarbon group are directly bonded]

［式中、Ｒ^1bは、下記（ｃ）〜（ｇ）からなる群より選択される二価の基を示す。
（ｃ）炭素数６〜１２の芳香族炭化水素から水素原子を２個除いてなる二価の基
（ｄ）炭素数６〜１２の芳香族炭化水素から水素原子を２個除いてなる二価の基と二価の直鎖又は分岐鎖状の脂肪族炭化水素基とが直接結合した二価の基
（ｅ）窒素原子、硫黄原子及び酸素原子からなる群より選択されるヘテロ原子を環内に１又は２個有する芳香族複素環から水素原子を２個除いてなる二価の基
（ｆ）窒素原子、硫黄原子及び酸素原子からなる群より選択されるヘテロ原子を環内に１又は２個有する芳香族複素環から水素原子を２個除いてなる二価の基と二価の直鎖又は分岐鎖状の脂肪族炭化水素基とが直接結合した二価の基
（ｇ）炭素数６〜１２の芳香族炭化水素の２以上が連結基を介して結合した基から水素原子を２個除いてなる二価の基

[Wherein, R ^1b represents a divalent group selected from the group consisting of the following (c) to (g).
(C) a divalent group formed by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms (d) a divalent group formed by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms A divalent group in which a divalent linear or branched aliphatic hydrocarbon group is directly bonded (e) a hetero atom selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring A divalent group formed by removing two hydrogen atoms from an aromatic heterocycle having 1 or 2 in the ring (f) 1 or 2 heteroatoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring A divalent group in which a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring and a divalent linear or branched aliphatic hydrocarbon group are directly bonded (g) 6 carbon atoms A divalent group obtained by removing two hydrogen atoms from a group in which two or more of -12 aromatic hydrocarbons are bonded via a linking group

The amine compound (B) may contain only one of the amine compound (BI) and the amine compound (BII), or may contain both the amine compound (BI) and the amine compound (BII).
The adhesion between the matrix resin and the additive (for example, reinforcing fiber) in the polymer composite (for example, fiber reinforced composite material) can be improved, and the compounding with other components such as the resin becomes easy, The amine compound (B) is an amine compound (BI) from the viewpoint that an effect of forming a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness) can be obtained. And an amine compound (BII).

  In the case where the amine compound (B) contains both the amine compound (BI) and the amine compound (BII), the ratio (molar ratio of amine compound (BI) / amine compound (BII)) is not particularly limited. 5-7.0 (mol / mol) is preferable and 5.0-6.5 (mol / mol) is preferable. When this ratio is lower than 4.5 (mol / mol), the water solubility tends to decrease, and when higher than 7.0 (mol / mol), the toughness of the epoxy-amine adduct becomes insufficient. There is a case.

R ^1a in the above formula (b-I) represents a divalent group selected from the group consisting of the following (a) and (b).
(A) a divalent group in which two or more divalent linear or branched aliphatic hydrocarbons are bonded via a linking group containing a heteroatom (b) a divalent linear or branched fatty acid Divalent group in which an aromatic hydrocarbon group and a divalent cyclic aliphatic hydrocarbon group are directly bonded

Examples of the divalent linear or branched aliphatic hydrocarbon include alkylene groups [eg, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene. Straight chain or branched chain alkylene having 1 to 30 carbon atoms (C _1-30 ) such as a group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, etc. 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 ( Preferred are C _2-18 alkenylene groups) and the like.

  The divalent linear or branched aliphatic hydrocarbon may have various substituents (that is, hydrogen contained in the divalent linear or branched aliphatic hydrocarbon). At least one of the atoms 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.

Examples of the divalent cyclic 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, 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. The divalent cyclic aliphatic hydrocarbon group may have a substituent, and as the substituent, for example, the divalent linear or branched aliphatic hydrocarbon has. In addition to the substituents that may be present, monovalent groups 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) A hydrocarbon group etc. are mentioned.

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.

In a preferred embodiment when R ^1a is (a), two or more of the linear or branched alkylene groups having 2 to 6 carbon atoms (in particular, ethylene group, trimethylene group, propylene group, etc.) are —NH—. Or it is a bivalent group couple | bonded through -O-.
A preferable embodiment when R ^1a is (b) is a linear or branched alkylene group having 1 to 6 carbon atoms (particularly a methylene group, ethylene group, trimethylene group, propylene group, etc.) and 3 to 3 carbon atoms. It is a divalent group in which 20 cycloalkylene groups are directly bonded.

  Only one type of amine compound (BI) may be used, or two or more types may be used in combination.

The amine compound (BI) includes an amine compound (BI) in which R ^1a is (a) (sometimes referred to as “amine compound (BIa)”) and an amine compound (BI) in which R ^1a is (b) (“ Any one of the amine compound (BIb) ”may be included, and both the amine compound (BIa) and the amine compound (BIb) may be included.
The adhesion between the matrix resin and the additive (for example, reinforcing fiber) in the polymer composite (for example, fiber reinforced composite material) can be improved, and the compounding with other components such as the resin becomes easy, The amine compound (BI) is an amine compound (BIa) from the viewpoint that an effect of forming a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness) can be obtained. And an amine compound (BIb).

  When the amine compound (BI) includes both the amine compound (BIa) and the amine compound (BIb), the ratio (molar ratio of amine compound (BIa) / amine compound (BIb)) is not particularly limited. 5-5.2 (mol / mol) is preferable and 3.0-4.8 (mol / mol) is preferable. When this ratio is lower than 1.5 (mol / mol), it tends to be brittle, and when it is higher than 5.2 mol / mol), tackiness may be exhibited.

R ^1b in the above formula (b-II) represents a divalent group selected from the group consisting of the following (c) to (g).
(C) a divalent group formed by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms (d) a divalent group formed by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms A divalent group in which a divalent linear or branched aliphatic hydrocarbon group is directly bonded (e) a hetero atom selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring A divalent group obtained by removing two hydrogen atoms from an aromatic heterocycle having 1 or 2 (hereinafter sometimes simply referred to as “aromatic heterocycle”); and (f) a hydrogen atom from an aromatic heterocycle A divalent group in which two divalent groups and two divalent linear or branched aliphatic hydrocarbon groups are directly bonded (g) 2 or more of aromatic hydrocarbons having 6 to 12 carbon atoms Is a divalent group formed by removing two hydrogen atoms from a group bonded through a linking group

  The divalent group in (d) is a divalent group in which one divalent linear or branched aliphatic hydrocarbon group is directly bonded to an aromatic hydrocarbon (that is,-(aromatic carbon Hydrogen)-(aliphatic hydrocarbon group)-), and a divalent group in which two divalent linear or branched aliphatic hydrocarbon groups are directly bonded to an aromatic hydrocarbon ( That is, it may be-(aliphatic hydrocarbon group)-(aromatic hydrocarbon)-(aliphatic hydrocarbon group)-). In the latter case, the two aliphatic hydrocarbon groups may be the same or different.

  The divalent group (f) is a divalent group in which one divalent linear or branched aliphatic hydrocarbon group is directly bonded to an aromatic heterocycle (that is,-(aromatic heterocycle). Ring)-(aliphatic hydrocarbon group)-), and a divalent group in which two divalent linear or branched aliphatic hydrocarbon groups are directly bonded to an aromatic heterocyclic ring ( That is, it may be-(aliphatic hydrocarbon group)-(aromatic heterocycle)-(aliphatic hydrocarbon group)-). In the latter case, the two aliphatic hydrocarbon groups may be the same or different.

Examples of the aromatic hydrocarbon having 6 to 12 carbon atoms include benzene, naphthalene, biphenyl and the like. The aromatic hydrocarbon may have a substituent, and as the substituent, for example, a substituent that the divalent linear or branched aliphatic hydrocarbon may have. In addition, an alkyl group (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group), a monovalent hydrocarbon group such as an alkenyl group, a cycloalkyl group, or a cycloalkenyl group can be used.

Examples of the aromatic heterocycle (aromatic heterocycle having one or two heteroatoms selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom in the ring) include, for example, an aromatic group containing an oxygen atom as a heteroatom. Aromatic heterocycles (eg, 5-membered rings such as furan ring and oxazole ring, condensed rings such as benzofuran ring and chroman ring), aromatic heterocycles containing sulfur atoms as heteroatoms (eg, thiophene ring, thiazole ring, thiadiazole) 5-membered rings such as rings, condensed rings such as benzothiophene rings), and aromatic heterocycles containing nitrogen atoms as heteroatoms (eg, pyrrole rings, pyrrolidine rings, pyrazole rings, imidazole rings, triazole rings, etc.) , Pyridine ring, pyridazine ring, pyrimidine ring, 6-membered ring such as pyrazine ring, indole ring, indoline ring, quinoline ring, acridine ring, naphthi Jin ring, a quinazoline ring, a condensed ring of the purine ring, etc.) and the like. The aromatic heterocyclic ring may have a substituent. Examples of the substituent include those of the substituent that the divalent linear or branched aliphatic hydrocarbon may have. In addition, monovalents such as alkyl groups (eg, C _1-4 alkyl groups such as methyl and ethyl groups), alkenyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups (eg, phenyl groups, naphthyl groups, etc.) And the like. In addition, the nitrogen atom constituting the aromatic heterocyclic ring 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). Group) and the like.

Examples of the divalent linear or branched aliphatic hydrocarbon include the divalent linear or branched aliphatic hydrocarbon exemplified as R ^1a .

Examples of the linking group (divalent group) include the divalent linear or branched aliphatic hydrocarbon, the divalent cyclic aliphatic hydrocarbon group, -CO-, -O-, —CO—O—, —O—CO—O—, —CO—NH—, —CO—NR ^a — (substituted amide group; R ^a represents an alkyl group), —NH—, —NR ^b — (R ^b represents an alkyl group), a divalent group containing a hetero atom (oxygen atom, nitrogen atom, sulfur atom, etc.) such as —SO— or —SO ₂ —, a divalent group in which a plurality of these are linked, and the like. Can be mentioned.

Among them, the R ^1b is preferably a divalent group (d), a divalent group (e), or a divalent group (g), more preferably an aromatic having 6 to 10 carbon atoms. A divalent group (for example, a xylene group) in which a divalent group (for example, a phenylene group) obtained by removing two hydrogen atoms from a hydrocarbon and an alkylene group having 1 to 4 carbon atoms (for example, a methylene group) is directly bonded. A divalent group obtained by removing two hydrogen atoms from an aromatic heterocycle (for example, a pyridine ring), two aromatic hydrocarbons having 6 to 10 carbon atoms (for example, a benzene ring) and a linking group (for example, A divalent group obtained by removing two hydrogen atoms from a group bonded via —SO ₂ — and the like.

More specifically, as the amine compound (BI), a compound represented by the following formula (b-1) (sometimes referred to as “amine compound (B1)”), represented by the following formula (b-2): And a compound represented by the following formula (b-3) (sometimes referred to as “amine compound (B3)”).

In said formula (b-1), R < ² > and R < ³ > are the same or different, and show a bivalent linear or branched aliphatic hydrocarbon. Examples of the divalent linear or branched aliphatic hydrocarbon include the divalent linear or branched aliphatic hydrocarbon exemplified as R ^1a .

Among them, R ² is preferably a linear or branched alkylene group having 2 to 6 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms (particularly, an ethylene group or a trimethylene group). , Propylene group).

Among them, R ³ is preferably a linear or branched alkylene group having 2 to 6 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms (particularly, an ethylene group or a 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 an integer of 1 or more. For example, q is preferably 1 to 100, more preferably 1 to 70, still more preferably 1 to 30, and particularly preferably 1 to 8. By setting q to 100 or less, the heat resistance and water solubility of the epoxy-amine adduct of the present invention are further improved, and the heat resistance and mechanical properties (toughness) of polymer composites (particularly fiber reinforced composite materials) are improved. Etc.) tend to improve further. On the other hand, when q is 1 or more, the adhesion between the matrix resin and the additive in the polymer composite using the epoxy-amine adduct of the present invention tends to be improved.

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

  Among them, as the compound represented by the above formula (b-1) (amine compound (B1)), adhesion to the additive (particularly reinforcing fiber) of the epoxy-amine adduct of the present invention, wettability, heat resistance, From the viewpoint of water solubility, 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).

In the above formula (b-2), R ⁴ represents a divalent linear or branched aliphatic hydrocarbon. 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 alkylene group having 2 to 6 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms (particularly, an ethylene group or a trimethylene group). , Propylene group).

In the above formula (b-2), R ⁵ represents a divalent linear or branched aliphatic hydrocarbon. 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 alkylene group having 2 to 6 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms (particularly, an ethylene group or a 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 heat resistance and water solubility of the epoxy-amine adduct of the present invention are further improved, and the heat resistance and mechanical properties (toughness of the polymer composite (particularly, fiber reinforced composite material)). Etc.) tend to improve further. On the other hand, by setting r to 1 or more, the adhesion between the matrix resin and the additive in the polymer composite using the epoxy-amine adduct of the present invention 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, as the compound represented by the above formula (b-2) (amine compound (B2)), the adhesiveness to the additive (especially reinforcing fiber) of the epoxy-amine adduct of the present invention, the wettability with the matrix resin. In view of the above, amine-terminated (both terminal amino groups) polyethylene glycol, amine-terminated polypropylene glycol, and amine-terminated polybutylene glycol are preferable, and amine-terminated polypropylene glycol is more preferable. 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.

In said formula (b-3), R < ⁶ > and R <^8> are the same or different and show a C1-C4 alkylene group. Specific examples of R ⁶ and R ⁸ include methylene group, ethylene group, propylene group, butylene group and the like.

  In the above formula (b-3), s represents 0 or 1.

In the above formula (b-3), R ⁷ 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, or a monovalent sulfur. An atom-containing group, a monovalent nitrogen atom-containing group, or a halogen atom is shown. Specific examples of R ⁷ include substituents that the divalent cyclic aliphatic hydrocarbon group may have. Further, in the above formula (b-3), t denotes 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 methylene-1,2-cyclohexylene-methylene group, methylene-1,3-cyclohexylene-methylene group, methylene 1,4-cyclohexylene - cyclohexylene - - alkylene such as a methylene group alkylene group, and the like.

  Especially, as a compound (amine compound (B3)) represented by the said Formula (b-3), an isophorone diamine is preferable from a heat resistant viewpoint of the epoxy-amine adduct of this invention. 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.

  As the amine compound (BI), in particular, a compound represented by the formula (b-1) from the viewpoints of improving the adhesion between the matrix resin and the additive by the epoxy-amine adduct of the present invention, heat resistance, toughness, etc. And a compound represented by formula (b-3) is preferred, and a compound represented by formula (b-1) is more preferred.

More specifically, the amine compound (BII) is represented by the following formula (b-5) (sometimes referred to as “amine compound (B5)”), and the following formula (b-6). Examples thereof include a compound (sometimes referred to as “amine compound (B6)”), a compound represented by the following formula (b-7) (sometimes referred to as “amine compound (B7)”), and the like.

In the above formula (b-5), A ¹ represents an aromatic hydrocarbon having 6 to 12 carbon atoms. The aromatic hydrocarbon of the 6 to 12 carbon atoms, for example, aromatic hydrocarbons having 6 to 12 carbon atoms exemplified as R ^1b.

In said formula (b-5), R < ¹¹ > and R <^13> are the same or different and show a C1-C4 alkylene group. As said C1-C4 alkylene group, the C1-C4 alkylene group illustrated as R < ⁶ > and R < ⁸ > in Formula (b-3) is mentioned.

  In the above formula (b-5), w1 and w3 are the same or different and represent 0 or 1.

In the above formula (b-5), R ¹² represents a monovalent organic group, oxygen atom-containing group, sulfur atom-containing group, nitrogen atom-containing group, or halogen atom. Examples of the monovalent organic group, oxygen atom-containing group, sulfur atom-containing group, nitrogen atom-containing group, and halogen atom include those exemplified as R ⁷ . Further, in the above formula (b-5), w2 indicates the number of substituents A ^1, shown in the formula (R ^12), an integer of 0-4. When w2 in the above formula (b-5) is an integer of 2 or more, each R ¹² 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-5) include 1,2-phenylene group and 1,3-phenylene. Group, arylene group such as 1,4-phenylene group, 1,2-phenylene-methylene group, 1,3-phenylene-methylene group, 1,4-phenylene-methylene group, 1,2-phenylene-ethylene group, 1 , 3-phenylene-ethylene group, 1,4-phenylene-ethylene group or other arylene-alkylene group, methylene-1,2-phenylene-methylene group, methylene-1,3-phenylene-methylene group, methylene-1,4 -An alkylene-arylene-alkylene group such as a phenylene-methylene group.

  Among these, as the compound represented by the above formula (b-5) (amine compound (B5)), a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness) can be formed. From the viewpoint, m-xylenediamine, p-xylenediamine, and o-xylenediamine are preferable. Moreover, a commercial item can also be used as a compound represented by the said Formula (b-5).

In the above formula (b-6), B ¹ represents an aromatic heterocycle having 1 or 2 heteroatoms in the ring selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom (aromatic heterocycle). Show. Examples of the aromatic heterocycle include the aromatic heterocycle exemplified as R ^1b .

In the above formula (b-6), R ¹⁴ and R ¹⁶ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. As said C1-C4 alkylene group, the C1-C4 alkylene group illustrated as R < ⁶ > and R < ⁸ > in Formula (b-3) is mentioned.

  In the above formula (b-6), x1 and x3 are the same or different and represent 0 or 1.

In the above formula (b-6), R ¹⁵ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. Examples of the monovalent organic group, oxygen atom-containing group, sulfur atom-containing group, nitrogen atom-containing group, and halogen atom include those exemplified as R ⁷ . Further, in the above formula (b-6), x2 represents the number of substituents B ^1, shown in the formula (R ^15), an integer of 0-4. When x2 in the above formula (b-6) is an integer of 2 or more, each R ¹⁵ 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-6) include, for example, pyridine-2,6-diyl group, pyridine-2. , 5-diyl group, pyridine-2,4-diyl group, pyridine-2,3-diyl group, and the like.

  Among them, as the compound represented by the above formula (b-6) (amine compound (B6)), a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness) can be formed. From the viewpoint, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyridine, and 2,3-diaminopyridine are preferable. Moreover, a commercial item can also be used as a compound represented by the said Formula (b-6).

In the formula (b-7), A ² and A ³ are the same or different and are each an aromatic hydrocarbon having 6 to 12 carbon atoms. The aromatic hydrocarbon of the 6 to 12 carbon atoms, for example, aromatic hydrocarbons having 6 to 12 carbon atoms exemplified as R ^1b.

In the formula (b-7), Y ¹ represents a linking group. Examples of the linking group include the linking groups exemplified as R ^1b .

In the formula (b-7), R ¹⁷ and R ¹⁸ are the same or different and each represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. Examples of the monovalent organic group, oxygen atom-containing group, sulfur atom-containing group, nitrogen atom-containing group, and halogen atom include those exemplified as R ⁷ . Further, in the above formula (b-7), y1 and y2, respectively, indicates the number of substituents A ² substituents (R ¹⁷⁾ and A ³ shown in the formula (R ^18), the same or different Represents an integer of 0 to 4. When y1 in the above formula (b-7) is an integer of 2 or more, each R ¹⁷ may be the same or different. When y2 in the above formula (b-7) is an integer of 2 or more, each R ¹⁸ may be the same or different.

  Among these, as the compound represented by the above formula (b-7) (amine compound (B7)), a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness) can be formed. From the viewpoint, 3,3-diaminodiphenyl sulfone, 4,4-diaminodiphenyl sulfone, and 2,2-diaminodiphenyl sulfone are preferable. Moreover, a commercial item can also be used as a compound represented by the said Formula (b-7).

  As the amine compound (BII), in particular, a compound represented by the formula (b-5) from the viewpoint of forming a polymer composite (for example, a fiber reinforced composite material) having excellent mechanical properties (particularly toughness). , A compound represented by formula (b-6) and a compound represented by formula (b-7) are preferred, a compound represented by formula (b-7) is more preferred, and 3,3 is more preferred. -Diaminodiphenyl sulfone.

  Only one type of amine compound (BII) may be used, or two or more types may be used in combination.

［式中、Ｒ^1'は、式中に示される窒素原子との結合部位に炭素原子を有する二価の有機基を示す。Ｘは単結合、又は１以上の原子を有する二価の基を示す。ｚは１以上の整数を示す。］ 3. Compound [I]
The compound [I] according to the first aspect of the present invention is, for example, an epoxy-amine adduct represented by the following formula (I) (hereinafter sometimes referred to as “epoxy-amine adduct (I)”). Preferably there is.

[Wherein, R ^{1 ′} represents a divalent organic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula. X represents a single bond or a divalent group having one or more atoms. z represents an integer of 1 or more. ]

The epoxy-amine adduct (I) has a molecular chain in which structural units derived from the epoxy compound (A) and structural units derived from the amine compound (B) are alternately arranged, and both ends of the molecular chain. Is an epoxy-amine adduct having an amino group (—NH ₂ ) (that is, 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), if the carbon atom to which X is bonded among the carbon atoms constituting the cyclohexane ring is the “first-position” carbon atom, it is bonded to each cyclohexane ring represented by formula (I). The bonding position of the nitrogen atom (—NH—) of the structural unit derived from the amine compound (B) is the 3-position carbon atom or 4-position carbon atom 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 carbon atom at the 4-position of the cyclohexane ring, the bonding position of the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is the carbon atom at the 3-position. 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.

R ^{1 ′} in the above formula (I) represents a divalent organic group (organic residue) having a carbon atom at the binding site with the nitrogen atom shown in the formula. For example, R ^{1 ′} in the above formula (b) And the like.

More specifically, examples of the divalent organic group represented by R ^{1 ′} in the above formula (I) include the following divalent groups (a) to (g).
(A) a divalent group in which two or more divalent linear or branched aliphatic hydrocarbons are bonded via a linking group containing a heteroatom (b) a divalent linear or branched fatty acid A divalent group in which an aromatic hydrocarbon group and a divalent cyclic aliphatic hydrocarbon group are directly bonded (c) a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms (D) a divalent group in which a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms and a divalent linear or branched aliphatic hydrocarbon group are directly bonded. Group (e) a divalent group (f) formed by removing two hydrogen atoms from an aromatic heterocycle having one or two heteroatoms in the ring selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom Hydrogen from an aromatic heterocycle having 1 or 2 heteroatoms in the ring selected from the group consisting of nitrogen, sulfur and oxygen A divalent group in which a divalent group obtained by removing two children and a divalent linear or branched aliphatic hydrocarbon group are directly bonded (g) an aromatic hydrocarbon having 6 to 12 carbon atoms A divalent group formed by removing two hydrogen atoms from a group in which two or more are bonded via a linking group

R ^{1 ′} in the above formula (I) may be composed of only one divalent group selected from the group consisting of the above (a) to (g), and the above (a) to (g) You may be comprised by 2 or more types chosen from the group which consists of.
In particular, it is possible to improve the adhesion between a matrix resin and an additive (for example, a reinforcing fiber) in a polymer composite (for example, a fiber reinforced composite material), and it becomes easy to mix with other components such as a resin. At the same time, from the viewpoint of being able to produce an effect that a polymer composite (for example, a fiber reinforced composite material) having excellent mechanical properties (particularly toughness) can be formed, R ^{1 ′} in the above formula (I) At least one is at least one divalent group selected from the group consisting of the following (a) and (b) (hereinafter sometimes referred to as “first divalent group”), and at least the other Is preferably at least one divalent group selected from the group consisting of the following (c) to (g) (hereinafter sometimes referred to as “second divalent group”). .

The first divalent group at R ^{1 ′} in the epoxy-amine adduct (I) is selected from the group consisting of (a) and (b) represented by R ^1a in the above formula (bI). And a divalent group.

Among them, the first divalent group of R ^{1 ′} is the divalent group of (a), which is a linear or branched alkylene group having 2 to 6 carbon atoms (in particular, an ethylene group or a trimethylene group). , A propylene group) is a divalent group bonded via —NH— or —O—, or a divalent group of (b), which is a straight chain or branched chain having 1 to 6 carbon atoms A divalent group in which a chain alkylene group (in particular, a methylene group, an ethylene group, a trimethylene group, a propylene group, etc.) and a cycloalkylene group having 3 to 20 carbon atoms are directly bonded is preferable.

The first divalent group of R ^{1 ′} may include only one of the divalent group (a) and the divalent group (b), and the divalent group (a) Both the group and the divalent group (b) may be contained.
The adhesion between the matrix resin and the additive (for example, reinforcing fiber) in the polymer composite (for example, fiber reinforced composite material) can be improved, and the compounding with other components such as the resin becomes easy, From the viewpoint that an effect of forming a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness) can be obtained, the first divalent group of R ^{1 ′} is It is preferable that both the divalent group of (a) and the divalent group of (b) are included.

When the first divalent group of R ^{1 ′} includes both the divalent group of (a) and the divalent group of (b), the ratio (divalent group of (a) / (b) Is not particularly limited, but is preferably 1.5 to 5.2 (mol / mol), and more preferably 3.0 to 4.8 (mol / mol). When this ratio is lower than 1.5 (mol / mol), it tends to be brittle, and when it is higher than 5.2 mol / mol), tackiness may be exhibited.

The second divalent group for R ^{1 ′} in the epoxy-amine adduct (I) is selected from the group consisting of (c) to (g) represented by R ^1b in the above formula (b-II). And a divalent group.

Among these, as the second divalent group for R ^{1 ′} , the divalent group (d), the divalent group (e), or the divalent group (g) is preferable, and more preferably, A divalent group in which a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms (for example, a phenylene group) and an alkylene group having 1 to 4 carbon atoms (for example, a methylene group) are directly bonded. A divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring (for example, pyridine ring), two aromatic hydrocarbons having 6 to 10 carbon atoms (for example, benzene) A divalent group obtained by removing two hydrogen atoms from a group in which a ring) is bonded via a linking group (for example, —SO ₂ — and the like).

More specifically, as the first divalent group of R ^{1 ′,} a divalent group represented by the following formula (II), a divalent group represented by the following formula (III), and the following formula (IV ) And the like.

R ^2, R ³ and q in the above formula (II) include the same R ^2, R ³ and q in the formula (b-1) is exemplified.

  Among them, as the divalent group represented by the above formula (II), in terms of adhesiveness, wettability, heat resistance, and water solubility to the additive (particularly reinforcing fiber) of the epoxy-amine adduct of the present invention, A divalent group excluding amino groups at both ends of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) is preferable, and more preferably amino groups at both ends of triethylenetetramine. It is a divalent group excluding.

R ^4, R ⁵ and r in the formula (III) include the same R ^4, R ⁵ and r in the formula (b-2) are exemplified.

  Among them, the divalent group represented by the above formula (III) includes an amine terminal from the viewpoint of adhesion to the additive (particularly reinforcing fiber) of the epoxy-amine adduct of the present invention and wettability with the matrix resin. (Both-terminal amino groups) Bivalent groups excluding amino groups at both ends of polyethylene glycol, amine-terminated polypropylene glycol, and amine-terminated polybutylene glycol are preferred, and more preferably amino groups at both ends of amine-terminated polypropylene glycol are removed. Is a valent group.

^{R 6, R 7, R 8} , s and t in the formula (IV) are the same as ^{R 6, R 7, R 8} , s and t in the above formula (b-3) can be exemplified.

  Among them, the divalent group represented by the above formula (IV) includes 1,2-cyclohexylene-methylene group, 1,3-cyclohexylene-methylene group, 1,4-cyclohexylene-methylene group, cyclohexylene. Den-methylene group, 1,2-cyclohexylene-ethylene group, 1,3-cyclohexylene-ethylene group, 1,4-cyclohexylene-ethylene group, cyclohexylidene-ethylene group, methylene-1,5,5- Cyclohexylene-alkylene group methylene-1,2-cyclohexylene-methylene group such as trimethyl-1,3-cyclohexylene group (a divalent group formed by removing two amino groups from isophoronediamine), methylene-1 , 3-cyclohexylene-methylene group, methylene-1,4-cyclohexylene-methylene group and other alkylene-cyclo Xylene - alkylene group, and the like.

  Among these, as the divalent group represented by the formula (IV), from the viewpoint of heat resistance of the epoxy-amine adduct of the present invention, a methylene-1,5,5-trimethyl-1,3-cyclohexylene group ( A divalent group formed by removing two amino groups from isophoronediamine is preferred.

As the first divalent group of R ^{1 ′} , in particular, from the viewpoint of the adhesion improving effect between the matrix resin and the additive by the epoxy-amine adduct of the present invention, heat resistance, toughness, etc. A compound represented by formula (IV) is preferred, and a compound represented by formula (II) is more preferred.

More specifically, as the second divalent group of R ^{1 ′,} a divalent group represented by the following formula (V), a divalent group represented by formula (VI), a formula ( VII) and the like.

^{A 1, R 11, R 12} , R 13, w1, w2 and w3 in the above formula (V), A ^1, R ¹¹ in the formula ^{(b-5), R 12} , R 13, w1, w2 and The same thing as w3 is illustrated.

  More specifically, examples of the divalent group represented by the above formula (V) include arylene groups such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2 -Phenylene-methylene group, 1,3-phenylene-methylene group, 1,4-phenylene-methylene group, 1,2-phenylene-ethylene group, 1,3-phenylene-ethylene group, 1,4-phenylene-ethylene group Arylene-alkylene groups such as methylene-1,2-phenylene-methylene group, methylene-1,3-phenylene-methylene group, methylene-1,4-phenylene-methylene group, and the like. It is done.

  Among them, the divalent group represented by the above formula (V) is m-xylene from the viewpoint of forming a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness). Divalent groups excluding amino groups at both ends of diamine, p-xylenediamine, and o-xylenediamine are preferred.

^{B 1, R 14, R 15} , R 16, x1, x2 and x3 in the formula ^{(VI), B 1, R 14, R} 15 in the above formula ^{(b-6), R 16} , x1, x2 and The same thing as x3 is illustrated.

  More specifically, examples of the divalent group represented by the formula (VI) include pyridine-2,6-diyl group, pyridine-2,5-diyl group, pyridine-2,4-diyl group, and pyridine. An aromatic heterocyclic-diyl group such as a -2,3-diyl group and the like can be mentioned.

  Among them, the divalent group represented by the above formula (VI) is preferably 2, 6 from the viewpoint of forming a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness). A divalent group excluding amino groups at both ends of -diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyridine, and 2,3-diaminopyridine is preferable.

^{A 2, A 3, Y 1} , R 17, R 18, y1 and y2 in the above formula (VII), A ^2, A ³ in the above formula ^{(b-7), Y 1} , R 17, R 18, The same thing as y1 and y2 is illustrated.

  Among these, as the divalent group represented by the formula (VII), from the viewpoint of forming a polymer composite (for example, a fiber reinforced composite material) having excellent mechanical properties (particularly toughness), 3,3- A divalent group excluding amino groups at both ends of diaminodiphenyl sulfone, 4,4-diaminodiphenyl sulfone, and 2,2-diaminodiphenyl sulfone is preferable.

As the second divalent group of R ^{1 ′} , in particular, from the viewpoint of forming a polymer composite (for example, fiber reinforced composite material) having excellent mechanical properties (particularly toughness), the formula (V) A divalent group represented by formula (VI), a divalent group represented by formula (VII) is preferred, and a divalent group represented by formula (VII) is more preferred. It is the basis of.

When both the first divalent group and the second divalent group of R ^{1 ′} are contained in the epoxy-amine adduct (I), the ratio (first divalent group / second divalent group) The molar ratio of the groups is not particularly limited, but is preferably 4.5 to 7.0 (mol / mol), and more preferably 5.0 to 6.5 (mol / mol). When this ratio is lower than 4.5 (mol / mol), the water solubility tends to decrease, and when higher than 7.0 (mol / mol), the toughness of the epoxy-amine adduct becomes insufficient. There is a case.

  X in the above formula (I) represents a single bond or a linking group (a divalent group having one or more atoms) and is the same as X in the above formula (a). In addition, when z is an integer greater than or equal to 2, each X may be the same and may differ.

In the above formula (I), z (the number of repeating structural units in parentheses to which z is attached) represents an integer of 1 or more. Although it does not specifically limit as z, 1-200 are preferable, More preferably, it is 2-150, More preferably, it is 2-100. When z exceeds 200, the compounding with respect to the other component of an epoxy-amine adduct may become difficult. Note that z in the above formula (I) can be controlled by, for example, the ratio of the epoxy compound (A) to the amine compound (B) subjected to the reaction, reaction conditions, and the like. When z is an integer of 2 or more, each structural unit (X, R ^{1 ′} ) in parentheses may be the same or different.

  When the epoxy-amine adduct of the present invention is represented by the above formula (I), the epoxy-amine adduct may be a mixture of two or more different z.

4). Production method of compound [I]; reaction of epoxy compound (A) and amine compound (B) Compound [I] can be produced by reacting epoxy compound (A) with amine compound (B). More specifically, compound [I] is produced by reacting an alicyclic epoxy group possessed by epoxy compound (A) with an amino group possessed by amine compound (B).

  In addition, in manufacture of compound [I], an epoxy compound (A) can also be used individually by 1 type, and can also be used in combination of 2 or more type. Similarly, amine compound (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

Specifically, the epoxy compound (A) and the amine compound (B) as the raw material of the compound [I] are particularly adhesive to additives (reinforcing fibers, etc.), wettability with a resin, heat resistance, handleability, From the viewpoint of water solubility when used as a salt and toughness of a polymer-based composite (for example, fiber-reinforced composite material), at least one compound selected from the compound represented by formula (a) and an amine compound (BI): An epoxy-amine adduct obtained by reacting an epoxy-amine adduct, or an epoxy-amine adduct obtained by reacting a compound represented by the formula (a) with both amine compounds (BI) and (BII) preferable.
In addition, in the epoxy-amine adduct of this invention, epoxy compounds other than the said essential epoxy compound (A) and amine compound (B) and amine compounds can also be used together. For example, as a raw material of the epoxy-amine adduct of the present invention, an alicyclic epoxy compound other than the compound represented by the formula (a), an amine compound (BI), and an amine compound other than the amine compound (BII) are used in combination. You can also.

  The ratio of the compound represented by the formula (a) in the total amount (100% by weight) of the epoxy compound (A) that is a raw material of the epoxy-amine adduct of the present invention is not particularly limited, but preferably 80% by weight or more. More preferably, it is 90 weight% or more, More preferably, it is 98-100 weight%. By setting the ratio of the compound represented by the formula (a) to 80% by weight or more, adhesion to additives (particularly reinforcing fibers such as carbon fibers), matrix resin in polymer-based composites (particularly fiber-reinforced composite materials) and There exists a tendency for the adhesiveness of an additive (especially reinforcing fiber) to improve efficiently.

  The ratio of the total amount of the amine compound (BI) and the amine compound (BII) in the total amount (100% by weight) of the amine compound (B) that is the raw material of the epoxy-amine adduct of the present invention 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 total amount of the amine compound (BI) and the amine compound (BII) within the above range, the adhesiveness to the additive (particularly reinforced fiber such as carbon fiber), wettability, polymer composite (particularly fiber reinforced composite) There is a tendency that adhesion between the additive (particularly reinforcing fiber) and the matrix resin, water solubility, and mechanical properties (particularly toughness) of the polymer composite (for example, fiber reinforced composite material) are further improved.

  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; dimethylsulfoxide; water 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 0.99, more preferably 0.15 to 0.98). 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 [2] or [ The method of 3] is preferable. On the other hand, it may be advantageous for the compound [I] to have a lower molecular weight depending on the application. In such a case, it is preferable to carry out the reaction 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 increases and the productivity of the compound [I] tends to be further improved. On the other hand, by setting the reaction temperature to 280 ° C. or lower, thermal decomposition of the epoxy compound (A) or the amine compound (B) is suppressed, and the yield of the compound [I] tends to be further improved. 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 setting the reaction time to 0.2 hours or longer, the yield of compound [I] tends to be further improved. On the other hand, when the reaction time is 20 hours or less, the productivity of the compound [I] 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.

  Compound [I] is obtained by the above reaction (reaction of epoxy compound (A) and amine compound (B)). After the above reaction, the obtained compound [I] is obtained by, for example, known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. Can be separated and purified.

The number of amino groups (—NH ₂ ; unsubstituted amino group) possessed by the compound [I] is 2 or more, preferably 2 to 10, more preferably 2 to 4, further preferably 2 or 3 It is a piece. Moreover, compound [I] 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 compound [I] is not particularly limited, but is usually the end of the molecular chain of compound [I] (especially in the case of linear compound [I], It is located at both ends of the molecular chain of compound [I]. However, it is not limited to this.

As described above, the compound [I] is produced by the reaction between the alicyclic epoxy group of the epoxy compound (A) and the amino group (—NH ₂ ; unsubstituted amino group) of the amine compound (B). Compound [I] is a —NH— group (substituted amino group) produced by the reaction of the alicyclic epoxy group and an amino group (in addition, when amine compound (B1) is used, amine compound (B1) is It is presumed that the reactivity between the —NH— group) and the alicyclic epoxy group of the epoxy compound (A) is poor, but usually the —NH— group remains in the molecule in an unreacted state. The number of —NH— groups in the molecule of compound [I] is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, and still more preferably 2 to 100. When the compound [I] does not have a —NH— group, the reactivity of the epoxy-amine adduct of the present invention is reduced, or depending on the use, the effect of improving the adhesion between the matrix resin and the reinforcing fiber in the fiber-reinforced composite material May not be sufficient. In addition, the water solubility of the epoxy-amine adduct of the present invention may decrease. The number of —NH— groups in the compound [I] is, for example, the epoxy compound (A) constituting the compound [I] using a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) method. ) And the number of amine compounds (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 compound [I] 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 of the present invention is increased to some extent, and contamination of the processing machine (roll or the like) tends to be suppressed. Moreover, there exists a tendency for the softness | flexibility and toughness of the epoxy-amine adduct of this invention to improve more. Furthermore, 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 of this invention. On the other hand, when the number average molecular weight is 40,000 or less, blending with the other components of the epoxy-amine adduct of the present invention is facilitated, and the solubility in water and the water solubility tend to be further improved. In addition, the number average molecular weight of compound [I] is calculated using the molecular weight of standard polystyrene conversion measured by a gel permeation chromatography (GPC) method.

  Although the glass transition temperature (Tg) of compound [I] 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 compound [I] to −50 ° C. or higher (particularly 20 ° C. or higher), the heat resistance and mechanical properties of polymer-based composites (particularly fiber-reinforced composite materials) using the epoxy-amine adduct of the present invention ( Toughness and the like) tend to be further improved. In addition, contamination of processing machines (rolls and the like) is suppressed, and there is a tendency that excellent texture and handleability can be imparted to reinforcing fibers (for example, sizing agent-coated carbon fibers) coated with the epoxy-amine adduct of the present invention. is there. On the other hand, when the Tg of compound [I] is 200 ° C. or lower, blending with other components of the epoxy-amine adduct of the present invention tends to be facilitated. In addition, Tg of compound [I] can be measured by differential scanning calorimetry (DSC), dynamic viscoelasticity measurement, etc., for example.

The 5% weight loss temperature (Td ₅ ) of compound [I] 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 compound [I] to 280 ° C. or higher (particularly 300 ° C. or higher), the epoxy-amine adduct of the present invention is processed at higher temperatures (for example, production of sizing agent-coated carbon fibers). Tend to be applicable to. The 5% weight loss temperature of compound [I] can be measured by TG / DTA.

  Next, the first and second embodiments of the epoxy-amine adduct of the present invention will be described.

<First Embodiment of Epoxy-Amine Adduct of the Present Invention>
The first embodiment of the epoxy-amine adduct of the present invention is compound [I] as described above. Compound [I] is as described above. Among these, the first aspect of the epoxy-amine adduct of the present invention includes adhesion to additives (reinforcing fibers, fillers, etc.), wettability with matrix resin, heat resistance, handleability, water solubility, polymer composite ( For example, from the viewpoint of toughness of a fiber-reinforced composite material or the like, an epoxy-amine adduct (“epoxy of the present invention”) obtained by reaction of an epoxy compound (A) with an amine compound (B1) or an amine compound (B3) -In some cases, it is referred to as “first aspect of amine adduct (1)”); an epoxy-amine adduct obtained by reaction of epoxy compound (A), amine compound (BI) and amine compound (BII) ( "Sometimes referred to as the first embodiment (2) of the epoxy-amine adduct of the present invention") is preferred. Hereinafter, the first aspects (1) and (2) of the epoxy-amine adduct of the present invention may be collectively referred to as “the first aspect of the epoxy-amine adduct of the present invention”. In particular, the first aspect (1) of the epoxy-amine adduct of the present invention is preferable in terms of heat resistance, adhesiveness to additives (reinforcing fibers, fillers, etc.), and wettability with a matrix resin, and further a polymer system. The first aspect (2) of the epoxy-amine adduct of the present invention is preferable in that the toughness of the composite (for example, fiber reinforced composite material) is improved.

  Specifically, the first aspect (1) of the epoxy-amine adduct of the present invention includes an epoxy compound (A) (preferably a compound represented by the formula (a)) and an amine compound (B). It can be obtained by reacting amine compound (B1) and amine compound (B3) as essential raw materials. In addition, the first aspect (2) of the epoxy-amine adduct of the present invention includes an epoxy compound (A) (preferably a compound represented by the formula (a)) and an amine compound (BI) as the amine compound (B). ) And amine compound (BII) as essential raw materials.

  The first aspect (1) of the epoxy-amine adduct of the present invention has a structural unit derived from the amine compound (B1) and the amine compound (B3) in the molecule. Adhesion to reinforced fibers such as fibers and additives such as fillers, adhesion between matrix resins and additives (reinforced fibers, etc.) in polymer composites (fiber reinforced composite materials, etc.), polymer composites (fiber reinforced composite materials, etc.) There is a tendency to exhibit more advanced characteristics in toughness.

  The first aspect (2) of the epoxy-amine adduct of the present invention includes a structural unit derived from the amine compound (BI) and a structural unit derived from the amine compound (BII), and thus is particularly superior in polymer composite. There is a tendency to exhibit the toughness of (for example, fiber-reinforced composite materials).

  The ratio of the compound represented by the formula (a) in the total amount (100% by weight) of the epoxy compound (A) that is the raw material of the first aspect of the epoxy-amine adduct of the present invention is not particularly limited, but is 80% by weight. % Or more is preferable, 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 additives (particularly reinforcing fibers such as carbon fibers), matrix resin in polymer-based composites (particularly fiber-reinforced composite materials) and There exists a tendency for the adhesiveness of an additive (especially reinforcing fiber) to improve efficiently.

  The proportion of the amine compound (B1) in the total amount (100% by weight) of the amine compound (B) that is the raw material of the first aspect (1) of the epoxy-amine adduct of the present invention is not particularly limited, but is 10% by weight. The above (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) to the above range, the adhesiveness to the additive (especially reinforcing fiber such as carbon fiber), wettability, additive (especially reinforced) in the polymer composite (especially fiber reinforced composite material) Fiber) and matrix resin tend to be further improved in adhesion and water solubility.

  The ratio of the amine compound (B3) in the total amount (100% by weight) of the amine compound (B) that is the raw material of the first aspect (1) of the epoxy-amine adduct of the present invention is not particularly limited, but is 10 to 70. % By weight is preferable, more preferably 20 to 60% by weight, and still more preferably 20 to 50% by weight. By controlling the ratio of the amine compound (B3) within the above range, the adhesiveness and wettability to the additive (particularly reinforcing fiber), the additive (particularly reinforcing fiber) and the matrix in the polymer composite (particularly fiber-reinforced composite material) The heat resistance tends to be further improved while the adhesiveness of the resin is ensured.

  The ratio of the amine compound (BI) in the total amount (100% by weight) of the amine compound (B) that is the raw material of the first aspect (2) of the epoxy-amine adduct of the present invention is not particularly limited, but is 10 to 90. % By weight is preferable, more preferably 40 to 85% by weight, and still more preferably 50 to 80% by weight. By controlling the ratio of the amine compound (BI) within the above range, the adhesiveness and wettability to the additive (particularly reinforcing fiber), the additive (particularly reinforcing fiber) and the resin in the polymer composite (particularly fiber-reinforced composite material) And the toughness of polymer composites (fiber reinforced composite materials, etc.) tend to be further improved.

  The ratio of the amine compound (BII) in the total amount (100% by weight) of the amine compound (B) that is the raw material of the first aspect (2) of the epoxy-amine adduct of the present invention is not particularly limited, but is 10 to 90. % By weight is preferable, more preferably 15 to 60% by weight, and still more preferably 20 to 50% by weight. By controlling the ratio of the amine compound (BII) within the above range, the adhesiveness and wettability to the additive (especially reinforcing fiber), the additive (especially reinforcing fiber) and the resin in the polymer composite (especially fiber-reinforced composite material) However, the heat resistance and the toughness of polymer composites (fiber reinforced composite materials, etc.) tend to be further improved.

  In the first aspect (1) of the epoxy-amine adduct of the present invention, in particular, when the compound represented by the above formula (a) is used as the epoxy compound (A), the configuration represented by the above formula (I). A unit (structural unit; a structural unit derived from the compound represented by the formula (a)), a structural unit represented by the above formula (II) (a structural unit derived from the amine compound (B1)), and the above formula ( IV) an epoxy-amine adduct having a structural unit represented by (IV) (a structural unit derived from the amine compound (B3)) and having amino groups at both ends.

  In the first aspect (2) of the epoxy-amine adduct of the present invention, particularly when the compound represented by the above formula (a) is used as the epoxy compound (A), the configuration represented by the above formula (I). At least one (amine compound (BI)) obtained from the group consisting of a unit (a structural unit derived from the compound represented by the formula (a)) and a structural unit represented by the above formulas (II) to (IV) And at least one (a structural unit derived from the amine compound (BII)) obtained from the group consisting of the structural units represented by the above formulas (V) to (VII), It is an epoxy-amine adduct having an amino group at the terminal.

  The 1st aspect of the epoxy-amine adduct of this invention can be used as it is, and can also be used as a solution or a dispersion liquid. In the first aspect of the epoxy-amine adduct of the present invention, a part or all of the amino group and —NH— group in the molecule is protonated to form a salt with an anion (eg, carbonate, carboxylate, bicarbonate) Etc.) (ie as a second embodiment of the epoxy-amine adducts of the invention). By making it into a salt, the effect of improving solubility in water can be obtained. By increasing the water solubility of the first aspect of the epoxy-amine adduct, it can be preferably used particularly for the water-dispersed resin composition of the present invention.

<Second Embodiment of Epoxy-Amine Adduct of the Present Invention>
As described above, the second embodiment of the epoxy-amine adduct of the present invention is a salt of compound [I]. Hereinafter, the second embodiment of the epoxy-amine adduct of the present invention will be described as “the salt of the epoxy-amine adduct of the present invention”.

  The salt of the epoxy-amine adduct of the present invention is a salt of the compound [I] and the acid [II] (an acid salt of an amine compound).

  Compound [I] which is a raw material of the salt of the epoxy-amine adduct of the present invention is as described above. In particular, when the above-mentioned epoxy-amine adduct (I) is used as the compound [I] which is a raw material for the salt of the epoxy-amine adduct of the present invention, the epoxy-amine adduct has a high thermal decomposition temperature and heat resistance. Therefore, 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.

  The formula (a) in the total amount (100% by weight) of the epoxy compound (A) that is a raw material of the compound [I] (for example, the epoxy-amine adduct (I)) constituting the salt of the epoxy-amine adduct of the present invention ) 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 matrix resin and the additive (particularly reinforcing fiber) in the material) is improved efficiently.

[Acid [II]]
The acid [II] constituting the salt of the epoxy-amine adduct of the present invention may be an acid capable of forming an acid-base reaction with a basic group such as an amino group of the compound [I] to form a salt. For example, inorganic acids such as hydrochloric acid, phosphoric acid, carbonic acid, sulfuric acid, nitric acid, hydrobromic acid; formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid And organic acids such as malic acid, lactic acid, maleic acid and fumaric acid. Acid [II] can also be used individually by 1 type, and can be used in combination of 2 or more type. Among them, the acid [II] is preferably carbonic acid or an organic acid, more preferably carbonic acid or acetic acid (especially carbonic acid (particularly carbonic acid)) in that it can be easily converted to the compound [I] by handling, thermal decomposition of a salt, or the like. ). That is, the salt of the epoxy-amine adduct of the present invention is preferably a carbonate, bicarbonate or organic acid salt, more preferably a carbonate or acetate (particularly preferably carbonate).

[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, the epoxy of the present invention is produced by reacting compound [I] (specifically, a basic group such as an amino group or the like possessed by compound [I]) with acid [II] (acid-base reaction). -A salt of an amine adduct 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 compound [I] and the acid [II] attached to the above reaction (reaction between the compound [I] and the acid [II]) is not particularly limited, and a basic group (for example, an amino group) of the compound [I] is not limited. , —NH— group, etc.) can be appropriately selected according to the ratio required to be converted into a salt (this ratio can be determined according to, for example, the desired water solubility).

  The operation for carrying out the above reaction is not particularly limited. For example, the compound [I] and the acid [II] can be charged into a reaction vessel in a lump and reacted, or the compound [I] and the acid [II] can be reacted. Any one of the above may be charged in a reaction vessel, and the other may be added (for example, sequentially added as described above) to cause the reaction. Further, after obtaining a water-dispersed resin composition containing the compound [I] described later, the acid [II] may be 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.

  The above reaction produces the salt of the epoxy-amine adduct of the present invention. 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. Further, since the epoxy-amine salt of the present invention has a feature that it is particularly excellent in water solubility, it can be preferably used in the state of an aqueous solution or a water-dispersed resin composition described later.

  The salt of the epoxy-amine adduct of the present invention is obtained by reacting at least part of the basic group (especially amino group, -NH- group) of the compound [I] with an acid-base reaction with an acid [II]. Since it has the structure which became, it has the outstanding water solubility, and can be preferably used especially in the state of aqueous solution or the water-dispersed resin composition mentioned later. Then, it can be easily converted into a basic group (particularly an amino group or —NH— group) by thermal decomposition or other treatment (for example, treatment with a strong base, etc.). Therefore, the effect of improving the adhesion between the resin and the additive in the polymer composite produced by the compound [I] can be exhibited. Needless to say, when 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 compound [I] is a salt (that is, an amino group or -When having an -NH- group), even if it is not converted into the compound [I] in particular, the effect of improving the adhesion between the matrix resin and the additive in the polymer composite such as a fiber reinforced composite material or nanocomposite itself Have

  The salt of the epoxy-amine adduct of the present invention can be used as it is, or as a solution or dispersion (including the water-dispersed resin composition of the present invention). 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 epoxy-amine adduct of the present invention (first and second embodiments of the epoxy-amine adduct of the present invention). ) As an essential component is referred to as “aqueous solution of the present invention”). Moreover, the salt of the epoxy-amine adduct of the present invention can also be preferably used in the form of the water-dispersed resin composition of the present invention. Since the salt of the epoxy-amine adduct of the present invention is less likely to cause precipitation of a dissolved substance, even when the concentration in the aqueous solution (the aqueous solution of the present invention) or the water-dispersed resin composition is low. It can be used in various ways. The aqueous solution of the present invention can be suitably used for the production of the water-dispersed resin composition of the present invention. In addition, the density | concentration of the epoxy-amine adduct of this invention in the aqueous solution of this invention is not specifically limited, It can select suitably.

  The epoxy-amine adduct of the present invention (first and second embodiments of the epoxy-amine adduct of the present invention) can be used for applications other than the water-dispersed resin composition of the present invention. The epoxy-amine adduct is an adhesion improver (adhesion improver) for improving the adhesion between the matrix resin and the additive in the polymer composite, and an adhesion improvement for improving the adhesion to the adherend. Agent (adhesion improver), compatibility improver (compatibilizer) to improve the solubility of two or more different components (especially polymer), dispersibility of additives in polymer composites Various additives such as a dispersibility improver, a flow improver, a flow suppressor, a plasticizer, a crosslinking agent such as an epoxy resin, etc .; an adhesive; a paint; a sealant; Moreover, it can be preferably used also for the use of the product (for example, water-based paint etc.) which used water or the solvent which has water as a main component as a medium. The water-based paint is a paint (usually including a binder component, a pigment, and the like) using water or a solvent mainly containing water as a medium. By using the epoxy-amine adduct of the present invention, an aqueous paint containing the epoxy-amine adduct as an essential component can be obtained.

  As the epoxy-amine adduct of the present invention as a constituent of the water-dispersed resin composition of the present invention, the second embodiment of the epoxy-amine adduct of the present invention is preferably used from the viewpoint of water solubility. In the water-dispersed resin composition of the present invention, the epoxy-amine adduct of the present invention can be used singly or in combination of two or more.

  The content (blending amount) of the epoxy-amine adduct of the present invention in the water-dispersed resin composition of the present invention is not particularly limited, but with respect to the nonvolatile content (100% by weight) of the water-dispersed resin composition, It is preferably 0.1 to 98% by weight, more preferably 1 to 90% by weight, still more preferably 10 to 85% by weight, and particularly preferably 20 to 80% by weight.

<Higher fatty acid ester>
The water-dispersed resin composition of the present invention contains a higher fatty acid ester as an essential component. When the water-dispersed resin composition of the present invention contains a higher fatty acid ester, the adhesion between the matrix resin and the additive (for example, reinforcing fiber) in the polymer composite (for example, fiber-reinforced composite material) is improved. It is possible to produce a polymer composite (for example, a fiber reinforced composite material) having excellent mechanical properties (particularly toughness).

  The higher fatty acid constituting the higher fatty acid ester is not particularly limited, but is preferably a saturated or unsaturated fatty acid having 8 to 24 carbon atoms, such as caprylic acid (C8), capric acid (C10), lauric acid (C12), C8-24 saturated fatty acids such as myristic acid (C14), palmitic acid (C16), stearic acid (C18), arachidic acid (C20), behenic acid (C22), oleic acid (18: 1 (n-9) And unsaturated fatty acids having 8 to 24 carbon atoms such as)). Moreover, fatty acids derived from animals and plants such as coconut oil fatty acid, palm kernel oil fatty acid, rice bran oil fatty acid, and beef tallow fatty acid can also be suitably used.

  The higher fatty acid constituting the higher fatty acid ester includes the adhesion between the matrix resin and the additive (for example, reinforcing fiber) in the polymer composite (for example, fiber reinforced composite material), the polymer composite (for example, fiber reinforced). From the viewpoint of mechanical properties (particularly toughness) of composite materials and the like, preferably a saturated or unsaturated fatty acid having 10 to 20 carbon atoms is preferable, and a saturated fatty acid having 14 to 18 carbon atoms (particularly palmitic acid or stearic acid). ) Is more preferable.

The alcohol constituting the higher fatty acid ester is not particularly limited, but is preferably a linear or branched alcohol having 1 to 16 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, Examples include isobutyl alcohol, t-butanol, pentanol, 2-pentanol, isopentanol, neopentanol, t-pentanol, n-hexanol, 2-hexanol, isohexanol, and ethylhexanol.
The alcohol constituting the higher fatty acid ester includes the adhesion between the matrix resin and the additive (eg, reinforcing fiber) in the polymer composite (eg, fiber reinforced composite material), and the polymer composite (eg, fiber reinforced composite). From the viewpoint of mechanical properties (particularly toughness) of materials, etc., linear or branched alcohols having 2 to 12 carbon atoms are preferable, and branched alcohols having 3 to 8 carbon atoms (particularly isopropanol, ethylhexanol). Is more preferable.

  Specific examples of higher fatty acid esters include methyl laurate, ethyl laurate, propyl laurate, isopropyl laurate, butyl laurate, isobutyl laurate, methyl myristate, ethyl myristate, propyl myristate, isopropyl myristate, myristic Butyl acid, isobutyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate, isopropyl palmitate, butyl palmitate, isobutyl palmitate, methyl stearate, ethyl stearate, propyl stearate, isopropyl stearate, butyl stearate , Isobutyl stearate, methyl oleate, ethyl oleate, propyl oleate, isopropyl oleate, butyl oleate, isobutyl oleate Le, ethylhexyl stearate and the like, preferably, isopropyl myristate, isobutyl myristate,.

  In the water-dispersed resin composition of the present invention, the higher fatty acid ester is preferably dispersed as emulsified particles in an aqueous medium described later. In this case, the average particle diameter (average emulsion particle diameter) of the emulsified particles of the higher fatty acid ester at 25 ° C. is preferably 0.1 to 0.4 μm, preferably 0.2 to 0.3 μm from the viewpoint of storage stability. More preferably. The average emulsified particle diameter can be measured by a dynamic light scattering method.

  In the water-dispersed resin composition of the present invention, the higher fatty acid ester can be used alone or in combination of two or more.

  In the water-dispersed resin composition of the present invention, the content (blending amount) of the higher fatty acid ester is not particularly limited, but the matrix resin and the additive (for example, reinforcing fiber) in the polymer composite (for example, fiber-reinforced composite material). Etc.), and from the viewpoint of mechanical properties (particularly toughness) of polymer composites (for example, fiber reinforced composite materials), 0.7 parts by weight with respect to 100 parts by weight of the epoxy-amine adduct of the present invention. -7.2 parts by weight is preferred, and 1.4-5.4 parts by weight is preferred.

<Surfactant>
The water-dispersed resin composition of the present invention contains a surfactant as an essential component. As the surfactant, known or commonly used surfactants can be used, and are not particularly limited, but are well-known anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants. Agents, polymer dispersants and the like. The surfactant mainly has a function of stably dispersing the epoxy-amine adduct and higher fatty acid ester of the present invention in the water-dispersed resin composition of the present invention.

  Examples of the anionic surfactant include dodecylbenzene sulfonate, alkylene disulfonate, dialkyl succinate sulfonate sodium salt, monoalkyl succinate sulfonate disodium salt, naphthalene sulfonate formalin condensate sodium salt, α- Sulfonate type such as olefin sulfonate; polyoxyethylene polycyclic phenyl ether sulfate, polyoxyethylene aryl ether sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene castor oil ether sulfate, etc. Sulfate ester type; phosphate ester type such as polyoxyalkylene alkyl ether phosphate; polyacrylic acid sodium salt and the like. Among these, as the anionic surfactant, a sulfate ester type surfactant is preferable. Specifically, trade names “NEWCOL707SF”, “NEWCOL707SFC”, “NEWCOL707SN”, “NEWCOL780SF” (above, Nippon Emulsifier Co., Ltd.) (Commercially available) can be used.

  In addition to the above, as the anionic surfactant, for example, a reactive surfactant having a polymerizable functional group capable of radical polymerization can be used, for example, a molecule of a sulfate ester salt of polyoxyethylene alkylphenyl ether. Examples thereof include a surfactant having a radical polymerizable unsaturated double bond introduced therein, and a surfactant having a radical polymerizable unsaturated double bond introduced into the molecule of the sulfosuccinic acid alkyl ester salt. Specifically, examples of the former include trade names “AQUALON KH-10” and “AQUALON HS-10” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); trade names “Adekaria Soap SE-10N” ( (Made by ADEKA Corporation). As examples of the latter, trade names “Eleminol JS2”, “Eleminol RN-30” (manufactured by Sanyo Chemical Industries, Ltd.); trade names “Latemul S-180”, “Latemul S-180A” (and above) , Manufactured by Kao Corporation).

  Nonionic surfactants include, for example, polyoxyethylene 2-ethylhexyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene castor oil ether, polyoxyethylene cetyl ether Polyoxyalkylene alkyl ether type such as polyoxyethylene stearyl ether, polyoxyalkylene 2-ethylhexyl ether, polyoxyalkylene nonyl ether, polyoxyalkylene tridecyl ether; polyoxyalkylene polycyclic such as polyoxyethylene polycyclic phenyl ether Phenyl ether type (polycyclic phenyl ether type); sorbitan laurate, sorbitan stearate, sorbitan oleate, sorbitan triole Sorbitan derivative types such as polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene sorbitan trioleate, polyoxyalkylene sorbitan fatty acid ester; polyoxyethylene aryl ether, poly Oxyethylene cumylphenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyalkylene fatty acid ester such as polyoxyethylene oleate, polyoxyethylene alkylamine ether, 2-butyl-2-ethyl-1,3-β- Examples include an alkylene oxide adduct of hydroxypropane, a fatty acid amide derivative, a polyhydric alcohol derivative, and the like. Among them, polyoxyalkylene alkyl ether type nonionic surfactants, sorbitan derivative type nonionic surfactants are preferred, and specifically, polyoxyalkylene alkyl ether type nonionic surfactants include: Trade names “Neugen EA-197D”, “Neugen XL”, “Neugen ET-B”, “Neugen TDS” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), trade names “Nonion K-220”, “Nonion P” -210 "," Nonion E-215 "," Nonion S-215 "," Nonion T-208 "(manufactured by NOF Corporation) and the like can be used. Examples of sorbitan derivative type nonionic surfactants include trade names “NONION OP-80R”, “NONION OP-85R”, “NONION LP-20R”, “NONION PP-40R”, “NONION SP-60R”. (Above, manufactured by NOF Corporation) can be used. Polyoxyalkylene fatty acid esters such as polyoxyethylene oleate are also preferable. Specifically, trade names “NEWCOL150”, “NEWCOL170”, “NEWCOL180”, “NEWCOL180T” (manufactured by Nippon Emulsifier Co., Ltd.), etc. Can be used.

  In addition to the above, as the nonionic surfactant, for example, a surfactant in which a radical polymerizable unsaturated double bond is introduced in the molecule of polyoxyethylene alkylphenyl ether, specifically, , Trade names "AQUALON RN-20", "AQUALON RN-50" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); trade names "Adekaria soap NE-20", "Adekaria soap NE-40" (above And ADEKA Co., Ltd.).

  Examples of the cationic surfactant include tetramethylammonium salts (eg, tetramethylammonium chloride, tetramethylammonium hydroxide), alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkyls. Quaternary ammonium salt types such as isoquinolinium salt and benzethonium chloride; amine salt types such as alkylamine salts (for example, monomethylamine hydrochloride, dimethylamine hydrochloride, etc.), amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; Examples thereof include pyridinium salt types such as butylpyridinium chloride and dodecylpyridinium chloride.

  Examples of amphoteric surfactants include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine.

  Polymeric dispersants include polyvinyl alcohol, polyvinyl pyrrolidone, maleic acid copolymers (ethyl vinyl ether-maleic acid copolymer, styrene-maleic acid copolymer, etc.), various metal salts, ammonium salts, acrylic acid Polymers (polyacrylic acid, copolymers of acrylic acid, etc.) and various metal salts and ammonium salts thereof, maleic acid monoester copolymer, acryloylmethylpropanesulfonic acid copolymer, polyester, CMC (carboxymethylcellulose), HEC (hydroxyethylcellulose), hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethyl starch, alginic acid, pectinic acid and the like can be mentioned.

  In the water-dispersed resin composition of the present invention, one type of surfactant can be used alone, or two or more types can be used in combination. Among these, nonionic surfactants are preferable, and it is particularly preferable to use a combination of a polyoxyalkylene alkyl ether type nonionic surfactant and a sorbitan derivative type nonionic surfactant.

  The content (blending amount) of the surfactant in the water-dispersed resin composition of the present invention is not particularly limited, but is 0.01 to 500 parts by weight with respect to 100 parts by weight of the epoxy-amine adduct of the present invention. More preferably, it is 0.1-200 weight part, More preferably, it is 0.5-100 weight part, Especially preferably, it is 1.5-80 weight part. By setting the content of the surfactant to 0.01 parts by weight or more, the epoxy-amine adduct and higher fatty acid ester of the present invention tend to be more stably dispersed. On the other hand, by making the surfactant content 500 parts by weight or less, it tends to be economically advantageous, and the heat resistance and mechanical properties (particularly toughness) of the fiber reinforced composite material tend to be maintained at a higher level. There is.

  When a polyoxyalkylene alkyl ether type nonionic surfactant and a sorbitan derivative type nonionic surfactant are used in combination as a surfactant, the ratio of the amount of these surfactants used [polyoxyalkylene alkyl ether type [Nonionic Surfactant / Sorbitan Derivative Nonionic Surfactant] (weight ratio) is not particularly limited, but is preferably 95/5 to 10/90, more preferably 90/10 to 30/70. More preferably, it is 85/15 to 50/50.

<Urethane resin>
The water-dispersed resin composition of the present invention may further contain a urethane resin in addition to the epoxy-amine adduct and the higher fatty acid ester. The water-dispersed resin composition of the present invention contains a urethane resin, thereby improving the adhesion between a matrix resin and an additive (for example, a reinforcing fiber) in a polymer composite (for example, a fiber-reinforced composite material). And a polymer composite (for example, a fiber reinforced composite material) having excellent mechanical properties (particularly toughness) can be formed. The urethane resin is not particularly limited, and a resin having a polyurethane structure obtained by reacting a polyfunctional isocyanate and a polyol can be used. In addition, a urethane resin can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The polyfunctional isocyanate is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule. Examples of the polyfunctional isocyanate include an aliphatic polyfunctional isocyanate, an alicyclic polyfunctional isocyanate, an aromatic polyfunctional isocyanate, and an araliphatic polyfunctional isocyanate. Polyfunctional isocyanate can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Examples of the aliphatic polyfunctional isocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1, , 2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate, etc. (excluding carbon in NCO) Examples include 2 to 12 aliphatic diisocyanates.

  Examples of the alicyclic polyfunctional isocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate). ), 4,4′-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) ) Aliphatic diisocyanates having 4 to 18 carbon atoms (excluding carbon in NCO) such as cyclohexane and norbornane diisocyanate.

  Examples of the aromatic polyfunctional isocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthylene-1,4-diisocyanate, and naphthylene-1,5- Diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2,2'-diphenylpropane Fragrance of 6 to 15 carbon atoms (excluding carbon in NCO) such as 4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate Group diisocyanate and the like.

  Examples of the araliphatic polyfunctional isocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis (1-isocyanate- Carbon number of 1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1,3-bis (α, α-dimethylisocyanatomethyl) benzene (excluding carbon in NCO) ) 8-15 aromatic aliphatic diisocyanates and the like.

  Examples of the polyfunctional isocyanate include 1,6-hexamethylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, norbornane diisocyanate, 1,3-bis (α , Α-dimethylisocyanatomethyl) benzene can be preferably used.

  In addition, as the polyfunctional isocyanate, the above-exemplified aliphatic polyfunctional isocyanate, alicyclic polyfunctional isocyanate, aromatic polyfunctional isocyanate, dimer or trimer by araliphatic polyfunctional isocyanate, reaction product, modified product Or a polymer (eg, diphenylmethane diisocyanate dimer or trimer, reaction product of trimethylolpropane and tolylene diisocyanate, reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, poly Ether polyfunctional isocyanate, polyester polyfunctional isocyanate, etc.) can also be used.

  Examples of the polyol include low molecular weight polyols; long-chain polyols such as polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and polyacryl polyols. The molecular weight of the low molecular weight polyol is less than 500, preferably 300 or less. The number average molecular weight of the long-chain polyol is usually 500 or more, preferably 500 to 10,000, more preferably 600 to 6000, and still more preferably 800 to 4000. A low molecular weight polyol and a long-chain polyol can each be used alone or in combination of two or more.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-pentanediol, 2 , 3-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, bisphenol Examples include polyols such as A (particularly diols).

  Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol (PTMG), and a plurality of alkylene oxides as monomer components such as an ethylene oxide-propylene oxide copolymer (alkylene). Oxide-other alkylene oxide) copolymers and the like.

  Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a reaction by three kinds of components: a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester. A thing etc. can be used. In the condensation polymerization product of polyhydric alcohol and polycarboxylic acid, examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, , 4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,4- Diethyl-1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), cyclohexanedimethanols (1,4-cyclohexane Methanol and the like), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol and sorbitol), or the like can be used. On the other hand, examples of polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexane Examples include alicyclic dicarboxylic acids such as dicarboxylic acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, and trimellitic acid. Examples of the cyclic ester in the ring-opening polymer of the cyclic ester include propiolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone. In the reaction product by three kinds of components, as the polyhydric alcohol, polyvalent carboxylic acid, and cyclic ester, those exemplified above can be used.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene, chloroformate, dialkyl carbonate or diaryl carbonate; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate). Specifically, in the reaction product of polyhydric alcohol and phosgene, the polyhydric alcohol includes the polyhydric alcohols exemplified above (for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol). Neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, etc.) can be used. In the ring-opening polymer of cyclic carbonate, examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. The polycarbonate polyol may be a compound having a carbonate bond in the molecule and a terminal being a hydroxy group, and may have an ester bond together with the carbonate bond. Representative examples of polycarbonate polyols include polyhexamethylene carbonate diol, diol obtained by ring-opening addition polymerization of lactone to polyhexamethylene carbonate diol, and co-condensate of polyhexamethylene carbonate diol with polyester diol or polyether diol. Etc.

  The polyolefin polyol is a polyol having an olefin as a component of the skeleton (or main chain) of the polymer or copolymer and having at least two hydroxy groups in the molecule (particularly at the terminal). The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, an α-olefin such as ethylene or propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal. (For example, isobutene) may be used, and diene (for example, butadiene, isoprene, etc.) may be used. Representative examples of polyolefin polyols include butadiene homopolymers, isoprene homopolymers, butadiene-styrene copolymers, butadiene-isoprene copolymers, butadiene-acrylonitrile copolymers, butadiene-2-ethylhexyl acrylate copolymers, butadiene-n-octadecyl acrylate copolymers, and the like. Or what modified | denatured the terminal of an isoprene-type polymer to the hydroxyl group is mentioned.

The polyacryl polyol is a polyol having (meth) acrylate as a component of the polymer (or copolymer) skeleton (or main chain) and having at least two hydroxy groups in the molecule (particularly at the terminal). As (meth) acrylate, (meth) acrylic acid alkyl ester [for example, (meth) acrylic acid C _1-20 alkyl ester, etc.] is preferably used. Also, for the polyol, any material other than those listed here can be used.

  The urethane resin may use polyamine as a chain extender. The molecular weight of the polyamine is usually less than 500, preferably 300 or less. Representative examples of polyamines include, for example, polyamines (particularly diamines) such as hexamethylenediamine, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-methylenebis-2-chloroaniline, and the like. Is mentioned.

  In the water-dispersed resin composition of the present invention, it is preferable to use an emulsion type urethane resin as the urethane resin. The emulsion type urethane resin may be either a forced emulsification type urethane resin using a surfactant as an emulsifier or a self-emulsification type urethane resin in which a hydrophilic group is introduced into the resin. Among these, self-emulsifying urethane resins are particularly preferable as the emulsion type urethane resins. Examples of the hydrophilic group possessed by the self-emulsifying urethane resin include a sulfonic acid group, a carboxy group, a hydroxy group, a polyethyleneoxy group, an amino group, a mono- or di-substituted amino group, and the like. Among these, as the hydrophilic group, a sulfonic acid group, a carboxy group, a hydroxy group, and a polyethyleneoxy group are preferable.

  As commercially available products of emulsion type urethane resin [polyurethane emulsion (urethane resin emulsion)], for example, Sanyo Kasei Kogyo Co., Ltd. trade names “Yukot UX-150”, “Yukot UX-200”, “Yukot UX-300”, “Ucote UX-310”, “Ucote UWS-145”, “Permarin UA-150”, “Permarin UA-300”, “Permarin UA-310”, “Permarin UA-368”, “Euprene UXA-307”; Matsumoto Product name “KP-2820” of Otsuka Pharmaceutical Co., Ltd .; Product name “Superflex 150HS” of Daiichi Kogyo Seiyaku Co., Ltd .; Product names “Hydran AP-20” and “Hydran AP-30F” of DIC Corporation , "Hydran AP-40F", "Hydran WLS-213", "Hydran W930 "; trade name of Taisei Fine Chemical Co., Ltd." ACRIT WBR-2018 "," ACRIT WBR-016U ", such as" ACRIT WEM-3008 "and the like.

  In the water-dispersed resin composition of the present invention, the urethane resin is preferably dispersed as emulsified particles in an aqueous medium described later. In that case, the average particle diameter (average emulsion particle diameter) of the emulsified particles at 25 ° C. of the urethane resin is preferably 0.1 to 0.4 μm, and preferably 0.2 to 0.3 μm from the viewpoint of storage stability. Is more preferable. The average emulsified particle diameter can be measured by a dynamic light scattering method.

  The content (blending amount) of the urethane resin in the water-dispersed resin composition of the present invention is not particularly limited, but is 0.1 to 98 wt% with respect to the nonvolatile content (100 wt%) of the water-dispersed resin composition. % Is preferable, more preferably 1 to 90% by weight, still more preferably 10 to 85% by weight, and particularly preferably 20 to 80% by weight.

  The ratio [the former / the latter (weight ratio; nonvolatile content)] of the epoxy-amine adduct of the present invention and the urethane resin in the water-dispersed resin composition of the present invention is not particularly limited, but is 1/99 to 99/1. Is more preferable, 10/90 to 95/5, more preferably 30/70 to 90/10, and particularly preferably 50/50 to 85/15.

  The water-dispersed resin composition of the present invention is a composition containing an aqueous medium. The aqueous medium is not particularly limited as long as it is a medium (medium) containing water as an essential component. That is, the water-dispersed resin composition of the present invention may contain only water as an aqueous medium, or may contain water and an organic solvent. Although it does not specifically limit as said organic solvent, Aliphatic hydrocarbons, such as hexane, heptane, and octane; Cycloaliphatic hydrocarbons, such as cyclohexane; Aromatic hydrocarbons, such as benzene, toluene, xylene, and ethylbenzene; Chloroform, dichloromethane Halogenated hydrocarbons such as 1,2-dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, etc. Esters; 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, an organic solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type. Of these, organic solvents miscible with water such as amides, alcohols, and dimethyl sulfoxide are preferable.

  The water-dispersed resin composition of the present invention preferably has a low content of organic solvent from the viewpoint of ensuring work safety and environmental protection. The content (blending amount) of the organic solvent in the water-dispersed resin composition of the present invention is not particularly limited, but is 10% by weight or less (for example, based on the total amount (100% by weight) of the water-dispersed resin composition) 0 to 10% by weight) is preferable, more preferably 5% by weight or less, still more preferably 1% by weight or less, and particularly preferably 0.1% by weight or less.

  The water-dispersed resin composition of the present invention may contain components other than the above-mentioned components (sometimes referred to as “other components”). Examples of other components include various additives such as lubricants such as fatty acids, amides and esters; coupling agents such as silane coupling agents and titanium coupling agents.

  As a preparation method (manufacturing method) of the water-dispersed resin composition of the present invention, for example, (i) an aqueous dispersion containing the epoxy-amine adduct of the present invention, a higher fatty acid ester, and a surfactant are mixed. And, if necessary, a method of mixing with a urethane resin emulsion, (ii) the epoxy-amine adduct of the present invention, a higher fatty acid ester, and a surfactant, and further, if necessary, a urethane resin (Iii) A higher fatty acid ester and a surfactant are added to and mixed with the aqueous dispersion containing the epoxy-amine adduct of the present invention, and a urethane resin is added if necessary. (Iv) Addition and mixing of the epoxy-amine adduct of the present invention and a urethane resin emulsion (if necessary) to an emulsion containing a higher fatty acid ester and a surfactant. Any method may be used. Among these, the method (i) or (ii) is preferable from the viewpoint that a stable emulsion can be easily obtained.

  “Mixing” in each of the above methods is, for example, a disperser such as a disper, homomixer, bead mill, jet mill, roll mill, hammer mill, vibration mill, ball mill, sand mill, pearl mill, spike mill, agitator mill, coball mill, etc. A stirring disperser).

  The aqueous dispersion containing the above-described epoxy-amine adduct of the present invention is, for example, a mixture of the epoxy-amine adduct of the present invention, an aqueous medium, and, if necessary, a surfactant and further other components. Thus, the epoxy-amine adduct of the present invention can be produced by dispersing (for example, suspending dispersion or emulsifying dispersion) in an aqueous medium. The order of adding various components during mixing is not particularly limited. Specifically, for example, it can be prepared by mixing a mixture containing the epoxy-amine adduct of the present invention and an aqueous medium using the above-mentioned disperser. In addition, in order to reduce the content of the organic solvent in the water-dispersed resin composition of the present invention, a treatment such as drying under reduced pressure may be further performed.

  Since the water-dispersed resin composition of the present invention contains the epoxy-amine adduct of the present invention, the reactivity with respect to functional groups such as hydroxy groups, carboxy groups, and epoxy groups present on the surface of the reinforcing fiber is high. A film formed by containing a higher fatty acid ester, a surfactant and, if necessary, a urethane resin is excellent in flexibility and toughness. For this reason, the adhesiveness of resin (especially matrix resin) and reinforced fiber (especially glass fiber or carbon fiber) in a fiber reinforced composite material, the softness | flexibility of a fiber reinforced composite material, and toughness can be improved effectively.

<Sizing agent>
Since the water-dispersed resin composition of the present invention takes the form of a water-dispersed resin composition (aqueous dispersion), it is easy to apply or impregnate reinforcing fibers. For this reason, the water-dispersed resin composition of the present invention is particularly useful as a sizing agent (particularly, a sizing agent for glass fibers or a sizing agent for carbon fibers). That is, a sizing agent containing the water-dispersed resin composition of the present invention can be used as a sizing agent for carbon fibers. 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 water-dispersed resin composition 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 water-dispersed resin composition of the present invention as an essential component, and includes a solvent and other additives in addition to the water-dispersed resin composition of the present invention. Or it may be composed only of the water-dispersed resin composition of the present invention (the water-dispersed resin composition of the present invention itself).

  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.

  The content (blending amount) of the water-dispersed resin composition of the present invention and the additive in the sizing agent of the present invention is not particularly limited and can be appropriately adjusted.

  The sizing agent (for example, sizing agent for carbon fiber) of the present invention can be preferably used for applications such as water-based paints.

<Carbon fiber coated with sizing agent>
By applying (coating) the sizing agent (carbon fiber sizing agent) of the present invention to carbon fiber, the sizing agent-coated carbon fiber (sizing agent-attached carbon fiber) (referred to as “the sizing agent-coated carbon fiber of the present invention”). In some cases). That is, the sizing agent-coated carbon fiber of the present invention is a carbon fiber sizing agent-coated carbon fiber.

  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 in which a thermoplastic resin is further applied after the sizing agent of the present invention is applied and heat-treated. Thereby, depending on the kind of the thermoplastic resin, the tack of the sizing agent-coated carbon fiber may be reduced, and the handleability (handling property) 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.

  The thermoplastic resin is not particularly limited. 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, Examples thereof include thermoplastic resins such as polyphenylene sulfide, polyethersulfone, and polyetheretherketone. However, the “thermoplastic resin” does not include the epoxy-amine adduct of the present invention. In addition, a thermoplastic resin can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  Since the sizing agent-coated carbon fiber of the present invention is coated with 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 of the present invention in the sizing agent of the present invention that is particularly excellent in heat resistance is applicable to processing at a high temperature (for example, production of sizing agent-coated carbon fiber), It can also contribute to improving the productivity of fiber-reinforced composite materials. Further, when an epoxy-amine adduct of the present invention in the sizing agent of the present invention having a somewhat high glass transition temperature is used, contamination of the processing machine (roll or the like) is prevented, and the sizing agent is applied. It is also possible to impart excellent texture and handleability to reinforcing fibers (for example, sizing agent-coated carbon fibers). 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 properties, a fiber-reinforced composite material including the sizing agent-coated carbon fiber and various matrix resins (thermoplastic resin) (fiber reinforced including the sizing agent-coated carbon fiber of the present invention) The composite material) has excellent heat resistance and mechanical strength (particularly toughness) and 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.

<Prepreg>
By using the water-dispersed resin composition of the present invention as a sizing agent and impregnating or coating the resin composition on reinforcing fibers, a prepreg that is a precursor material of a fiber-reinforced composite material (“prepreg of the present invention”) May be obtained).

  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 usual 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 of the present invention is not particularly limited and can be appropriately adjusted.

  The method for producing the prepreg of the present invention by impregnating or coating the water-dispersed resin composition of the present invention on the reinforcing fiber is not particularly limited, and is carried out by the impregnation or coating method in a known or conventional prepreg production method. can do. Specifically, for example, a method of immersing the reinforcing fiber in the water-dispersed resin composition of the present invention, a method of bringing the reinforcing fiber into contact with a roller to which the water-dispersed resin composition of the present invention is attached, and the water dispersion of the present invention Known or conventional methods such as a method of spraying the mold resin composition on the reinforcing fiber in the form of a mist are exemplified. In addition, application | coating of the water-dispersed resin composition of this invention may be performed with respect to the whole surface of a reinforced fiber, and may be performed with respect to one part surface. The coating thickness, coating amount, and impregnation amount can be adjusted as appropriate, and are not particularly limited.

  The prepreg of the present invention may be obtained by impregnating or coating the reinforcing fiber with the water-dispersed resin composition of the present invention, and then performing heat treatment 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. Moreover, the said heat processing may be performed continuously in one step, or may be performed intermittently in two or more steps. The heat treatment is generally performed to promote the impregnation of the water-dispersed resin composition of the present invention into the reinforcing fibers and to remove volatile components (aqueous medium or the like) by drying. The heat treatment can be performed by a known or conventional method (for example, heating using a hot air oven).

  The prepreg of the present invention may be obtained by impregnating or coating the reinforcing fiber with the water-dispersed resin composition of the present invention, and further applying the thermoplastic resin described above. Thereby, depending on the kind of the thermoplastic resin, tack of the prepreg of the present invention may be reduced, and handling (handling) may be further improved. The method of application is not particularly limited, and for example, it can be carried out in the same manner as the method of applying the water-dispersed resin composition of the present invention to reinforcing fibers. In addition, the said application | coating may be performed with respect to the whole surface of a prepreg (thing which has not apply | coated the thermoplastic resin), 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. Thereby, the prepreg of this invention which consists of the epoxy-amine adduct of this invention, a thermoplastic resin, and a reinforced fiber (especially carbon fiber) is obtained.

  Among the prepregs of the present invention, a prepreg coated with a thermoplastic resin (thermoplastic prepreg) is particularly effective, and is shorter than a normal curable prepreg (for example, a thermosetting prepreg, a photocurable prepreg, etc.). It has the advantage that it can be molded in time. For this reason, the thermoplastic prepreg of the present invention can be particularly preferably used for applications requiring a reduction in molding time (for example, automotive parts applications).

  It does not specifically limit as said thermoplastic resin, For example, the thermoplastic resin illustrated above can be used. In addition, a thermoplastic resin can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The content (blending amount) of the matrix resin and the like in the prepreg using the water-dispersed resin composition of the present invention is not particularly limited, but is 0.1 with respect to the total amount (100% by weight) of the prepreg excluding the reinforcing fibers. ˜99.9% by weight is preferable, more preferably 1 to 99% by weight, and still more preferably 2 to 98% by weight. By setting the content to 0.1% by weight or more, the heat resistance and mechanical properties (toughness, etc.) of the 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 matrix resin and the reinforcing fibers in the fiber-reinforced composite material tends to be further improved.

  The content (blending amount) of the epoxy-amine adduct of the present invention in the prepreg using the water-dispersed resin composition of the present invention is not particularly limited, but is 0.1 to 100 parts by weight of the matrix resin and the like. 200 parts by weight is preferable, more preferably 1 to 100 parts by weight, and still more preferably 2 to 50 parts by weight. By setting the content of the epoxy-amine adduct of the present invention to 0.1 parts by weight or more, the adhesion between the matrix resin and the reinforcing fibers in the fiber-reinforced composite material tends to be further improved. On the other hand, when the content 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 fiber-reinforced composite material tend to be secured at a higher level. is there.

  The prepreg of the present invention is, for example, a polymerization initiator (thermal polymerization initiator, photopolymerization initiator, etc.), curing agent, curing accelerator, antifoaming agent, leveling agent, coupling agent (silane coupling agent, etc.). Including conventional additives such as surfactants, inorganic fillers (silica, alumina, etc.), flame retardants, colorants, antioxidants, UV absorbers, ion adsorbents, pigments, phosphors, release agents, etc. May be. The amount of these additives is not particularly limited.

  From the prepreg of the present invention, a fiber reinforced composite material (sometimes referred to as “the fiber reinforced composite material of the present invention”) is formed. More specifically, for example, in the prepreg of the present invention, a fiber-reinforced composite material is produced by molding the prepreg.

[Fiber-reinforced composite materials]
As described above, the fiber-reinforced composite material of the present invention is formed from a prepreg using the water-dispersed resin composition of the present invention, and its production method is not particularly limited, but is a known or conventional method, for example, the above-mentioned examples It can be manufactured by the method. The fiber-reinforced composite material of the present invention has excellent adhesion between the matrix resin and the reinforcing fibers, and has high mechanical properties (particularly toughness).

  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).

<Carbon fiber treatment agent>
A carbon fiber treating agent can be obtained using the water-dispersed resin composition of the present invention. The “carbon fiber treatment agent” is a coating agent used by applying (coating) to carbon fiber. That is, the carbon fiber treating agent of the present invention is a carbon fiber coating agent containing the water-dispersed resin composition of the present invention as an essential component. This carbon fiber treating agent may be applied to carbon fibers and used as a binder for maintaining the shape of the nonwoven fabric. Furthermore, the structure which consists of the carbon fiber which processed the processing agent for carbon fibers of this invention can be impregnated with matrix resin, and it can be set as a fiber reinforced composite material.

  The treatment agent for carbon fiber of the present invention only needs to contain the water-dispersed resin composition of the present invention as an essential component, and includes a solvent and other additives in addition to the water-dispersed resin composition of the present invention. It may be a thing, and what was comprised only from the water dispersion type resin composition of this invention (The water dispersion type resin composition itself of this invention) may be sufficient. However, as described above, it is different from the matrix resin that is the main component of the fiber-reinforced composite material. Examples of other additives include, but are not limited to, lubricants such as fatty acids, amides, and esters; coupling agents such as silane coupling agents and titanium coupling agents.

  The content (blending amount) of the water-dispersed resin composition of the present invention and other additives in the carbon fiber treating agent of the present invention is not particularly limited and can be adjusted as appropriate.

  By treating the carbon fiber with the carbon fiber treating agent of the present invention, the carbon fiber having the epoxy-amine adduct of the present invention attached to the surface can be obtained. The method of the treatment using the carbon fiber treating agent of the present invention is not particularly limited, and examples thereof include the method exemplified as a method of applying the above-described sizing agent of the present invention to carbon fiber.

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

Production Example 1
[Production of carbonate 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 280.0 g of triethylenetetramine and 70.0 g of isophoronediamine, and 573.9 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 924 g of adduct was obtained.
Thereafter, 800 g of the epoxy-amine adduct obtained above was dissolved in 1200 g of water in a 3 L flask (reaction vessel) to obtain 2 kg of 40% aqueous solution.

Production Example 2
[Production of carbonate 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 3,3-diaminodiphenylsulfone [Tokyo Kasei Sales] were used.
In a 1 L stainless steel reaction vessel, a mixture of 250.0 g of triethylenetetramine and 75.0 g of 3,3-diaminodiphenylsulfone was put, and the epoxy compound (A) 500 was added thereto at 160 ° C. in a nitrogen atmosphere. 0.0 g was added dropwise over 60 minutes. 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 825 g of adduct was obtained.
Thereafter, 800 g of the epoxy-amine adduct obtained above was dissolved in 1200 g of water in a 3 L flask (reaction vessel) to obtain 2 kg of 40% aqueous solution.

Example 1
[Production of emulsion containing carbonate of epoxy-amine adduct and higher fatty acid ester]
1 kg of the epoxy-amine adduct aqueous solution obtained in Production Example 1 was placed in a 2 L plastic container and stirred at a rotational speed of 5000 to 10000 rpm using a homogenizer. 14.7 g of isopropyl palmitate (manufactured by NOF Corporation, trade name “IPP-R”), 2.4 g of Nonion OP-80R (manufactured by NOF Corporation), and nonion K-220 [ A product of 3.9 g of NOF Corporation] was slowly added dropwise over 5 minutes. After dropping, the mixture was stirred and emulsified by stirring at 10,000 rpm × 20 minutes.
1 kg of 40% aqueous solution of the obtained mixture was put into a 2 L flask (reaction vessel), and carbon dioxide gas 110 g was blown in over 5 hours while stirring, whereby the carbonate of the epoxy-amine adduct obtained in Production Example 1 An emulsion containing was obtained.

Example 2
[Production of emulsion containing carbonate of epoxy-amine adduct and higher fatty acid ester]
1 kg of the epoxy-amine adduct aqueous solution obtained in Production Example 2 was placed in a 2 L plastic container and stirred at a rotational speed of 5000 to 10000 rpm using a homogenizer. 14.7 g of isopropyl palmitate (manufactured by NOF Corporation, trade name “IPP-R”), 2.4 g of Nonion OP-80R (manufactured by NOF Corporation), and nonion K-220 [ A product of 3.9 g of NOF Corporation] was slowly added dropwise over 5 minutes. After dropping, the mixture was stirred and emulsified by stirring at 10,000 rpm × 20 minutes.
1 kg of 40% aqueous solution of the obtained mixture was put into a 2 L flask (reaction vessel), and carbon dioxide gas 110 g was blown in over 5 hours while stirring, so that the carbonate of the epoxy-amine adduct obtained in Production Example 2 An emulsion containing was obtained.

Example 3
[Production of emulsion containing carbonate of epoxy-amine adduct, higher fatty acid ester and urethane resin]
To the emulsion obtained in Example 1, 266.4 g of Hydran HW930 [manufactured by DIC, 50 wt% polyurethane emulsion] was added. After the addition, the mixture was stirred at 150 rpm × 15 minutes to obtain an emulsion.

Example 4
[Production of emulsion containing carbonate of epoxy-amine adduct, higher fatty acid ester and urethane resin]
To the emulsion obtained in Example 2, 266.4 g of Hydran HW930 [manufactured by DIC, 50 wt% polyurethane emulsion] was added. After the addition, the mixture was stirred at 150 rpm × 15 minutes to obtain an emulsion.

Comparative Example 1
1 kg of 40% aqueous solution of the epoxy-amine adduct obtained in Production Example 1 is placed in a 2 L flask (reaction vessel), and 110 g of carbon dioxide gas is blown in over 5 hours while stirring the aqueous solution. An aqueous solution containing a carbonate of the resulting epoxy-amine adduct was obtained.

Comparative Example 2
Obtained in Production Example 2 by putting 1 kg of 40% aqueous solution of the epoxy-amine adduct obtained in Production Example 2 into a 2 L flask (reaction vessel) and blowing 110 g of carbon dioxide gas over 5 hours while stirring the aqueous solution. An aqueous solution containing a carbonate of the resulting epoxy-amine adduct was obtained.

  The following evaluations were performed on the emulsions of Examples 1 and 3 and the aqueous solutions of Comparative Examples 1 and 2.

・ Adhesion evaluation (cross cut test)
Nylon 6 (NY6) film (surface untreated) using an emulsion prepared in the above examples and an aqueous solution of the carbonate of the epoxy-amine adduct prepared in the production example using a bar coater (No. 6) After coating on top, it is dried with a dryer (40 ° C. × 12 hours + 80 ° C. × 2 hours) to remove the solvent (water), and the coating film containing the epoxy-amine adduct on the base film (thickness: 6 μm) was formed. The obtained test piece was subjected to adhesion evaluation (100 square cross-cut test) in accordance with the old JIS-K-5400 (established year: February 17, 1959 issue). The results are shown in the “cross cut test” column of Table 1. The cross cut test was performed in a glove box.
The numerical values in Table 1 represent the number of squares to which the coating film has adhered without peeling from the substrate film before and after peeling the tape. That is, the maximum value of 100 is the highest, and the larger the value, the better the adhesiveness.

・ Flexibility evaluation (mandrel test)
A test piece obtained by applying and drying in the same manner as in the cross cut test is a mandrel tester (diameter: 2, 3, 4, 6, 8) according to the old JIS-K-5600-5-1. 10 mm), and the flexibility was evaluated so that the coating film side became a convex side. Table 1 shows the bending diameter (mm) at which the coating film was not broken. A smaller bend diameter (mm) indicates higher bendability (toughness). The mandrel test was conducted in a glove box.

Evaluation of wettability 1) Drying step An aqueous solution of the emulsion prepared in the above example and the aqueous solution of the carbonate of the epoxy-amine adduct prepared in the production example was added to an aluminum cup (diameter: 55 mm) and the epoxy-amine added after drying. The product was placed so that its weight was 1.5 g, and dried by heating at 105 ° C. for 2 hours under reduced pressure.
2) Muffle furnace heating step Ten muffle furnaces (Yamato Scientific Co., Ltd.) were placed in the aluminum cup obtained in 1) above by sorting nylon 6 (UBE MYLON, manufactured by Ube Industries) into 11.5 ± 5 mg. Nylon 6 was melted by heating at 290 ° C. for 5 minutes under an argon atmosphere.
3) Wettability evaluation The area (mm ² ) and the median value of each nylon 6 melted by using a microscope were measured for the aluminum cup obtained in 2) above. The results are shown in Table 2. A wider area (mm ² ) of the melted nylon 6 indicates higher wettability.

  The water-dispersed resin composition of the present invention is, for example, an adhesion improver (adhesion improver) for improving the adhesion between the resin and the additive in the polymer composite and the adhesion to the adherend. 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 inhibitors, plasticizers, crosslinkers such as epoxy resins, etc .; adhesives; paints; sealants; sizing agents, etc. Can be used.

Claims (20)

A compound selected from the group consisting of compound [I] having two or more amino groups in the molecule and a salt of compound [I],
Compound [I] is an adduct of 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,
The epoxy compound (A) includes a compound represented by the following formula (a),
The amine compound (B) includes a compound represented by the following formula (b),
A water-dispersed resin composition comprising an epoxy-amine adduct which is a compound having amino groups at both ends, a higher fatty acid ester, and a surfactant.

[Wherein, X represents a single bond or a divalent group having one or more atoms. ]

[Wherein, R ¹ represents a p-valent organic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula. p represents an integer of 2 or more. ]   The water-dispersed resin composition according to claim 1, further comprising a urethane resin.   The water-dispersed resin composition according to claim 2, wherein the urethane resin is an emulsion type urethane resin. The compound [I] having two or more amino groups in the molecule is a compound having two or more amino groups in the molecule represented by the following (I). The water-dispersed resin composition described in 1.

[Wherein, R ^{1 ′} represents a divalent organic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula. X represents a single bond or a divalent group having one or more atoms. z represents an integer of 1 or more. ]   The water-dispersed resin composition according to any one of claims 1 to 4, wherein the epoxy-amine adduct is a carbonate or an organic acid salt of the compound [I].   The water-dispersed resin composition according to any one of claims 1 to 5, wherein the surfactant is a nonionic surfactant.   7. The surfactant according to claim 6, wherein the surfactant is at least one surfactant selected from the group consisting of a polyoxyalkylene alkyl ether type nonionic surfactant and a sorbitan derivative type nonionic surfactant. Water-dispersed resin composition. A compound selected from the group consisting of compound [I] having two or more amino groups in the molecule and a salt of compound [I],
Compound [I] is an adduct of 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,
The epoxy compound (A) includes a compound represented by the following formula (a),
The amine compound (B) includes a compound represented by the following formula (b),
A method for producing a water-dispersed resin composition, comprising mixing an aqueous dispersion containing an epoxy-amine adduct, which is a compound having an amino group at both ends, a higher fatty acid ester, and a surfactant.

[Wherein, X represents a single bond or a divalent group having one or more atoms. ]

[Wherein, R ¹ represents a p-valent organic group having a carbon atom at the bonding site with the nitrogen atom shown in the formula. p represents an integer of 2 or more. ]   Furthermore, the manufacturing method of the water-dispersed resin composition of Claim 8 which mixes a urethane resin.   The method for producing a water-dispersed resin composition according to claim 9, wherein the urethane resin is an emulsion type urethane resin.   The method for producing a water-dispersed resin composition according to any one of claims 8 to 10, wherein the surfactant is a nonionic surfactant.   12. The surfactant according to claim 11, wherein the surfactant is at least one surfactant selected from the group consisting of a polyoxyalkylene alkyl ether type nonionic surfactant and a sorbitan derivative type nonionic surfactant. A method for producing a water-dispersed resin composition.   A sizing agent for carbon fiber comprising the water-dispersed resin composition according to any one of claims 1 to 7.   A carbon fiber sizing agent-coated carbon fiber coated with the carbon fiber sizing agent according to claim 13.   The fiber reinforced composite material containing the carbon fiber sizing agent application | coating carbon fiber of Claim 14.   The processing agent for carbon fibers containing the water-dispersed resin composition as described in any one of Claims 1-7.   A carbon fiber bundle to which the sizing agent for carbon fiber according to claim 13 is applied.   The prepreg by the carbon fiber sizing agent application | coating carbon fiber of Claim 14.   A fiber-reinforced composite material formed from the prepreg according to claim 18.   The fiber reinforced composite material containing the carbon fiber sizing agent application | coating carbon fiber of Claim 14, and a thermoplastic resin.