TW201510053A - Water-dispersed epoxy-amine additive resin composition, method for producing same, prepreg, and fiber-reinforced composite material - Google Patents

Abstract

The purpose of the present invention is to provide a water-dispersed epoxy-amine additive resin composition which is highly reactive, is capable of improving adhesion between reinforcing fibers and a resin in a fiber-reinforced composite material, and is particularly useful as a sizing agent. The present invention pertains to a water-dispersed epoxy-amine additive resin composition characterized by containing a surfactant and an epoxy-amine additive represented by formula (I), and by the epoxy-amine additive being dispersed in a water-based medium. (In formula (I), each R1 may be the same or different, and represents a bivalent organic group having a carbon atom at the bonding sites with the nitrogen atoms depicted in the formula. X represents a single bond or a bivalent group having one or more atoms. q represents an integer of 1 or higher.)

Description

Epoxy-amine adduct water-dispersed resin composition, method for producing the same, prepreg, and fiber reinforced composite material

The present invention relates to an epoxy-amine adduct water-dispersed resin composition, a method for producing the same, a prepreg, and a fiber-reinforced composite material. More specifically, the epoxy-amine adduct water-dispersed resin composition obtained by dispersing an epoxy-amine adduct in an aqueous medium, a method for producing the same, and a water-dispersible resin A prepreg obtained by impregnating or coating a composition on a reinforcing fiber and a fiber-reinforced composite material formed from the prepreg. Priority is claimed on Japanese Patent Application No. 2013-122669, filed on Jun.

A fiber-reinforced composite material which is a composite material of a reinforcing fiber and a resin such as carbon fiber or glass fiber has excellent heat resistance and mechanical properties, and thus has been used in various applications. In such a fiber-reinforced composite material, a sizing agent (contracting agent) is usually used. The sizing agent is applied as a slurry to a reinforcing fiber such as carbon fiber, and is used for the purpose of improving the high-order workability of the reinforcing fiber lacking the converging property.

As the sizing agent, for example, diepoxypropyl ether of bisphenol A (refer to Patent Documents 1, 2) and polyalkylene oxide of bisphenol A are known. The product (see Patent Documents 3 and 4), the addition of an epoxy group to the polyalkylene oxide adduct of bisphenol A (see Patent Documents 5 and 6), and the epoxy addition of a polyolefin-based diol. Products (see Patent Documents 7 to 9) and the like.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 50-059589

[Patent Document 2] Japanese Laid-Open Patent Publication No. SHO 57-171767

[Patent Document 3] Japanese Laid-Open Patent Publication No. 07-009444

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-336577

[Patent Document 5] Japanese Patent Laid-Open Publication No. 61-028074

[Patent Document 6] Japanese Laid-Open Patent Publication No. 01-272867

[Patent Document 7] Japanese Laid-Open Patent Publication No. SHO 57-128266

[Patent Document 8] Japanese Laid-Open Patent Publication No. 59-009273

[Patent Document 9] Japanese Laid-Open Patent Publication No. 62-033872

However, in the fiber-reinforced composite material using the sizing agent disclosed in the cited documents 1 to 9, the problem that the adhesion between the resin and the reinforcing fiber is insufficient is generated. Therefore, in the sizing agent in the fiber-reinforced composite material, not only a sizing agent capable of improving the high-order workability of the reinforcing fiber such as carbon fiber but also a reinforcing fiber and a resin (matrix resin) in the fiber-reinforced composite material are required. Adhesive (adhesive) enhanced sizing agent.

Also, reinforcing fibers and bases in fiber reinforced composites The size of the adhesion of the resin is affected by the compatibility of the sizing agent with the matrix resin. Particularly in the case where a thermoplastic resin is used as the matrix resin, it is necessary to appropriately use a sizing agent suitable for the resin. Therefore, development of a sizing agent capable of exhibiting good adhesion to reinforcing fibers in a wide range of cases even when a matrix resin is used has been sought.

In addition, when the sizing agent is used as an additive for improving the adhesion between the resin and the reinforcing fiber in the fiber-reinforced composite material, it is required to be easily hardened to other components (for example, a thermoplastic resin or an epoxy compound). Resin, etc.) blending. However, for example, an adduct of an epoxy compound having a glycidyl group such as bisphenol A diglycidyl ether or the like and a polyamine compound other than the above may form a crosslinked structure, thereby allowing even heating. It does not soften or even melt, and it is difficult to mix with other ingredients, and a uniform composition cannot be obtained. Further, since the above-mentioned adduct has a crosslinked structure as described above, it is difficult to form a solution or an aqueous dispersion.

Accordingly, an object of the present invention is to provide an epoxy-amine adduct water-dispersible resin composition and a process for producing the same, which are highly reactive and can be made to have a high reactivity. The adhesion of the resin to the reinforced fiber in the fiber reinforced composite material is particularly useful as a sizing agent.

Further, another object of the present invention is to provide a prepreg of a fiber-reinforced composite material which is excellent in adhesion between a resin and a reinforcing fiber.

Furthermore, another object of the present invention is to provide a resin having excellent adhesion to a reinforcing fiber and having high mechanical properties (for example, toughness). Fiber reinforced composites.

The present inventors have intensively studied to solve the above problems, and as a result, found that water containing a specific epoxy-amine adduct (Amine Adduct) and a surfactant and the above epoxy-amine adduct is dispersed in an aqueous medium The dispersion-type resin composition has high reactivity, and can improve the adhesion of the resin and the reinforcing fiber in the fiber-reinforced composite material, and is particularly useful as a sizing agent system, and the present invention has been completed.

That is, the present invention provides an epoxy-amine adduct water-dispersed resin composition comprising an epoxy-amine adduct represented by the following formula (I) and a surfactant, and the epoxy The base-amine adduct is dispersed in an aqueous medium, [In the formula (I), R ¹ is the same or different, and represents a divalent organic group having a carbon atom at a bonding position to a nitrogen atom represented by the formula, and X represents a single bond or has one or more atoms. The divalent group, q represents an integer of 1 or more].

Furthermore, the epoxy group-amine adduct water-dispersed resin composition is provided, wherein the surfactant is at least one selected from the group consisting of an anionic surfactant and a nonionic surfactant. Surfactant.

Moreover, the present invention provides a method for producing an epoxy group-amine adduct water-dispersed resin composition, which comprises the epoxy group-amine adduct represented by the following formula (I) and a surfactant; A method for dispersing an epoxy-amine addition product in an aqueous medium, wherein the epoxy-amine addition product, surfactant, and water are mixed medium, [In the formula (I), R ¹ is the same or different, and represents a divalent organic group having a carbon atom at a bonding position to a nitrogen atom represented by the formula, and X represents a single bond or has one or more atoms. The divalent group, q represents an integer of 1 or more].

Further, a method for producing a water-dispersed resin composition of an epoxy group-amine adduct as described above, wherein the surfactant is selected from the group consisting of an anionic surfactant and a nonionic surfactant At least one surfactant.

Moreover, the present invention provides a prepreg which is obtained by impregnating or applying the epoxy group-amine adduct water-dispersed resin composition to a reinforcing fiber.

Further, the present invention provides a fiber-reinforced composite material which is a fiber-reinforced composite material formed of the aforementioned prepreg.

Further, the present invention provides a novel epoxy-amine adduct suitable for producing the above epoxy-amine adduct water-dispersed resin composition.

That is, the present invention relates to the following invention.

[1] An epoxy-amine adduct water-dispersible resin composition comprising an epoxy-amine adduct represented by the following formula (I) and a surfactant, and the epoxy group- The amine adduct is dispersed in an aqueous medium, [In the formula (I), R ¹ is the same or different, and represents a divalent organic group having a carbon atom at a bonding position to a nitrogen atom represented by the formula, and X represents a single bond or has one or more atoms. The divalent group, q represents an integer of 1 or more].

[2] The epoxy group-amine adduct water-dispersed resin composition according to [1], wherein the epoxy resin is a nonvolatile component (100% by weight) of the water-dispersible resin composition The content of the base-amine adduct is preferably from 0.1 to 98% by weight, more preferably from 1 to 90% by weight, still more preferably from 10 to 85% by weight, particularly preferably from 20 to 80% by weight.

[3] The epoxy group-amine adduct water-dispersed resin composition according to [1] or [2], wherein the number average molecular weight of the epoxy group-amine adduct is preferably from 200 to 40,000. Good for 300~30000, and even better for 400~20000.

[4] The epoxy-amine adduct water-dispersed resin composition according to any one of [1] to [3] wherein the glass transition temperature (Tg) of the epoxy group-amine adduct is higher than Preferably, it is -50 to 200 ° C, more preferably -40 to 190 ° C, and even more preferably -30 to 180 ° C.

[5] The epoxy-amine adduct water-dispersed resin composition according to any one of [1] to [4], wherein the epoxy-amine adduct 100 is relative to the foregoing epoxy-amine adduct 100 The content of the surfactant is preferably from 0.01 to 500 parts by weight, more preferably from 0.1 to 200 parts by weight, still more preferably from 0.5 to 100 parts by weight, per part by weight.

[6] The epoxy-amine addition product water-dispersed resin composition according to any one of [1] to [5], wherein the total amount (100% by weight) relative to the water-dispersed resin composition The content of the organic solvent is preferably 10% by weight or less (for example, 0 to 10% by weight), 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 epoxy-amine addition product water-dispersed resin composition as described in any one of [1] to [6] wherein the surfactant is selected from an anionic surfactant and a nonionic At least one surfactant in the group of sexual surfactants.

[8] A method for producing an epoxy group-amine adduct water-dispersed resin composition, which comprises producing an epoxy group-amine adduct represented by the following formula (I) and a surfactant A method for dispersing an epoxy-amine adduct water-dispersible resin composition in an aqueous medium, characterized in that the epoxy group-amine adduct, a surfactant, and an aqueous medium are mixed. [In the formula (I), R ¹ is the same or different, and represents a divalent organic group having a carbon atom at a bonding position to a nitrogen atom represented by the formula, and X represents a single bond or has one or more atoms. The divalent group, q represents an integer of 1 or more].

[9] The method for producing an epoxy group-amine adduct water-dispersed resin composition according to [8], wherein the surfactant is selected from the group consisting of an anionic surfactant and a nonionic surfactant. At least one surfactant in the group.

[10] A prepreg obtained by impregnating or coating a epoxy-amine adduct water-dispersed resin composition according to any one of [1] to [7] on a pre-impregnated fiber. Things.

[11] The prepreg according to [10], which contains a thermoplastic resin, a curable resin, or a precursor of a curable resin, wherein the total amount (100% by weight) of the prepreg from which the reinforcing fibers are removed is The content of the thermoplastic resin, the curable resin or the curable resin is preferably from 0.1 to 99.9% by weight, more preferably from 1 to 99% by weight, still more preferably from 2 to 98% by weight.

[12] The prepreg according to [11], wherein the content of the epoxy group-amine adduct is preferably 0.1 to 200 with respect to 100 parts by weight of the thermoplastic resin, the curable resin or the precursor thereof. The parts by weight are more preferably 1 to 100 parts by weight, still more preferably 2 to 50 parts by weight.

[13] A fiber-reinforced composite material, which is a fiber-reinforced composite material formed from the prepreg according to any one of [10] to [12].

[14] An epoxy-amine addition product which is an epoxy-amine addition product having two or more amine groups in a molecule, which has two or more alicyclic groups in a molecule. An epoxy group-amine adduct obtained by a reaction of an epoxy group-containing epoxy compound (A), an amine compound represented by the following formula (b-1), and an amine compound represented by the following formula (b-2).

[15] The epoxy group-amine adduct according to [14], wherein the epoxy compound (A) having two or more alicyclic epoxy groups in the molecule is a compound represented by the following formula (a) .

[16] The epoxy group-amine adduct according to [14] or [15], wherein the epoxy compound (A) having two or more alicyclic epoxy groups in the molecule is represented by the following formula (a) -1) a compound represented.

[17] The epoxy group-amine adduct according to any one of [14] to [16] wherein the number average molecular weight is preferably from 200 to 40,000, more preferably from 300 to 30,000, still more preferably from 400 to 400. 20000.

[18] The epoxy group-amine adduct according to any one of [14] to [17] wherein the glass transition temperature (Tg) is preferably -50 to 200 ° C, more preferably -40 to 190 ° C. More preferably, it is -30~180°C.

[19] The epoxy-amine addition product according to any one of [1] to [18] wherein the number of -NH- groups in the molecule is preferably from 1 to 200, more preferably 1 ~150, and even better 2~100.

Since the epoxy-amine adduct water-dispersed resin composition of the present invention contains the above epoxy group-amine adduct, it is reactive with functional groups such as a hydroxyl group, a carboxyl group or an epoxy group which are present on the surface of the reinforcing fiber. High, it can effectively improve the adhesion of the resin and the reinforcing fiber in the fiber-reinforced composite material. In particular, the epoxy-amine adduct water-dispersible resin composition of the present invention can broadly exhibit a good adhesion to the reinforcing fibers of the resin even when a matrix resin is used. ,very useful. Further, since it is in the form of a water-dispersed resin composition, impregnation or coating of the reinforcing resin can be easily performed. Further, the epoxy-amine adduct water-dispersible resin composition of the present invention can be selected without forming an aqueous dispersion-type resin composition (aqueous dispersion) containing no organic solvent or a small amount thereof. It is used in the working environment and is also advantageous in terms of environmental protection. Therefore, when the epoxy-amine adduct water-dispersible resin composition of the present invention is used, it is possible to obtain a prepreg of a fiber-reinforced composite material which is excellent in adhesion between a resin and a reinforcing fiber by excellent productivity. Further, by using the above prepreg, it is possible to obtain a fiber-reinforced composite material which is excellent in adhesion between a resin and a reinforcing fiber and has high mechanical properties (especially toughness).

Fig. 1 is a chart showing the ¹ H-NMR spectrum of an epoxy compound (CELLOXIDE 2021P) used as a raw material of an epoxy-amine adduct in Production Examples 1 and 2.

Fig. 2 is a chart showing the ¹ H-NMR spectrum of an amine compound (JEFFAMINE D-230) used as a raw material of an epoxy-amine adduct in Production Examples 1 and 2.

Fig. 3 is a chart showing the ¹ H-NMR spectrum of the epoxy group-amine adduct obtained in Production Example 1.

[Formation of the Invention]

<Epoxy-amine adduct water-dispersed resin composition>

The epoxy-amine adduct water-dispersible resin composition of the present invention (an aqueous dispersion of an epoxy-amine adduct; sometimes referred to simply as "the water-dispersed resin composition of the present invention") is a kind A water-dispersed resin composition comprising a compound represented by the following formula (I) (epoxy-amine addition product; sometimes referred to as "the epoxy group-amine addition product of the present invention") and an interface The active agent is an essential component, and the above epoxy-amine adduct is dispersed in an aqueous medium.

In the water-dispersed resin composition of the present invention, the state in which the "epoxy-amine adduct is dispersed" means that at least a part of the epoxy-amine adduct is not dissolved in the aqueous medium. The state is suspended or dispersed, or emulsified and dispersed. In the water-dispersed resin composition of the present invention, the epoxy group-amine adduct is preferably emulsified and dispersed in an aqueous medium. In the present specification, the term "amino group" means -NH ₂ (unsubstituted amino group), and the "-NH- group" does not include the unsubstituted amine group (-NH). ₂ ).

[Epoxy-amine adduct represented by formula (I)]

R ¹ in the above formula (I) is identical or different from each other to represent a divalent organic group (organic residue) having a carbon atom at a bonding position to a nitrogen atom represented by the formula. Examples of the above R ¹ include a divalent linear or branched aliphatic hydrocarbon group; a divalent cyclic aliphatic hydrocarbon group; a divalent aromatic hydrocarbon group; and such a group (straight chain or branch) Two or more of a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aromatic hydrocarbon group, or a divalent group obtained by bonding a hetero atom-containing bond group (divalent group).

The above-mentioned divalent linear or branched aliphatic hydrocarbon group may, for example, be an alkyl group [e.g., methylene, ethyl, propyl, butyl, pentyl, hexyl) , stretching heptyl, stretching octyl, stretching sulfhydryl, stretching hydrazine, stretching undecyl, stretching lauryl, stretching tridecyl, stretching tetradecyl, stretching pentadecyl, stretching sixteen a linear or branched alkyl group having a carbon number of 1 to 30 (C _1-30 ) such as an alkyl group, a heptadecyl group or an octadecyl group (preferably a C _1-18 alkyl group), etc.] And an alkenyl group [corresponding to an extended alkenyl group of the above alkyl group, for example, a vinyl group or a propylene group having a linear or branched alkenyl group having 2 to 30 carbon atoms (preferably a C _2-18 extension) Alkenyl), etc.].

The above-mentioned divalent linear or branched aliphatic hydrocarbon group may have various substituents (that is, at least one of hydrogen atoms of the above-mentioned divalent linear or branched aliphatic hydrocarbon group may be subjected to various substitutions Base substitution). Examples of the above substituents include a halogen atom, a pendant oxy group, a hydroxyl group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, a decyloxy group, etc.), a carboxyl group, and a Substituted oxycarbonyl (alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, etc.), substituted or unsubstituted aminemethanyl, cyano, nitro, substituted or unsubstituted amine Sulfo, Heterocyclic group and the like. The above hydroxyl group or carboxyl group may be protected by a protecting group conventionally used in the field of organic synthesis (for example, mercapto group, alkoxycarbonyl group, organodecyl group, alkoxyalkyl group, oxacycloalkyl group, etc.).

With respect to the above substituted or unsubstituted amine carbenyl group, for example, an alkyl group having a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, a tertiary butyl group or the like may be mentioned. Or an amine-methyl group such as an oxime group such as an acetyl group or a benzyl group or an unsubstituted aminomethyl group. Further, examples of the above substituted or unsubstituted amino group include an alkyl group having a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, and a tertiary butyl group. Or an amine group such as an alkyl group or a fluorenyl group or an unsubstituted amino group.

The heterocyclic ring constituting the above heterocyclic group includes an aromatic hetero ring and a non-aromatic hetero ring. Examples of such a heterocyclic ring include a hetero 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 oxycyclobutane ring, a furan ring, or a tetrahydrofuran ring, a 5-membered ring such as an azole ring or a γ-butyrolactone ring, a 4-side oxy-4H-pyran ring, a tetrahydropyran ring, 6-membered ring such as porphyrin ring, benzofuran ring, 4-side oxy-4H- a terpene ring, a chrome ring, a condensed ring, a 3-oxatricyclo[4.3.1.1 ^4,8 ]undec-2-one ring, a 3-oxatricyclo ring [4.2. 1.0 ^4,8 ]Heterane-2-one ring bridging ring), heterocyclic ring containing a sulfur atom as a hetero atom (for example: thiophene ring, thiazole ring, thiadiazole ring, etc. 5-membered ring, 4-side oxygen- a 6-membered ring such as a 4H-thiopyran ring or a condensed ring such as a benzothiophene ring, or a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, or a triazole) 5-membered ring, pyridine ring, hydrazine Ring, pyrimidine ring, pyridyl Ring, piperidine ring, piperazine 6-membered ring, anthracene ring, isoindoline ring, quinoline ring, acridine ring, a fused ring such as a pyridine ring, a quinazoline ring or an anthracene ring). The heterocyclic group may have an alkyl group (for example, a C _1-4 alkyl group such as a methyl group or an ethyl group) or a cycloalkane in addition to the substituent of the above-mentioned divalent linear or branched aliphatic hydrocarbon group. a substituent such as a aryl group (e.g., phenyl, naphthyl, etc.). Further, as the nitrogen atom constituting the hetero ring, a conventional protecting group (for example, an alkoxy group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an aralkoxycarbonyl group, an aralkyl group, an anthracenyl group, an arylsulfonyl group, or the like) may be used. Alkylsulfonyl, etc.) to protect.

The divalent cyclic aliphatic hydrocarbon group may, for example, be a cycloalkyl group (for example, a cyclopropyl group, a cyclopentene group, a cyclopentylene group, a cyclohexylene group or the like) having a carbon number of 3 to 20 a cycloalkyl group (preferably a C _3-15 cycloalkyl group), etc., a cycloalkenyl group [corresponding to a cycloalkenyl group of the above cycloalkyl group, for example, a cyclohexene group such as a cyclopentene group having a carbon number of 3 to 20 a cycloalkenyl group (preferably a C _3-15 cycloalkenyl group), etc., a cycloalkylidene [corresponding to a cycloalkylene group of the above cycloalkyl group, for example, a cyclopentylene group, a sub a cycloalkylene group having a carbon number of 3 to 20, preferably a C _3-15 cycloalkylene group, etc., a cycloalkadienylene group (a ring-shaped diene corresponding to the above cycloalkyl group) a group, for example, a cyclopentadienyl group having a carbon number of 4 to 20 such as cyclopentadienylene (preferably a C _4-15 ring-opening diene group), or a divalent polycyclic hydrocarbon group [ For example: a spiro hydrocarbon (for example, spiro[4.4]decane, spiro[4.5]decane, etc.)-divalent spirohydrocarbyl group; a bicyclic ring such as a cyclocarbon (for example, a bicyclopropyl group)-diyl group Agglomerated cyclic hydrocarbons; bridging cyclic hydrocarbons (eg, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane Norbornane, norbornene, adamantane) - divalent cyclic hydrocarbon bridging group and the like, etc.] and the like. The divalent cyclic aliphatic hydrocarbon group may have an alkyl group (for example, a C _1-4 alkane such as a methyl group or an ethyl group, in addition to the substituent which the above-mentioned divalent linear or branched aliphatic hydrocarbon group may have. Substituents such as aryl (for example, phenyl, naphthyl, etc.).

The above-mentioned divalent aromatic hydrocarbon group may be a group which removes two hydrogen atoms from an aromatic hydrocarbon. Examples of the aromatic hydrocarbons include benzene, naphthalene, anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, fused tetraphenyl, anthracene, anthracene, biphenyl, binaphthyl, and hydrazine ( Bianthryl) and so on. Further, the divalent aromatic hydrocarbon group may have an alkyl group (for example, a C _1-4 alkane such as a methyl group or an ethyl group, in addition to a substituent which the divalent linear or branched aliphatic hydrocarbon group may have. Substituents such as a group such as a cycloalkyl group.

Examples of the divalent group in which two or more of the linear or branched aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group, and the aromatic hydrocarbon group are directly bonded are, for example, a cyclohexylene-methylene group. a group in which an aliphatic hydrocarbon group is bonded to an alicyclic hydrocarbon group; a phenyl-methylene group, a phenyl-phenylene group, and the like, and a aryl group-alkylene group having a carbon number of 7 to 18 (especially a total carbon) An aliphatic hydrocarbon group such as a C _6-10 extended aryl-C _2-6 extended alkenyl group such as a 7 to 10 aryl-alkylene group, a phenyl-extended propylene group, a phenyl-extended vinyl group, or the like A group bonded to an aromatic hydrocarbon group or the like.

Examples of the linking group (divalent group) containing the above hetero atom include -CO-(carbonyl), -O-(ether bond), -CO-O-(ester bond), -O-CO. -O-(carbonate group), -CO-NH-(nonylamino), -CO-NR ^a - (substituted amidoxime; R ^a represents an alkyl group), -NH-, -NR ^b - (R ^b is an alkyl group), a divalent group containing a hetero atom (such as an oxygen atom, a nitrogen atom or a sulfur atom) such as -SO- or -SO ₂ -, or a divalent group in which a plurality of these bonds are bonded. .

R ¹ in the formula (I) may be the same or different.

X in the above formula (I) represents a single bond or a bond group (having a divalent group of one or more atoms). Examples of the above-mentioned linking group include a divalent hydrocarbon group, a part or all of a carbon-carbon double bond, an epoxidized alkenyl group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amidino group, Two or more groups of these groups are bonded to each other.

The divalent hydrocarbon group in the above X may, for example, be a linear or branched alkylene group having a carbon number of 1 to 18, a divalent alicyclic hydrocarbon group or the like. 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 exoethyl group, a propyl group, and a trimethylene group. (trimethylene) and so on. The above-mentioned divalent alicyclic hydrocarbon group may, for example, be 1,2-cyclopentenyl, 1,3-cyclopentyl, cyclopentylene, 1,2-extended cyclohexyl, 1,3. a divalent cycloalkyl group (including a cycloalkylene group) such as a cyclohexyl group, a 1,4-cyclohexylene group or a cyclohexylene group.

Examples of the alkenyl group in the epoxidized alkenyl group (sometimes referred to as "epoxidized alkenyl group") of a part or all of the above carbon-carbon double bond include, for example, a vinyl group and a propenyl group. a 1- or 2-butenyl group, a 2-butenbutenyl group, a butadienyl group, a pentenyl group, a hexenylene group, a heptenyl group, a exemplified alkenyl group, and the like, or a straight chain having 2 to 8 carbon atoms; Branched alkenyl group and the like. In particular, in the case of the above epoxidized alkenyl group, it is preferred that all of the epoxidized alkenyl group of the carbon-carbon double bond, more preferably the carbon-carbon double bond, of all the epoxidized carbon number of 2 to 4 Alkenyl.

The above-mentioned bond group X is particularly preferably a bond group containing an oxygen atom, and specific examples thereof include -CO-, -O-CO-O-, -CO-O-, -O-, -CO-NH-, epoxidized alkenyl group; such a group of a plurality of bonded groups; one or more of these groups and a divalent hydrocarbon group A base or the like formed by bonding one or more bonds. The divalent hydrocarbon group may be exemplified above.

Further, when q is an integer of 2 or more, each X may be the same or different.

q in the above formula (I) (the number of repetitions of the structural unit in parentheses appended with q) means an integer of 1 or more. As far as q is concerned, there is no particular limitation, but it is preferably 1 to 200, more preferably 2 to 150, and even more preferably 2 to 100. When q is 200 or less, the epoxy group-amine adduct is more likely to be blended with other components or the water-dispersed resin composition. Further, the q in the above formula (I) can be controlled, for example, according to the ratio of the epoxy compound (A) to the amine compound (B) subjected to the reaction described later, reaction conditions, and the like.

In the above formula (I), among the carbon atoms constituting the cyclohexane ring, when the carbon atom to which the X bond is bonded is a carbon atom of "position 1", it is bonded to the ring represented by the formula (I). The bonding position of the nitrogen atom (-NH-) of the alkane ring is a carbon atom at the position 3 or a carbon atom at the position 4. When the bonding position of the nitrogen atom is a carbon atom at the position of No. 3, the bonding position of the hydroxyl group (-OH) bonded to the cyclohexane ring represented by the formula (I) is a carbon atom at the position of No. 4. Further, when the bonding position of the nitrogen atom is a carbon atom at the position 4 of the cyclohexane ring, the bonding position of the hydroxyl group (-OH) bonded to the cyclohexane ring represented by the formula (I) is No. 3 The carbon atoms in the position. The bonding position (or the bonding position of the hydroxyl group) of the nitrogen atom in the plurality of (two or more) cyclohexane rings in the above formula (I) may be the same or different. Further, when the above position number is attached to the carbon atom constituting the cyclohexane ring in the formula (I), it is as shown in the following formula.

The epoxy group-amine adduct of the present invention may be a mixture of two or more epoxy-amine adducts different in q.

The epoxy group-amine adduct of the present invention is represented by the following formula (b) by a compound represented by the following formula (a) (epoxy compound; sometimes referred to as "epoxy compound (A)")) The compound (amine compound; sometimes referred to as "amine compound (B)") is obtained by an addition reaction.

H ₂ N-R ¹ -NH ₂    (b)

The X system in the above formula (a) is the same as X in the formula (I), and represents a single bond or a bond group (having a divalent group of one or more atoms).

The epoxy compound (A) wherein X is a single bond in the above formula (a) is exemplified by 3,4,3',4'-dicyclooxybicyclohexane.

Representative examples of the alicyclic epoxy compound represented by the above formula (a) include compounds represented by the following formulas (a-1) to (a-10), and 2,2-bis (3,4). -epoxycyclohexane-1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 1,2-epoxy-1,2-dual ( 3,4-epoxycyclohexane-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl)ether, and the like. Further, 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, and examples thereof include a methylene group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a stretching group. Ding A straight or branched alkyl group such as a butyl group, a butyl group, a hexyl group, a hexyl group, a heptyl group or a octyl group. Among these, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an exoethyl group, a propyl group and an isopropyl group is preferable. In the following formulas (a-9) and (a-10), n1 to n6 each represent an integer of 1 to 30.

Among the compounds represented by the above formula (a), particularly in the viewpoint of heat resistance or handleability, the compound represented by the above formula (a-1) [3,4-epoxycyclohexylmethyl group is preferred. (3,4-Ethoxy)cyclohexanecarboxylate; trade name "CELLOXIDE 2021P" (manufactured by DAICEL Co., Ltd.).

In the above formula (b) R ¹ the same lines of formula (I), the R ^1, which represents a carbon atom of a divalent organic group (organic residue) bonding position of the nitrogen atom shown in the formula.

In particular, the amine compound (B) is preferably a compound represented by the following formula (b-1) ((poly)ether diamine).

R ² in the above formula (b-1) represents a divalent linear, branched or cyclic aliphatic hydrocarbon group, or one or more of a linear or branched aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. A divalent group formed by one or more bonds. The divalent linear, branched or cyclic aliphatic hydrocarbon group may, for example, be a divalent linear, branched or cyclic aliphatic hydrocarbon group exemplified as the above R ¹ . In addition, the divalent linear, branched or cyclic aliphatic hydrocarbon group of the above R ² may have a substituent, and examples of the substituent include, for example, the substituent as the above R ¹ . The same substituents.

Wherein, in the above R ² , a divalent linear or branched aliphatic hydrocarbon group is preferred, and a linear or branched alkylene group having a carbon number of 2 to 6 is more preferred, and more preferably carbon. A linear or branched alkyl group of 2 to 4 (especially an ethyl group, a trimethylene group, a propyl group).

R ³ in the above formula (b-1) represents a divalent linear, branched or cyclic aliphatic hydrocarbon group, or one or more of a linear or branched aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. A divalent group formed by one or more bonds. The divalent linear, branched or cyclic aliphatic hydrocarbon group may, for example, be a divalent linear, branched or cyclic aliphatic hydrocarbon group exemplified as the above R ¹ . In addition, the divalent linear, branched or cyclic aliphatic hydrocarbon group of the above R ³ may have a substituent, and examples of the substituent include, for example, the substituent as the above R ¹ . The same substituents.

Wherein, in the above R ³ , a divalent linear or branched aliphatic hydrocarbon group is preferred, and a linear or branched alkyl group having 2 to 6 carbon atoms is more preferred, and more preferably carbon. A linear or branched alkyl group of 2 to 4 (especially an ethyl group, a trimethylene group, a propyl group). Further, when p is an integer of 2 or more, R ³ (plurality of R ³ ) in each parenthesis may be the same or different. Further, when two or more kinds of R ³ are present, the addition form (polymerization form) of the structure in the parentheses attached to p may be a random type or a block type.

p in the above formula (b-1) (the number of repeating structural units in parentheses attached to p) means an integer of 1 or more. In the case of p, for example, it is preferably from 1 to 100, more preferably from 1 to 70, still more preferably from 1 to 30. When p is 100 or less, the heat resistance of the epoxy-amine adduct of the present invention, the heat resistance of the fiber-reinforced composite material, or the mechanical properties (such as toughness) tend to be further improved.

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

Further, the amine compound (B) may, for example, be a compound represented by the following formula (b-2) (a diamine having a cyclohexane ring).

In the above formula (b-2), R ⁴ and R ⁵ are the same or different, and represent an alkylene group having 1 to 4 carbon atoms or an exoaryl group having 6 to 12 carbon atoms; and R ⁶ is a cyclohexane represented by the formula: The substituent on the alkane ring, which is the same or different, represents an alkyl group having 1 to 6 carbon atoms; the r system represents 0 or 1; and the s represents a substituent (R ⁶ ) on the cyclohexane ring shown in the formula; The number is an integer from 0 to 10. Further, when there are two or more R ⁶ , each of R ⁶ may be the same or different.

More specifically, the compound represented by the above formula (b-2) may, for example, be isophorone diamine.

For the amine compound (B), for example, the trade names "JEFFAMINE D-230", "JEFFAMINE D-400", "JEFFAMINE D-2000", "JEFFAMINE D-4000", " JEFFAMINE HK-511", "JEFFAMINE ED-600", "JEFFAMINE ED-900", "JEFFAMINE ED-2003", "JEFFAMINE EDR-148", "JEFFAMINE EDR-176", "JEFFAMINE XTJ-582", "JEFFAMINE" XTJ-578", "JEFFAMINE XTJ-542", "JEFFAMINE XTJ-548", "JEFFAMINE XTJ-559" (above is HUNTSMAN); trade names "VESTAMIN IPD", "VESTAMIN TMD", "VESTAMIN A139" ( The above is a commercial item such as EVONIK.

The molecular weight of the amine compound (B) is not particularly limited, but is preferably from 80 to 10,000, more preferably from 100 to 5,000, still more preferably from 200 to 1,000. By making the molecular weight 80 or more, the amount of the -NH- group (substituted amino group) described later in the epoxy-amine addition product is not too large but is an appropriate amount, for example, with a curable resin ( The toughness of the cured product (hardened resin) obtained by curing the composition of the curable compound) tends to be improved. On the other hand, when the molecular weight is 10,000 or less, it is possible to ensure good reactivity with the epoxy compound (A) and to more effectively enjoy the effect obtained by blending the epoxy-amine adduct ( For example, there is a tendency that the heat resistance of the cured product (hardened resin) is improved, the heat resistance of the fiber-reinforced composite material, and the toughness is improved.

The epoxy group-amine adduct of the present invention can be produced by reacting the epoxy compound (A) with the amine compound (B) as described above. More specifically, the epoxy group-amine adduct of the present invention is produced by reacting an alicyclic epoxy group of the epoxy compound (A) with an amine group of the amine compound (B).

Further, in the production of the epoxy-amine adduct of the present invention The epoxy compound (A) may be used alone or in combination of two or more. Similarly, the amine compound (B) may be used alone or in combination of two or more.

The above reaction (reaction of the epoxy compound (A) with the amine compound (B)) can also be carried out in the presence of a solvent or in the absence of a solvent (i.e., in the absence of a solvent). The solvent is not particularly limited as long as it is capable of uniformly dissolving or dispersing the epoxy compound (A) and the amine compound (B). More specifically, examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Halogenated hydrocarbon such as chloroform, dichloromethane or 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, Ethers such as alkane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; N, N-dimethyl A guanamine such as methotrexate or N,N-dimethylacetamide; a nitrile such as acetonitrile, propionitrile or benzonitrile; an alcohol such as methanol, ethanol, isopropanol or butanol; and dimethyl hydrazine. Further, the solvent may be used singly or in combination of two or more.

The above reaction may also be carried out in the presence of a catalyst or may be carried out in the absence of a catalyst (substantially absent). More specifically, in the case of using an aromatic amine compound (a compound having an amine group substituted on an aromatic ring) as the amine compound (B), it is preferred to carry out the above reaction in the presence of a catalyst; When a compound other than the aromatic amine compound (non-aromatic amine compound) is used as the amine compound (B), it is preferred to carry out the above reaction in the absence of a catalyst.

Also, there is no special limitation on the above catalysts. For example, a curing accelerator or the like used for curing an epoxy resin (epoxy compound) using an amine-based curing agent may, for example, be specifically a tertiary amine [for example, lauryl dimethylamine or N). , N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, (N,N-dimethylaminomethyl)phenol, 2,4,6 - ginseng (N,N-dimethylaminomethyl)phenol, 1,8-dioxinbicyclo[5.4.0]undec-7-ene (DBU), 1,5-dioxinbicyclo[4.3.0壬-5-ene (DBN), etc.; tertiary amine salt [eg, carboxylate, sulfonate, inorganic acid salt, etc. of the above tertiary amine]; imidazoles [eg 2-methylimidazole, 2 -ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazolium, etc.; organophosphorus compounds [eg triphenylphosphine, triphenyl phosphite, etc.]; quaternary ammonium salts [eg tetraethylammonium bromide, tetrabutylammonium bromide, etc.] a quaternary phosphonium salt [eg, tetrabutyl decanoate, tetrabutyl laurate, tetrabutyl phosphonium tetradecanoate, tetrabutyl phosphonium hexate, tetrabutyl phosphonium cations and bicyclic rings [2.2.1] a salt of heptane-2,3-dicarboxylic acid and/or methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid anion, tetrabutylphosphonium cation and 1,2 a salt of an anion of 4,5-cyclohexanetetracarboxylic acid, etc.], a sulfonium salt such as a quaternary phosphonium salt, a tertiary sulfonium salt, a tertiary selenium salt, a secondary sulfonium salt, or a diazonium salt; : Sulfate, sulfonate, phosphate, phosphinate, phosphonate, etc.]; complex of Lewis acid with base [eg boron trifluoride. Aniline complex, boron trifluoride. p-Chloroaniline complex, boron trifluoride. Ethylamine complex, boron trifluoride. Isopropylamine complex, boron trifluoride. Benzylamine complex, boron trifluoride. Dimethylamine complex, boron trifluoride. Diethylamine complex, boron trifluoride. Dibutylamine complex, boron trifluoride. Piperidine complex, boron trifluoride. Dibenzylamine complex, three Boron chloride. Dimethyloctylamine complex, etc.]; an organic metal salt [stanny octoate, zinc octoate, dibutyltin dilaurate, acetone acetamidium complex, etc.] and the like.

In particular, the amount of the catalyst used when the non-aromatic amine compound is used as the amine compound (B) is not particularly limited, but is preferably less than 1 weight based on 100 parts by weight of the epoxy compound (A). Parts (for example, 0 parts by weight or more and less than 1 part by weight), more preferably less than 0.5 parts by weight, still more preferably less than 0.3 parts by weight. By using the catalyst in an amount of less than 1 part by weight, the -NH- group formed by the reaction of the epoxy compound (A) and the amine compound (B) can further inhibit the alicyclic formula with the epoxy compound (A). The epoxy group is reacted, and the blending of other components is more likely to occur, and a highly reactive epoxy-amine adduct tends to be obtained.

On the other hand, the amount of the catalyst used when the aromatic amine compound is used as the amine compound (B) is not particularly limited, but is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy compound (A). The parts by weight are more preferably 0.5 to 8 parts by weight, still more preferably 1 to 5 parts by weight. When the amount of the catalyst used is 0.1 part by weight or more, the reaction between the epoxy compound (A) and the amine compound (B) tends to proceed more efficiently. On the other hand, it is economically more advantageous to use the catalyst in an amount of 10 parts by weight or less.

The ratio of the epoxy compound (A) to the amine compound (B) subjected to the above reaction is not particularly limited, but the epoxy compound (A) in the above reaction has an alicyclic epoxy group (cyclohexenyloxy group ( The ratio of the cyclohexene oxide group)) to the amine group of the amine compound (B) [alicyclic epoxy group/amino group] is controlled at 0.05 to 1.00 (more preferably 0.10 to 0.95). More preferably, it is 0.15~0.90). When the ratio [alicyclic epoxy group/amine group] is 0.05 or more, it is difficult to leave the unreacted amine compound (B) in the epoxy group-amine adduct. On the other hand, when the ratio [alicyclic epoxy group/amine group] is 1.00 or less, it is difficult to leave the unreacted epoxy compound (A) in the epoxy group-amine adduct.

The temperature (reaction temperature) in the above reaction is not particularly limited, but is preferably from 30 to 250 ° C, more preferably from 80 to 200 ° C, still more preferably from 120 to 180 ° C. When the reaction temperature is 30° C. or more, a sufficient reaction rate is ensured and the productivity of the epoxy group-amine adduct is further improved. On the other hand, by setting the reaction temperature to 250 ° C or lower, the decomposition reaction of the epoxy compound (A) or the amine compound (B) is suppressed and the yield of the epoxy group-amine adduct is further improved. Further, in the above reaction, the reaction temperature may be controlled so as to be always fixed (substantially fixed), or may be controlled to be changed stepwise or continuously.

The time (reaction time) for carrying out the above reaction is not particularly limited, but is preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours, still more preferably 1 to 5 hours. When the reaction time is 0.2 hours or more, the yield of the epoxy group-amine adduct tends to be further improved. On the other hand, when the reaction time is 20 hours or less, the productivity of the epoxy-amine adduct tends to be further improved.

The above reaction can be carried out under any of normal pressure, under pressure and under reduced pressure. Further, the gas atmosphere for carrying out the above reaction is not particularly limited, and it can be carried out in a gas atmosphere of any of an inert gas (for example, nitrogen, argon, or the like) or air.

The above reactions are not particularly limited and may also be through batches. It is implemented in any of a mode (batch type), a semi-batch mode, and a continuous flow mode. For example, when the above reaction is carried out in a batch mode, other components such as an epoxy compound (A), an amine compound (B), and an optional solvent may be placed in a batch reactor, and Further, it is carried out by heating or stirring as needed.

The epoxy group-amine adduct of the present invention can be obtained by the above reaction (reaction of the epoxy compound (A) with the amine compound (B)). After the above reaction, the epoxy group-amine adduct of the present invention can be used, for example, by filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or the like, or a conventional separation means or combination thereof. Separation means for separation and purification.

The epoxy-amine adduct of the present invention is an alicyclic epoxy group of the epoxy compound (A) and an amine group of the amine compound (B) as described above (-NH ₂ ; an unsubstituted amine Based on the reaction. The epoxy group-amine adduct of the present invention is presumed to be an -NH- group (substituted amino group) which is produced by the reaction of the above alicyclic epoxy group with an amine group as shown in the formula (I). It has insufficient reactivity with the alicyclic epoxy group of the epoxy compound (A) and has a -NH- group in the molecule. The number of the -NH- group which the epoxy group-amine adduct of the present invention has in the molecule is not particularly limited, but is preferably from 1 to 200, more preferably from 1 to 150, still more preferably 2 ~100. When the epoxy group-amine adduct does not have a -NH- group, the reactivity may be lowered, or the effect of improving the adhesion of the resin and the reinforcing fiber in the fiber-reinforced composite material may not be sufficiently obtained depending on the use. . Further, the amount of the -NH- group in the epoxy group-amine adduct can be obtained, for example, by using a standard polystyrene-converted molecular weight measured by a gel permeation chromatography (GPC) method. The number of the epoxy compound (A) unit and the amine compound (B) unit constituting the epoxy group-amine adduct was calculated.

With respect to the above, for example, a compound obtained by a reaction of an epoxy compound having a glycidyl group with an amine compound (B) (epoxy-amine adduct), by epoxypropyl group and The -NH- group formed by the reaction of an amine group (unsubstituted amino group) has a very high reactivity with a glycidyl group, and therefore, in general, the -NH- group does not substantially remain.

The number average molecular weight of the epoxy group-amine adduct of the present invention is not particularly limited, but is preferably from 200 to 40,000, more preferably from 300 to 30,000, still more preferably from 400 to 20,000. When the number average molecular weight is 200 or more, the function as an epoxy group-amine adduct can be more effectively exhibited. On the other hand, when the number average molecular weight is 40,000 or less, the blending of other components or the preparation of the aqueous dispersion tends to be easier. Further, the number average molecular weight of the epoxy group-amine adduct can be calculated, for example, by using a standard polystyrene-equivalent molecular weight measured by a gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the epoxy-amine adduct of the present invention is not particularly limited, but is preferably -50 to 200 ° C, more preferably -40 to 190 ° C, still more preferably -30 °. 180 ° C. When the Tg of the epoxy group-amine adduct is -50 ° C or more, the heat resistance or mechanical properties (such as toughness) of the fiber-reinforced composite material tend to be further improved. On the other hand, when the Tg of the epoxy group-amine adduct is 200 ° C or less, the blending of other components or the preparation of the aqueous dispersion tends to be easier. Further, the glass transition temperature of the epoxy group-amine adduct can be measured by, for example, differential scanning calorimetry (DSC), dynamic viscoelasticity measurement, or the like.

Here, the epoxy-amine adduct of the present invention is obtained by using the compound represented by the formula (a-1) as the epoxy compound (A) and using the compound represented by the formula (b-1) and Either or both of the compounds represented by the formula (b-2) are used as the amine compound (B), and the epoxy group obtained by subjecting the epoxy compound (A) to the amine compound (B) is subjected to an addition reaction - Amine adducts are preferred.

For example, when the epoxy group-amine adduct of the present invention is used as the amine compound (B), the compound represented by the formula (b-1) is represented by the following formula (I-1). In the epoxy group-amine adduct of the present invention, when the compound represented by the formula (a-1) is used as the epoxy compound (A), the following may be mentioned. The epoxy group-amine adduct represented by the formula (I-2). Further, X in the following formula (I-1) and q in the following formula (I-2) each represent the same as X and q in the above formula (I). The p in the following formulas (I-1) and (I-2) represents an integer of 1 or more and is the same as p in the above formula (b-1). Further, R ² and R ³ in the following formulas (I-1) and (I-2) each represent a divalent linear, branched or cyclic aliphatic hydrocarbon group or a linear or branched chain. The divalent group formed by bonding one or more aliphatic aliphatic hydrocarbon groups to one or more of the cyclic aliphatic hydrocarbon groups is the same as R ² and R ³ in the above formula (b-1). Further, when p is an integer of 2 or more, each R ³ may be the same or different. Further, when two or more kinds of R ³ are present, the addition form (polymerization form) of the structure in the parentheses attached to p may be a random type or a block type. R ² and R ³ may be the same group or may be a different group.

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

[Surfactant]

As the surfactant in the water-dispersed resin composition of the present invention, a well-known surfactant can be used without particular limitation, and a well-known anionic surfactant and nonionic interfacial activity are exemplified. Agent, cationic surfactant, amphoteric surfactant, polymer dispersant, and the like. The surfactant mainly has a function of stably dispersing the epoxy group-amine adduct in the water-dispersed resin composition of the present invention.

Examples of the anionic surfactant include dodecylbenzenesulfonate, alkylenedisulfonate, sodium dialkylsulfosuccinate, disodium monoalkylsulfosuccinate, and naphthalene. a sulfonate type such as a sodium sulfonate condensate or an α-olefin sulfonate; a polyoxyethylene polycyclic phenyl ether sulfate Sulfate salt type such as ester salt, polyoxyethylene aryl ether sulfate salt, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene castor oil ether sulfate salt; phosphate ester type such as polyoxyalkylene alkyl ether phosphate ; sodium polyacrylate salt. In particular, the anionic surfactant is preferably a sulfate salt type surfactant, and specifically, the trade names "NEWCOL707SF", "NEWCOL707SFC", and "NEWCOL707SN" (the above are Japanese emulsifiers) Commercial products such as system).

For the anionic surfactant other than the above, for example, a reactive surfactant having a radically polymerizable polymerizable functional group can be used, and for example, a sulfate salt of a polyoxyethylene alkylphenyl ether can be mentioned. A surfactant having a radically polymerizable unsaturated double bond introduced into the molecule, and a surfactant having a radical polymerizable unsaturated double bond introduced into the molecule of the alkyl sulfosuccinate salt. Specifically, the former example includes "Aqualon KH-10" and "Aqualon HS-10" (the above is the first industrial pharmaceutical company); the product name "ADEKA REASOAP SE-10N" (ADEKA (share) system) and so on. In addition, examples of the latter include the brand names "ELEMINOL JS2" and "ELEMINOL RN-30" (the above are manufactured by Sanyo Chemical Industries Co., Ltd.); the trade names "LATEMUL S-180" and "LATEMUL S-180A". (The above is the Kao (share) system) and so on.

Examples of the nonionic surfactant include polyoxyethylene 2-ethylhexyl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene castor oil ether, and polyoxyethylene ten. Polyoxyalkylene alkyl ether type such as hexaether, polyoxyethylene stearyl ether, polyoxyalkylene 2-ethylhexyl ether, polyoxyalkylene decyl ether, polyoxyalkylene tridecyl ether; polyoxyethylene Polyoxyalkylene polycyclic phenyl ether type (polycyclic phenyl ether type) such as polycyclic phenyl ether; sorbitan laurate, sorbitan stearate, sorbitan oleate, go Sorbitan trioleate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene sorbitan Desorbed sorbitol derivatives such as oleate, polyoxyalkylene sorbitan fatty acid ester; polyoxyethylene aryl ether, polyoxyethylene cumene phenyl ether, polyoxyethylene polyoxypropylene block polymerization , polyoxyethylene oleate, polyoxyethylene alkylamine ether, alkylene oxide adduct of 2-butyl-2-ethyl-1,3-β-hydroxypropane, fatty acid decylamine derivative, diversified Alcohol derivatives and the like. Among them, a polyoxyalkylene alkyl ether type nonionic surfactant is preferable, and specifically, the trade names "NOIGEN EA-197D", "NOIGEN XL", "NOIGEN ET-B", and "NOIGEN TDS" can be used. (The above is the first industrial pharmaceutical (share) system) and so on.

The non-ionic surfactant other than the above may, for example, be a surfactant in which a radical polymerizable unsaturated double bond is introduced into a molecule of a polyoxyethylene alkylphenyl ether, and specifically, Listed the trade names "Aqualon RN-20" and "Aqualon RN-50" (above the first industrial pharmaceutical company); the trade names "ADEKA REASOAP NE-20" and "ADEKA REASOAP NE-40" (above ADEKA) (share) system, etc.

The cationic surfactant may, for example, be a tetramethylammonium salt (for example, tetramethylammonium chloride or tetramethylammonium hydroxide), an alkyltrimethylammonium salt or a dialkyldimethyl group. Alkyl ammonium salt, alkyl dimethyl benzyl ammonium salt, pyridinium salt, alkyl isoquinolinium salt, Grade 4 ammonium salt type such as positive soap (benzethonium chloride); alkylamine salt (eg monomethylamine hydrochloride, dimethylamine hydrochloride, etc.), amino alcohol fatty acid derivative, polyamine fatty acid derivative An amine salt type such as an imidazoline; a pyridinium cation such as a butylpyridine cation or a dodecylpyridine cation; and the like.

Examples of the amphoteric surfactant include alanine, dodecyl bis(aminoethyl)glycine, bis(octylaminoethyl)glycine, and N-alkyl-N. N-dimethylammonium betaine and the like.

Further, examples of the polymer dispersant include polyvinyl alcohol, polyvinylpyrrolidone, and maleic acid copolymer (ethyl vinyl ether-maleic acid copolymer, styrene-butylene) Diacid copolymers, etc.) and various metal or ammonium salts thereof, acrylic polymers (polyacrylic acid, copolymers of acrylic acid, etc.) and various metal or ammonium salts thereof, maleic acid monoester copolymers, acrylonitrile groups Methylpropanesulfonic acid copolymer, polyester system, CMC (carboxymethyl cellulose), HEC (hydroxyethyl cellulose), hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl starch, algae Acid, pectic acid, etc.

In the water-dispersible resin composition of the present invention, the surfactant may be used singly or in combination of two or more. Among them, an anionic surfactant and a nonionic surfactant are preferred, and a combination of an anionic surfactant and a nonionic surfactant is particularly preferred.

The content (mixing amount) of the surfactant in the water-dispersed resin composition of the present invention is not particularly limited, but it is preferably 100 parts by weight based on 100 parts by weight of the epoxy-amine adduct of the present invention. 0.01 to 500 parts by weight, more preferably 0.1 to 200 parts by weight, still more preferably 0.5 to 100 parts by weight . When the content of the surfactant is 0.01 parts by weight or more, the epoxy group-amine adduct can be more stably dispersed. On the other hand, by setting the content of the surfactant to 500 parts by weight or less, it is economically advantageous and the heat resistance or mechanical properties of the fiber-reinforced composite material tend to be maintained at a higher level.

When an anionic surfactant and a nonionic surfactant are used in combination as a surfactant, the ratio of the amount of these surfactants used [anionic surfactant/nonionic surfactant] (weight ratio) There is no particular limitation, but it is preferably 90/10~10/90, more preferably 70/30~30/70, and even more preferably 60/40~30/70.

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 be a composition containing only water as an aqueous medium, or may be a composition containing water and an organic solvent. The organic solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Hydrocarbon; halogenated hydrocarbon such as chloroform, dichloromethane, 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, Ethers such as alkane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; N, N-dimethyl A guanamine such as methotrexate or N,N-dimethylacetamide; a nitrile such as acetonitrile, propionitrile or benzonitrile; an alcohol such as methanol, ethanol, isopropanol or butanol; and dimethyl hydrazine. Further, the organic solvent may be used singly or in combination of two or more. Among them, an organic solvent which can be mixed with water, such as guanamine, alcohol or dimethyl hydrazine, is preferred.

The water-dispersible resin composition of the present invention preferably has a small content of an organic solvent from the viewpoint of ensuring work safety or environmental protection. The content (mixing amount) of the organic solvent in the water-dispersed resin composition of the present invention is not particularly limited, but is preferably 10% by weight or less based on the total amount (100% by weight) of the resin composition. (for example, 0 to 10% by weight), 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 components (may be referred to as "other components"). Examples of the other components include various additives such as a lubricant such as a fatty acid, a guanamine or an ester, and a coupling agent such as a decane coupling agent or a titanium coupling agent.

The water-dispersed resin composition of the present invention can be prepared (manufactured) by a conventionally known method, and is not particularly limited, and, for example, by the epoxy group-amine adduct of the present invention, The surfactant and the aqueous medium are mixed with other components which are further added as needed, and the epoxy group-amine adduct is dispersed (for example, suspended dispersion, emulsified and dispersed) in an aqueous medium. The order of addition of the various components at the time of mixing is not particularly limited. Specifically, for example, it can be pulverized by using a disper, a homomixer, a bead mill, a jet mill, a roll mill, a hammer mill, a vibration mill, a ball mill, a sand mill, and a pearl. A disperser (especially a media agitation type disperser) such as a pearl mill, a spike mill, a stirring mill, or a coball mill will contain Mixture of epoxy-amine adducts, surfactants and mixtures of aqueous media The water-dispersed resin composition of the present invention is prepared. In addition, in order to reduce the content of the organic solvent in the water-dispersed resin composition of the present invention, treatment such as drying under reduced pressure may be further carried out.

[prepreg]

Since the water-dispersible resin composition of the present invention contains the epoxy-amine adduct of the present invention, it has high reactivity with functional groups such as a hydroxyl group, a carboxyl group or an epoxy group which are present on the surface of the reinforcing fiber, and can be used for fiber strengthening. The adhesion of the resin in the composite material to the reinforcing fibers (especially glass fibers or carbon fibers) is more effectively enhanced. Moreover, since the water-dispersible resin composition of the present invention has a form of a water-dispersible resin composition (aqueous dispersion), it is easy to apply or impregnate the reinforcing fibers. Therefore, the water-dispersible 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). Further, the sizing agent means impregnation or coating (coating) on the reinforcing fibers in order to improve the workability in the manufacturing step of the reinforcing fibers or the high-order processing steps (fabric step, prepreg step, other forming step). Treatment agents, sometimes referred to as sizing agents.

By using the water-dispersed resin composition of the present invention as a sizing agent and impregnating or coating the resin composition on the reinforcing fibers, a prepreg of a precursor material of the fiber-reinforced composite material is obtained (sometimes referred to as " Prepreg of the invention").

As the reinforcing fiber, a known reinforcing fiber can be used without any particular limitation, and examples thereof include carbon fiber, glass fiber, aramid fiber, boron fiber, graphite fiber, and cerium carbide fiber. , high-strength polyethylene fiber, tungsten carbide fiber, poly-p-phenylene benzoate Oxazole fiber (PBO fiber) and the like. Examples of the carbon fibers include polyacrylonitrile (PAN)-based carbon fibers, pitch-based carbon fibers, and vapor-grown carbon fibers. Among them, carbon fibers, glass fibers, and polyarsenamide fibers are preferred from the viewpoint of mechanical properties (such as toughness). Further, the reinforcing fibers may be used singly or in combination of two or more.

Further, the reinforcing fiber may be a surface treatment which is known to be conventionally used, such as a coupling treatment, an oxidation treatment, and a coating treatment.

The form of the reinforcing fiber is not particularly limited, and examples thereof include a form of a fiber (long fiber), a form of a fiber bundle, a form of a unidirectional material in which a fiber bundle is arranged in a unidirectional manner, a form of a woven fabric, and a form of a non-woven fabric. Wait. The fabric of the reinforced fiber may, for example, be a plain weave, a twill weave, a satin weave, or a sheet obtained by arranging a bundle of fibers represented by a non-curved fabric in a unidirectional manner or for laminating if the angle is changed. A stitching sheet obtained by sewing a sheet without being loosened.

The content of the reinforcing fibers in the prepreg of the present invention is not particularly limited and can be appropriately adjusted.

The method of producing the prepreg of the present invention by impregnating or coating the water-dispersed resin composition of the present invention on reinforcing fibers is not particularly limited, and it may be impregnated or coated in a method for producing a conventional prepreg which is conventionally used. The method is implemented. 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 roll to which the water-dispersible resin composition of the present invention adheres, and the water of the present invention The dispersed resin composition is formed into a mist and A method of spraying on a reinforcing fiber is known to a conventional method. Further, the coating system of the water-dispersed resin composition of the present invention may be applied to the entire surface of the reinforcing fiber or may be applied to a part of the surface. Further, the coating thickness, the coating amount, and the impregnation amount may be appropriately adjusted, and are not particularly limited.

The prepreg of the present invention may be a prepreg obtained by impregnating or applying the water-dispersed resin composition of the present invention to a reinforcing fiber, optionally after heat treatment. The conditions of the above heat treatment are not particularly limited, but the heating temperature is preferably from 40 to 300 ° C, more preferably from 60 to 250 ° C. Further, the heating time can be appropriately adjusted depending on the heating temperature, and is not particularly limited, but is preferably from 1 second to 60 minutes, more preferably from 5 seconds to 10 minutes. In the above heat treatment, the heating temperature may be fixed or may be changed continuously or in stages. Further, the heat treatment may be continuously performed in one stage or intermittently in two or more stages. In addition, the heat treatment may be carried out, for example, in order to promote impregnation of the reinforcing fibers with the epoxy-amine adduct water-dispersible resin composition, and to dry and remove volatile components (aqueous medium or the like). The above heat treatment can be carried out by a conventionally known method (for example, heating using a hot air oven or the like).

The prepreg of the present invention may be obtained by impregnating or coating a water-dispersible resin composition of the present invention with a reinforcing fiber, and further applying a resin such as a thermoplastic resin or a curable resin or a precursor thereof (sometimes referred to as " Resin, etc."). As a result, the viscosity of the prepreg of the present invention is lowered and the workability (handleability) is further improved depending on the type of the resin or the like. The above coating method is not particularly limited, and for example, the water-dispersible resin composition of the present invention can be applied to the reinforcement. The method of the fiber is carried out in the same manner. Further, the above coating may be performed on the entire surface of the prepreg (uncoated resin or the like) or on a part of the surface. Further, the coating thickness or the coating amount can be appropriately adjusted, and is not particularly limited.

The resin or the like is not particularly limited, and examples thereof include polyolefin (for example, polyethylene, polypropylene, polybutadiene, etc.) and ethylene-based polymers (for example, acrylic resin, polystyrene, etc.). ), polyamine (for example: nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 61, nylon 6T, nylon 9T, etc.), polyester (for example) : polyethylene terephthalate, polybutylene terephthalate), polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyacetal, polyphenylene ether, polyphenylene sulfide, polyether oxime, A thermoplastic resin such as polyetheretherketone; an epoxy resin, an unsaturated polyester, a vinyl ester resin, an allyl resin (for example, a diallyl phthalate resin, etc.), a phenol resin, a polyimine, and a cyanate ester ( Cyanate) a curable resin (curable compound) such as a resin, a maleimide resin, a urea resin, a melamine resin, or a polysiloxane resin [for example, a thermosetting resin (thermosetting compound), a photocurable resin) (photocurable compound), etc.]. In addition, one type of resin may be used alone or two or more types may be used in combination.

Among them, a thermoplastic resin is used as a prepreg of the above resin, that is, a thermoplastic prepreg, in particular, compared to a curable prepreg (for example, a thermosetting prepreg or a photocurable prepreg). The advantage of being able to form in a short time. Therefore, the above-mentioned thermoplastic prepreg can be particularly suitably used for applications requiring a shortened travel time (for example, for automobile parts and the like).

The content (doping amount) of the above-mentioned resin or the like in the prepreg of the present invention is not particularly limited, but is preferably 0.1% with respect to the total amount (100% by weight) of the prepreg excluding the reinforcing fibers. 99.9% by weight, more preferably 1 to 99% by weight, still more preferably 2 to 98% by weight. When the content is 0.1% by weight or more, the heat resistance or mechanical properties (such as toughness) of the fiber-reinforced composite material tend to be further improved. On the other hand, when the content is 99.9% by weight or less, the adhesion between the resin and the reinforcing fibers in the fiber-reinforced composite material tends to be further improved.

The content (doping amount) of the epoxy group-amine adduct of the present invention in the prepreg of the present invention is not particularly limited, but is preferably 0.1 to 200 with respect to 100 parts by weight of the above resin or the like. The parts by weight are more preferably 1 to 100 parts by weight, still more preferably 2 to 50 parts by weight. When the content of the epoxy group-amine adduct of the present invention is 0.1 part by weight or more, the adhesion between the resin and the reinforcing fiber in the fiber-reinforced composite material tends to be further improved. On the other hand, when the content of the epoxy group-amine adduct of the present invention is 200 parts by weight or less, the heat resistance or mechanical properties (toughness, etc.) of the fiber-reinforced composite material can be ensured at a higher level. tendency.

The prepreg of the present invention may contain other, for example, a polymerization initiator (thermal polymerization initiator, photopolymerization initiator, etc.), a hardener, a hardening accelerator, an antifoaming agent, a leveling agent, a coupling agent (decane). Coupling agents, etc., surfactants, inorganic fillers (vermiculite, alumina, etc.), flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, release agents, etc. Additives. The amount of such additives is not particularly limited.

Also, the prepreg of the present invention is a curable prepreg In this case, the prepreg may be formed by hardening (i.e., semi-hardening) a part of the curable resin by heating or active energy ray irradiation.

A fiber-reinforced composite material (sometimes referred to as "the fiber-reinforced composite material of the present invention") can be formed from the prepreg of the present invention. More specifically, for example, when the prepreg of the present invention is a thermoplastic prepreg, the fiber reinforced composite material can be produced by molding the prepreg. On the other hand, for example, when the prepreg of the present invention is a curable prepreg, the fiber-reinforced composite material can be produced by curing and molding the curable resin in the prepreg.

[Fiber reinforced composite material]

The fiber-reinforced composite material of the present invention is formed from the prepreg of the present invention as described above, and the production method thereof is not particularly limited, but can be carried out by a conventionally known method such as a manual coating method or a prepreg method. , RTM method, pultrusion method, wire-wound method, spray up method, pultrusion method, etc. The fiber-reinforced composite material-based resin of the present invention is excellent in adhesion to reinforcing fibers and has high mechanical properties (especially toughness).

The fiber reinforced composite material of the present invention can be used as a material of various structures, and is not particularly limited, but for example, it can be preferably used as an airframe structure of an aircraft, a main wing, a empennage, a rotating blade, a fairing, and an engine. Cowl, door, etc.; motor shell, main wing, etc.; main structure of artificial satellite; automobile parts such as chassis of automobile; body structure of railway vehicle; body structure of bicycle; hull structure of ship; Blade; pressurized container; fishing rod; tennis racket; golf club shaft; mechanical arm; cable (eg cable core) Materials such as materials, etc.).

[Examples]

The invention is illustrated in more detail below on the basis of the examples, but the invention is not limited by the examples.

Manufacturing example 1

[Manufacture of epoxy-amine adduct (Amine Adduct D230)]

3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate (trade name "CELLOXIDE 2021P", manufactured by DAICEL Co., Ltd.) 30.0 parts by weight and amine-terminated polypropylene glycol (commercial product) 35.9 parts by weight of "JEFFAMINE D-230", manufactured by HUNTSMAN Co., Ltd., and then reacted at 160 ° C for 2 hours to produce an epoxy-amine adduct (sometimes called "Amine Adduct" D230").

Fig. 3 is a graph showing the ¹ H-NMR spectrum of the obtained epoxy-amine adduct.

Manufacturing Example 2

[Manufacture of epoxy-amine adduct (Amine Adduct IPD)]

3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexanecarboxylate (trade name "CELLOXIDE 2021P", manufactured by DAICEL Co., Ltd.), 30.0 parts by weight, and amine-terminated polypropylene glycol (commercial product) 18.0 parts by weight of "JEFFAMINE D-230", manufactured by HUNTSMAN Co., Ltd., and 18.0 parts by weight of isophorone diamine (trade name "VESTAMIN IPD", manufactured by EVONIK Co., Ltd.), and then stirred at 160 ° C for 2 hours. The reaction is followed by the production of an epoxy-amine adduct (sometimes referred to as "Amine Adduct IPD").

Example 1

70 parts by weight relative to the epoxy-amine adduct obtained in Production Example 1. In addition, 30 parts by weight of a product name "NEWCOL170" (manufactured by a surfactant, a Japanese emulsifier, and an active ingredient: 100% by weight) was placed and dissolved. Next, 300 parts by weight of deionized water was added dropwise under stirring for 10 minutes, and after the completion of the dropwise addition, the mixture was forcedly emulsified at 10,000 rpm for 1 minute using a homomixer to obtain an epoxy-amine adduct water-dispersed type. Resin composition. Next, the organic solvent contained in the water-dispersed resin composition was removed under reduced pressure to obtain a solid content weight of 15% and a viscosity of 30 mPa. The epoxy group-amine adduct water-dispersed resin composition (aqueous dispersion of epoxy-amine adduct) which is the target of pH 9.2.

Example 2

With respect to 70 parts by weight of the epoxy-amine adduct obtained in Production Example 2, the product name "NEWCOL780SF" (manufactured by a surfactant, a Japanese emulsifier, and an active ingredient: 30% by weight) was placed in an amount of 100% by weight. Make it dissolve. Next, 300 parts by weight of deionized water was added dropwise under stirring for 10 minutes, and after the completion of the dropwise addition, the mixture was forced-emulsified at 10,000 rpm for 1 hour using a homomixer to obtain an epoxy-amine adduct water-dispersed type. Resin composition. Next, the organic solvent contained in the water-dispersed resin composition was removed under reduced pressure to obtain a solid content weight of 14% and a viscosity of 10 mPa. An epoxy-amine adduct water-dispersible resin composition (aqueous dispersion of an epoxy-amine adduct) which is the target of pH 9.0.

Comparative example 1

The same operation as in Example 1 was carried out except that an alicyclic epoxy resin (trade name "CELLOXIDE 2021P", manufactured by DAICEL Co., Ltd.) was used instead of the epoxy-amine adduct (Amine Adduct D230). As a result, the alicyclic epoxy resin cannot be stably dispersed in water, and moisture cannot be obtained. Bulk resin composition.

Comparative example 2

The same operation as in Example 2 was carried out, except that an alicyclic epoxy resin (trade name "CELLOXIDE 2021P", manufactured by DAICEL Co., Ltd.) was used instead of the epoxy-amine adduct (Amine Adduct IPD). As a result, the alicyclic epoxy resin could not be stably dispersed in water, and the water-dispersed resin composition could not be obtained.

[assessment test]

The water-dispersed resin composition obtained in the examples was diluted with water so that the nonvolatile component became about 2% by weight to obtain a sizing agent. This sizing agent was applied onto the carbon fibers previously removed by acetone using a dipping method, and then heat-treated at a temperature of 210 ° C for 90 seconds. Then, it was immersed in a bisphenol A type epoxy resin (trade name "EPOTORT YD128", manufactured by Nippon Steel Chemical Co., Ltd.), and taken out at 100 ° C for 30 minutes to obtain a non-sticky carbon fiber bundle (pre-impregnation). ()).

[Industrial availability]

Since the epoxy-amine adduct water-dispersed resin composition of the present invention contains the above epoxy group-amine adduct, it is reactive with functional groups such as a hydroxyl group, a carboxyl group or an epoxy group which are present on the surface of the reinforcing fiber. High, it can effectively improve the adhesion of the resin and the reinforcing fiber in the fiber-reinforced composite material. In particular, the epoxy-amine adduct water-dispersible resin composition of the present invention can broadly exhibit a good adhesion to the reinforcing fibers of the resin even when a matrix resin is used. ,very useful. Further, since it is in the form of a water-dispersed resin composition, impregnation or coating of the reinforced resin can be easily performed. Again The epoxy-amine adduct water-dispersible resin composition of the present invention can be used without a working environment by preparing a water-dispersed resin composition (aqueous dispersion) which does not contain an organic solvent or has a small content. It is used underneath and is also environmentally friendly. Therefore, when the epoxy-amine adduct water-dispersible resin composition of the present invention is used, it is possible to obtain a prepreg of a fiber-reinforced composite material which is excellent in adhesion between a resin and a reinforcing fiber by excellent productivity. Further, by using the above prepreg, it is possible to obtain a fiber-reinforced composite material which is excellent in adhesion between a resin and a reinforcing fiber and has high mechanical properties (especially toughness).

Claims (6)

An epoxy-amine adduct water-dispersible resin composition characterized by containing an epoxy-amine adduct represented by the following formula (I) and a surfactant, and the epoxy-amine addition Disperse in an aqueous medium, In the formula (I), R ¹ is the same or different, and represents a divalent organic group having a carbon atom at a bonding position to a nitrogen atom represented by the formula, and X represents a single bond or has one or more atoms. The divalent group and q represent an integer of 1 or more. The epoxy-amine adduct water-dispersible resin composition of claim 1, wherein the surfactant is at least one selected from the group consisting of an anionic surfactant and a nonionic surfactant. Active agent. A method for producing an epoxy group-amine adduct water-dispersed resin composition, which comprises an epoxy group-amine adduct represented by the following formula (I) and a surfactant, and the epoxy group-amine A method for dispersing an adduct of an epoxy-amine adduct water-dispersible resin composition in an aqueous medium, characterized in that the epoxy-amine adduct, a surfactant, and an aqueous medium are mixed. In the formula (I), R ¹ is the same or different, and represents a divalent organic group having a carbon atom at a bonding position to a nitrogen atom represented by the formula, and X represents a single bond or has one or more atoms. The divalent group and q represent an integer of 1 or more. The method for producing an epoxy group-amine adduct water-dispersed resin composition according to claim 3, wherein the surfactant is selected from the group consisting of an anionic surfactant and a nonionic surfactant. At least one surfactant. A prepreg obtained by impregnating or coating a epoxy-amine adduct water-dispersed resin composition of claim 1 or 2 with a reinforcing fiber. A fiber reinforced composite material comprising a fiber reinforced composite material formed from the prepreg of claim 5.