TW201905021A - Epoxy-amine adduct, thermoplastic resin composition, sizing agent, sizing agent-coated carbon fibers, and fiber-reinforced composite material - Google Patents

Abstract

The purpose of the present invention is to provide a compound which is capable of forming a polymer composite (such as a fiber-reinforced composite material) having excellent mechanical properties (especially, toughness), while being easily blended with other components such as resins, and which is also capable of improving adhesion between a resin and an additive in the polymer composite. The present invention provides an epoxy-amine adduct which is a compound [I] having two or more amino groups in each molecule or a salt thereof, and which has amino groups at both ends. The compound [I] is an adduct of an epoxy compound (A) that has two or more alicyclic epoxy groups in each molecule and an amine compound (B) that has two or more amino groups in each molecule; the epoxy compound (A) contains a compound of formula (a); and the amine compound (B) contains at least one compound selected from among compounds of formula (b-I) and at least one compound selected from among compounds of formula (b-II). R1a(NH2)2 (b-I) R1b(NH2)2 (b-II).

Description

 Epoxy-amine adduct, thermoplastic resin composition, sizing agent, carbon fiber coated with sizing agent, and fiber reinforced composite material  

The present invention relates to an epoxy-amine adduct, a thermoplastic resin composition containing the epoxy-amine adduct, and a fiber formed by impregnating or coating the thermoplastic resin composition with a prepreg obtained by reinforcing the fiber. Reinforced composites. The present application claims priority to Japanese Patent Application No. 2017-113036, filed on Jan. 7,,,,,,,,

Conventionally, an epoxy-amine adduct (referred to as an "amine adduct") which is produced by reacting an amine compound with an epoxy compound is known. As the amine adduct, for example, an addition compound obtained by reacting a dialkylamine with an epoxy resin having a glycidyl group disclosed in Patent Document 1 and Patent Document 2, and a surface of the addition compound powder A neutralized treatment using an acidic substance. Further, Patent Document 3 discloses that, for example, an amine compound having an amine group and an N,N-dialkylamine group and an epoxy resin having an average of more than one epoxy group in the molecule are reacted in a specific ratio. And get the epoxy-amine adduct. Further, Patent Document 4 and Patent Document 5 disclose an amine adduct obtained by reacting an aliphatic diamine with an epoxy resin having an alicyclic epoxy group.

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 56-155222

Patent Document 2 Japanese Patent Laid-Open No. 57-100127

Patent Document 3 Japanese Patent Laid-Open No. 61-228018

Patent Document 4 International Publication WO2013/172200

Patent Document 5 International Publication WO2013/172199

Patent Documents 1 to 3 describe the use of the above amine adduct as a curing agent (latent curing agent) for an epoxy resin. However, since the above-mentioned amine adduct has the possibility of exhibiting various properties by the selection of the amine compound and the epoxy compound of the raw material, it is not limited to the above-mentioned curing agent, and it is expected to be used for various other purposes. Be applicable. Specifically, in order to utilize the reactivity of the above-mentioned amine adduct, for example, it is expected to use an adhesion improver which is used as an adhesion between a reinforcing material such as a reinforcing fiber or a filler in a polymer-based composite and a resin. The polymer-based composite is a composite material of a reinforcing fiber and a resin (fiber-reinforced composite material) such as carbon fiber, or a nano-composite filler in which a nano-sized filler such as talc, kaolin or layered niobate is dispersed in a resin. Things and so on. In addition, it is also expected to use, as an adhesive, a paint, or the like, or as an adhesive improver for improving the adhesion of the adhesive or the like to the adherend.

However, the amine adducts disclosed in Patent Documents 1 to 3 have no active hydrogen such as a hydrogen atom directly bonded to a nitrogen atom, or the active hydrogen is a compound (for example, an inorganic acid, an organic acid, or a phenol). In the case of being used as an adhesion improver in a polymer-based composite, it is difficult to sufficiently obtain the effect of improving the adhesion between the resin and the additive.

In addition, when the above-mentioned amine adduct is used as an additive to other materials (for example, a curable resin such as a thermoplastic resin or an epoxy compound), it is required to be easily blended with other materials. However, for example, an adduct of an epoxy compound having a glycidyl group and a polyamine compound, such as bisphenol A diglycidyl ether known as an amine adduct, has a crosslinked structure and is heated. It does not soften or melt, and uniform blending of other materials is difficult.

The amine adducts described in Patent Documents 4 and 5 have the disadvantages of the amine adducts of Patent Documents 1 to 3, and have high reactivity with functional groups such as a hydroxyl group, a carboxyl group, and an epoxy group present on the surface of the reinforcing fiber. The adhesion between the resin and the reinforced fiber in the fiber-reinforced composite material can be effectively improved. Further, it is described that it can be softened or melted by heating, or is excellent in solubility to a solvent or a resin. Other ingredients can be easily blended.

However, the amine adducts described in Patent Documents 4 and 5 have a problem that they are brittle and have insufficient strength and toughness.

When the amine adduct is used as an adhesive or a sizing agent or the like, it is required to be strong in order to exhibit excellent adhesion or to exhibit sufficient converging properties. If it is brittle itself, it will not be able to exhibit the desired characteristics as an adhesive or the like, or it may cause problems such as contamination due to fragments generated by crushing. Further, in the case of use as an additive, there is a concern that the properties (e.g., mechanical properties, etc.) of the polymer-based composite are lowered.

In addition, as the above-mentioned amine adduct, it is preferably excellent in solubility (water solubility) in water in order to be used in the form of an aqueous solution or an aqueous dispersion from the viewpoint of environmental protection and safety of the working environment. By. For example, those which are excellent in water solubility can be suitably used as a product (for example, an aqueous paint (water-soluble paint)) which uses water or a solvent containing water as a main component. Further, the amine adduct is required to have excellent heat resistance which can be withstood even when the above polymer-based composite is processed at a high temperature; in order to prevent adhesion to a processing machine or the like. The contamination has a glass transition temperature as high as a certain degree (for example, a glass transition temperature above room temperature, etc.).

Therefore, an object of the present invention is to provide a compound (epoxy-amine adduct) which can improve the adhesion of a resin in a polymer-based composite (fiber-reinforced composite material, etc.) to an additive (reinforcing fiber or the like). It is easy to blend other components such as a resin, and it is possible to form a polymer-based composite (fiber-reinforced composite material or the like) excellent in mechanical properties (especially, toughness).

Further, another object of the present invention is to provide a compound (epoxy-amine adduct) which is excellent in reactivity, excellent in heat resistance, excellent in water solubility, and has a glass transition temperature as high as a certain degree. More than one feature.

Further, another object of the present invention is to provide a thermoplastic resin composition which is highly reactive and can form a polymer composite having excellent adhesion between a thermoplastic resin and an additive and mechanical properties (especially toughness). .

Further, another object of the present invention is to provide a sizing agent which can improve the high-order workability of carbon fibers, and can improve the adhesion of carbon fibers to a matrix resin, and can form a fiber reinforced composite excellent in mechanical properties (especially toughness). material.

Furthermore, another object of the present invention is to provide a sizing agent-coated carbon fiber which is excellent in high-order workability, excellent in adhesion between carbon fibers and a matrix resin, and a fiber-reinforced composite material which contains the coating. The carbon fiber of the sizing agent is excellent in mechanical properties (especially toughness).

Furthermore, another object of the present invention is to provide a water-dispersed resin composition capable of improving the adhesion and mechanical properties of a thermoplastic resin and a reinforcing fiber in a fiber-reinforced composite material, and a method for producing the same ( Especially strong toughness), and especially used as a sizing agent.

Further, another object of the present invention is to provide a prepreg which can form a fiber-reinforced composite material excellent in adhesion between a thermoplastic resin and a reinforcing fiber and mechanical properties (especially, toughness).

Further, another object of the present invention is to provide a fiber-reinforced composite material which is excellent in adhesion between a thermoplastic resin and a reinforcing fiber and has high mechanical properties (especially toughness).

As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy-amine adduct obtained by reacting a specific epoxy compound, a specific aliphatic amine compound, and a specific aromatic amine compound in combination is used. The adhesion between the resin in the polymer composite (such as a fiber-reinforced composite material) and the additive (such as a reinforcing fiber) can be improved, and the blending of other components such as a resin can be facilitated, and mechanical properties can be formed (especially The present invention has been completed by a polymer-based composite (fiber-reinforced composite material or the like) excellent in toughness.

That is, the present invention provides an epoxy-amine adduct selected from the group consisting of a compound [I] having a molecular group having two or more amine groups in the molecule, and a salt of the compound [I]. The 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 amine groups in the molecule. The epoxy compound (A) contains a compound represented by the following formula (a), and the amine compound (B) contains at least one compound selected from the group consisting of the following formula (bI), and is selected from the following formula (b-). At least one of the compounds shown in II), and the epoxy-amine addition product is a compound having an amine group at both terminals.

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

R ^1a (NH ₂ ) ₂ (bI)

[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 through a linking group containing a hetero atom

(b) a divalent group in which a divalent linear or branched aliphatic hydrocarbon group is directly bonded to a divalent cyclic aliphatic hydrocarbon group]

R ^1b (NH ₂ ) ₂ (b-II)

[wherein R ^1b represents a divalent group selected from the group consisting of the following (c) to (g).

(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 is directly bonded to a divalent linear or branched aliphatic hydrocarbon group

(e) a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring.

(f) a divalent group and a divalent linear chain obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. Or a divalent group directly bonded to a branched aliphatic hydrocarbon group

(g) a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons having 6 to 12 carbon atoms through a group bonded to a linking group]

In the above epoxy-amine addition product, the compound represented by the above formula (bI) may be a compound selected from the group consisting of the compound represented by the following formula (b-1) and the compound represented by the following formula (b-2). And at least one group of the compounds represented by the following formula (b-3).

[wherein R ² and R ³ represent the same or different divalent linear or branched aliphatic hydrocarbons. q represents an integer of 1 or more. ]

[wherein R ⁴ and R ⁵ are the same or different and represent a divalent linear or branched aliphatic hydrocarbon. r represents an integer of 1 or more. ]

[wherein R ⁶ and R ⁸ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. s means 0 or 1. R ⁷ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. t represents an integer from 0 to 10. ]

In the above epoxy-amine adduct, the compound represented by the above formula (b-II) may be selected from the group consisting of a compound represented by the following formula (b-5) and represented by the following formula (b-6). At least one of the group of the compound and the compound represented by the following formula (b-7).

[In the formula, A ¹ represents an aromatic hydrocarbon having 6 to 12 carbon atoms. R ¹¹ and R ¹³ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. R ¹² represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. W1 and w3 are the same or differently representing 0 or 1. W2 represents an integer from 0 to 4. ]

[wherein, B ¹ represents an aromatic heterocyclic ring having 1 or 2 hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. R ¹⁴ and R ¹⁶ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. 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. X1 and x3 are the same or differently representing 0 or 1. X2 represents an integer from 0 to 4. ]

[In the formula, A ² and A ³ represent the same or different aromatic hydrocarbons having 6 to 12 carbon atoms. Y ¹ represents a linking group. R ¹⁷ and R ¹⁸ are the same or different and each represent a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. Y1 and y2 represent the same or different integers from 0 to 4. ]

In the epoxy-amine addition product, the compound [I] having two or more amine groups in the molecule may be a compound having two or more amine groups in the molecule represented by the following (I).

Wherein R ^{1 '} is a divalent organic group having a carbon atom at a bonding site to a nitrogen atom represented by the formula, and at least one is selected from the group consisting of the following (a) and (b) At least one divalent group, and at least one other represents at least one divalent group selected from the group consisting of the following (c) to (g). X represents a single bond or a divalent group having one or more atoms. z represents an integer of 1 or more.

(a) a divalent group in which two or more divalent linear or branched aliphatic hydrocarbons are bonded through a linking group containing a hetero atom

(b) a divalent group directly bonded to a divalent linear or branched aliphatic hydrocarbon group and a divalent cyclic aliphatic hydrocarbon group

(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 is directly bonded to a divalent linear or branched aliphatic hydrocarbon group

(e) a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring.

(f) a divalent group and a divalent linear chain obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. Or a divalent group directly bonded to a branched aliphatic hydrocarbon group

(g) A divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons having 6 to 12 carbon atoms through a group bonded to a linking group.

In the above epoxy-amine addition product, the divalent group of the above (a) may be a divalent group represented by the following formula (II) or a divalent group represented by the following formula (III), and the above (b) The divalent group of the formula may be a divalent group represented by the following formula (IV).

[wherein R ² and R ³ represent the same or different divalent linear or branched aliphatic hydrocarbons. q represents an integer of 1 or more. ]

[wherein R ⁴ and R ⁵ are the same or different and represent a divalent linear or branched aliphatic hydrocarbon. r represents an integer of 1 or more. ]

[wherein R ⁶ and R ⁸ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. s means 0 or 1. R ⁷ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. t represents an integer from 0 to 10. ]

In the above epoxy-amine addition product, the divalent group of the above (c) or the divalent group of the above (d) may be a divalent group represented by the following formula (V), and the divalent group of the above (e) The divalent group of the group (f) may be a divalent group represented by the following formula (VI), and the divalent group of the above (g) may be a divalent group represented by the following formula (VII).

[In the formula, A ¹ represents an aromatic hydrocarbon having 6 to 12 carbon atoms. R ¹¹ and R ¹³ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. R ¹² represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. W1 and w3 are the same or differently representing 0 or 1. W2 represents an integer from 0 to 4. ]

[wherein, B ¹ represents an aromatic heterocyclic ring having 1 or 2 hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. R ¹⁴ and R ¹⁶ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. 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. X1 and x3 are the same or differently representing 0 or 1. X2 represents an integer from 0 to 4. ]

[In the formula, A ² and A ³ represent the same or different aromatic hydrocarbons having 6 to 12 carbon atoms. Y ¹ represents a group of a linking group. R ¹⁷ and R ¹⁸ are the same or different and each represent a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. Y1 and y2 represent the same or different integers from 0 to 4. ]

The epoxy-amine adduct may be a salt of the compound [I] having two or more amine groups in the molecule, and may be a salt of the compound [I] and the acid [II].

The aforementioned epoxy-amine adduct may be a carbonate or an organic acid salt.

Further, the present invention provides a thermoplastic resin composition comprising the aforementioned epoxy-amine adduct and a thermoplastic resin.

The thermoplastic resin composition may be a resin composition for a fiber-reinforced composite material.

Further, the present invention provides an aqueous coating comprising the aforementioned epoxy-amine adduct.

Further, the present invention provides an aqueous solution containing the aforementioned epoxy-amine adduct.

Moreover, the present invention provides a water-dispersed resin composition containing the above-described epoxy-amine adduct and a urethane resin.

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

In the water-dispersible resin composition, the surfactant may be at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant.

Moreover, the present invention provides a method for producing a water-dispersed resin composition, which comprises mixing an aqueous dispersion containing the epoxy-amine adduct with an urethane resin emulsion.

In the method for producing a water-dispersible resin composition, the aqueous dispersion containing the epoxy-amine adduct may contain a surfactant.

In the method for producing a water-dispersible resin composition, the surfactant may be at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant.

Further, the present invention provides a sizing agent for carbon fibers containing the aforementioned epoxy-amine adduct.

Furthermore, the present invention provides an aqueous coating comprising the aforementioned sizing agent for carbon fibers.

Further, the present invention provides an aqueous solution containing the aforementioned sizing agent for carbon fibers.

Furthermore, the present invention provides a water-dispersed resin composition comprising the above-mentioned sizing agent for carbon fibers and a urethane resin.

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

In the water-dispersible resin composition, the surfactant may be at least one surfactant selected from the group consisting of an anionic surfactant and a nonionic surfactant.

In the above sizing agent for carbon fibers, the epoxy-amine adduct may be water-soluble.

Moreover, the present invention provides a sizing agent for carbon fibers containing the above-described water-dispersed resin composition.

Moreover, the present invention provides a carbon fiber coated with a sizing agent for carbon fibers, which is coated with the sizing agent for carbon fibers.

Further, the present invention provides a fiber-reinforced composite material comprising the above-mentioned carbon fiber coated with a sizing agent for carbon fibers.

Further, the present invention provides a fiber-reinforced composite material comprising the aforementioned thermoplastic resin composition and carbon fibers.

Moreover, the present invention provides a treatment agent for carbon fibers comprising the above epoxy-amine adduct.

Further, the present invention provides a carbon fiber bundle coated with the above sizing agent for carbon fibers.

Further, the present invention provides a prepreg obtained by coating the carbon fibers of the sizing agent for carbon fibers.

Further, the present invention provides a prepreg comprising the aforementioned epoxy-amine adduct, thermoplastic resin, and carbon fiber.

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

Further, the present invention provides a fiber-reinforced composite material comprising the above-mentioned carbon fiber coated with a sizing agent for carbon fibers and a thermoplastic resin.

Since the epoxy-amine adduct of the present invention has the above-described configuration, for example, a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group (especially a glycidyl group) present on the surface of an additive such as a reinforcing fiber or a filler. The base (reactive functional group) has high reactivity, and can effectively improve the adhesion between the thermoplastic resin and the additive in the polymer composite such as the fiber-reinforced composite material or the nano-composite. Further, since it can be softened or melted at least by heating, or is excellent in solubility to a solvent or a resin, it can be easily blended with other components. In addition, since the fiber-reinforced composite material or the nano-composite obtained is excellent in mechanical properties (especially, toughness), it can exhibit excellent adhesion or confinement when used as an adhesive or a sizing agent. Sex and so on.

Further, the epoxy-amine adduct of the present invention can be used as a raw material by using a specific compound (particularly a combination of a specific aliphatic amine compound and a specific aromatic amine compound), and can be made into a high thermal decomposition temperature and heat resistant. In this case, it is suitable for processing at a high temperature, and contributes to productivity improvement of the polymer-based composite. Further, it is possible to produce a glass transition temperature which is high to a certain extent. In this case, contamination of a processing machine (roller or the like) or the like is prevented, and workability is also excellent. Further, since the epoxy-amine adduct of the present invention is particularly excellent in water solubility, it is easily prepared in the form of an aqueous solution or an aqueous dispersion. It can be used in the form of such an aqueous solution or an aqueous dispersion, and it is advantageous in terms of environmental protection or work safety.

Therefore, by using the epoxy-amine adduct of the present invention, a polymer-based composite excellent in adhesion and mechanical properties (especially toughness) capable of forming a thermoplastic resin and an additive (such as a reinforcing fiber) can be obtained. A thermoplastic resin composition (fiber reinforced composite material, etc.). Moreover, it is possible to obtain a fiber-reinforced composite material which is excellent in adhesion between a thermoplastic resin and a reinforcing fiber and has high mechanical properties (especially toughness) with high productivity.

Moreover, since the sizing agent of the present invention has the above-described configuration, the high-order workability of the carbon fiber can be improved, and the adhesion between the carbon fiber and the matrix resin can be improved. Moreover, by using an epoxy-amine adduct having excellent heat resistance, it can be applied to heat processing at a high temperature (for example, production of a carbon fiber coated with a sizing agent), and can also contribute to production of a fiber-reinforced composite material. Sexual improvement. Further, it is possible to prevent contamination of a processing machine (roller or the like) and the like, and to impart excellent texture and workability to the reinforcing fiber to which the sizing agent is applied (for example, the carbon fiber to which the sizing agent is applied). Therefore, the sizing agent-coated carbon fiber obtained by applying the sizing agent of the present invention to the carbon fiber is excellent in high-order workability, and is excellent in adhesion and adhesion between the carbon fiber and the matrix resin. Further, the fiber-reinforced composite material containing the carbon fiber coated with the sizing agent described above has excellent heat resistance and mechanical strength (especially toughness) and high productivity.

Since the water-dispersed resin composition of the present invention contains the above-mentioned epoxy-amine adduct, it has high affinity for functional groups such as a hydroxyl group or a carboxyl group present on the surface of the reinforcing fiber, and also contains the above epoxy-amine. Since the adduct and the urethane resin are effective, the adhesion between the thermoplastic resin and the reinforcing fiber in the fiber-reinforced composite material can be effectively improved. In particular, the water-dispersible resin composition of the present invention is very useful in that it can widely exhibit good adhesion of the resin to the reinforcing fibers regardless of the matrix resin used. Moreover, since the form of the water-dispersed resin composition is used, impregnation or coating of the reinforcing resin can be easily performed. In addition, the water-dispersed resin composition of the present invention can be used without using an operating environment by using a water-dispersible resin composition (aqueous dispersion) containing no organic solvent or a small amount thereof, and environmental protection. It is also beneficial. Therefore, when the water-dispersible resin composition of the present invention is used, a prepreg of a fiber-reinforced composite material excellent in adhesion between a thermoplastic resin and a reinforcing fiber can be obtained with excellent productivity, and the prepreg can be obtained by the above-mentioned The impregnation body can obtain a fiber-reinforced composite material which is excellent in adhesion between a thermoplastic resin and a reinforced fiber and has high mechanical properties (especially toughness).

Form for implementing the invention  <epoxy-amine adduct>  

The epoxy-amine adduct of the present invention is an epoxy-amine adduct selected from a compound [I] containing two or more amine groups in a molecule (there is only referred to as "compound [I]" And a compound of the group of the salt of the compound [I], wherein the compound [I] is an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule, and an intramolecular compound a compound having an adduct of an amine compound (B) having two or more amine groups, the epoxy compound (A) containing a compound represented by the following formula (a), and the amine compound (B) containing a compound selected from the following formula ( At least one of the compounds represented by bI) and at least one compound selected from the group consisting of the following formula (b-II), and the epoxy-amine addition product is a compound having an amine group at both terminals.

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

R ^1a (NH ₂ ) ₂ (bI)

[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 through a linking group containing a hetero atom

(b) a divalent group in which a divalent linear or branched aliphatic hydrocarbon group is directly bonded to a divalent cyclic aliphatic hydrocarbon group]

R ^1b (NH ₂ ) ₂ (b-II)

[wherein R ^1b represents a divalent group selected from the group consisting of the following (c) to (g).

(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 is directly bonded to a divalent linear or branched aliphatic hydrocarbon group

(e) a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring.

(f) a divalent group and a divalent linear chain obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. Or a divalent group directly bonded to a branched aliphatic hydrocarbon group

(g) a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons having 6 to 12 carbon atoms through a group bonded to a linking group]

In the present specification, the compound [I] is referred to as "the first aspect of the epoxy-amine adduct of the present invention", and the salt of the compound [I] is referred to as "the epoxy-amine addition of the present invention". The second aspect of the object. In addition, the first and second aspects of the epoxy-amine adduct of the present invention are collectively referred to as "the epoxy-amine adduct of the present invention".

That is, the first and second aspects of the epoxy-amine adduct of the present invention each have an epoxy compound (A) derived from the compound [I] [having two or more alicyclic epoxy groups in the molecule] A compound having a structure of an adduct of an amine compound (B) having two or more amine groups in the molecule and a compound having two or more amine groups in the molecule. The first and second aspects of the epoxy-amine adduct of the present invention exhibit such a common structure and can enhance the thermoplastic resin in a polymer-based composite (for example, a fiber-reinforced composite material). The adhesion of an additive (for example, a reinforced fiber) is easy to blend with other components such as a resin, and a polymer-based composite excellent in mechanical properties (especially, toughness) can be formed (for example, fiber-reinforced composite) The effect of materials, etc.).

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

 [Compound [I]]  

The compound [I] is a compound having two or more amine groups (-NH ₂ ) in the molecule, and is an epoxy-amine adduct of the epoxy compound (A) and the amine compound (B). More specifically, the compound [I] is one molecule or more produced by reacting an alicyclic epoxy group of the epoxy compound (A) with an amine group of the amine compound (B). An adduct of the epoxy compound (A) and one or more (preferably two or more molecules) of the amine compound (B). In the present specification, the case of simply referring to "amino group" means -NH ₂ (unsubstituted amino group), and the "-NH- group" does not include the unsubstituted amine group (-NH ₂ ).

 Epoxy compound (A)  

The epoxy compound (A) which is a raw material of the compound [I] is a polyepoxy compound (alicyclic epoxy compound) having two or more alicyclic epoxy groups in the molecule, and is characterized by the following formula (a) the compound shown.

X in the above formula (a) represents a single bond or a linking group (having a divalent group of one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a part or all of a carbon-carbon double bond, an epoxidized extended alkenyl group, a carbonyl group, an ether bond, an ester bond, a carbonate group, a guanamine group, and two or more. The base of these bases, etc. Further, in one or more carbon atoms constituting the alicyclic ring (alicyclic epoxy group) in the formula (a), a substituent such as an alkyl group may be bonded.

The epoxy compound (A) wherein X is a single bond in the above formula (a) is, for example, a (3,4,3',4'-diepoxy)dicyclohexyl group.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and 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, a trimethylene group, and the like. . Examples of the divalent alicyclic hydrocarbon group include a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-extended cyclohexyl group, and a 1,3-extension ring. A divalent cycloalkylene group (including a cycloalkylene group) such as a hexyl group, a 1,4-cyclohexylene group or a cyclohexylene group.

Examples of the alkenyl group in the case where a part or all of the carbon-carbon double bond is epoxidized to an alkenyl group (in the case of "epoxidized alkenyl group") are, for example, a vinyl group, a propenyl group, and 1 - a linear or branched carbon number of 2 to 8 such as a 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. Chain-like alkenyl group and the like. In particular, as the above epoxidized alkenyl group, it is preferred that all of the epoxidized alkenyl group of the carbon-carbon double bond, more preferably a carbon-carbon double bond, of all epoxidized carbon atoms of from 2 to 4 base.

The linking group X is particularly preferably a linking group containing an oxygen atom, and specific examples thereof include -CO-, -O-CO-O-, -CO-O-, -O-, -CO-NH-, An epoxidized extended alkenyl group; a plurality of groups in which these groups are bonded; a group in which one or two or more such groups are bonded to one or two or more divalent hydrocarbon groups. Examples of the divalent hydrocarbon group include the above-exemplified ones.

Further, in the case where the epoxy compound (A) contains an ester bond (-CO-O-), the ester bond undergoes an exchange reaction with the amine group of the amine compound (B) upon reaction with the amine compound (B). Inevitably, a by-product of amide amination (which is simply referred to as "deuterated by-product") is formed, and the epoxy-amine adduct of the present invention is within the range which does not impair the effects of the present invention. It may contain an epoxy compound (A), a decomposition product of the amine compound (B), or a by-product such as the aforementioned guanamine by-product.

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-). 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-ring) Oxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane), bis(3,4-epoxycyclohexylmethyl)ether, and the like. Further, l and m in the following formulas (a-5) and (a-7) 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 an extended butyl group. A linear or branched alkyl group having a base, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among them, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylidene group, a propyl group or an extended isopropyl group is preferable. In the following formulas (a-9) and (a-10), n1 to n6 each represent an integer of 1 to 30.

The epoxy compound (A) is preferably a compound [(3,4-epoxy)cyclohexanecarboxylic acid 3,4-epoxy compound represented by the above formula (a-1) from the viewpoint of heat resistance or handleability. Cyclohexylmethyl ester; trade name "Celloxide 2021P" (DAICEL (manufactured by DAICEL), etc.].

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

 2. Amine compound (B)  

The amine compound (B) which is a raw material of the compound [I] is a polyamine compound having two or more amine groups (-NH ₂ ; an unsubstituted amino group) in the molecule, and is characterized by containing a compound (bI) selected from the above formula (bI). At least one of the compounds shown (hereinafter referred to as "amine compound (BI)") and a compound selected from the above formula (b-II) (hereinafter, referred to as "amine compound (BII) At least one of the cases of ").

The amine compound (B) functions to enhance the thermoplastic resin and the additive in the polymer-based composite (for example, a fiber-reinforced composite material, etc.) by containing both the amine compound (BI) and the amine compound (BII). For example, the adhesion of a reinforcing fiber or the like is improved, and the blending of other components such as a resin is facilitated, and a polymer-based composite excellent in mechanical properties (especially, toughness) can be formed (for example, a fiber-reinforced composite material). Etc.)

The ratio of the amine compound (BI) to the amine compound (BII) in the amine compound (B) (weight ratio of the amine compound (BI) / amine compound (BII)) is not particularly limited, but is preferably 1.5 to 4.0 (g/g). ), more preferably 1.7~3.0 (g/g). When the ratio is less than 1.5 (g/g), the water solubility tends to decrease, and in the case of more than 4.0 (g/g), the toughness of the epoxy-amine adduct may be insufficient.

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. When the molecular weight is less than 80, the amount of the -NH- group (substituted amino group) described later in the epoxy-amine adduct of the present invention is excessive, and for example, the composition of the curable resin (curable compound) is hardened. The resulting cured product (hardened resin) becomes too brittle. On the other hand, when the molecular weight exceeds 10,000, the effect of reacting the epoxy compound (A) is small, or the effect obtained by blending the epoxy-amine adduct of the present invention (for example, a cured product (hardened resin) The heat resistance is improved, and the heat resistance and toughness of the fiber-reinforced composite material are insufficient.

R ^1a in the above formula (bI) represents a divalent group selected from the group consisting of the following groups (a) and (b).

(a) a divalent group in which two or more divalent linear or branched aliphatic hydrocarbons are bonded through a linking group containing a hetero atom

(b) a divalent group directly bonded to a divalent linear or branched aliphatic hydrocarbon group and a divalent cyclic aliphatic hydrocarbon group

Examples of the divalent linear or branched aliphatic hydrocarbon include an alkylene group [e.g., methylene, ethyl, propyl, butyl, pentyl, hexyl, and hexylene). Base, octyl, hydrazine, hydrazine, undecyl, dodecyl, thirteen, tetradecyl, pentadecyl, hexadecyl, a linear or branched alkylene group (preferably a C _1-18 alkylene group) _having a carbon number of 1 to 30 (C _1-30 ) such as a heptadecyl group or an octadecyl group; Alkenyl group (corresponding to an extended alkenyl group of the above alkylene group, for example, a linear or branched alkenyl group having 2 to 30 carbon atoms such as a vinyl group or an allyl group (preferably a C _2-18 alkylene group) Base) etc.].

The divalent straight-chain or branched aliphatic hydrocarbon may have various substituents (that is, at least one of hydrogen atoms of the above-mentioned divalent linear or branched aliphatic hydrocarbon may be Substituted by various substituents). Examples of the substituent 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 group (alkane). An oxycarbonyl group, an aryloxycarbonyl group, an aralkoxycarbonyl group, etc., a substituted or unsubstituted aminemethanyl group, a cyano group, a nitro group, a substituted or unsubstituted amine group, a sulfo group, a 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, organic mercapto group, alkoxyalkyl group, oxacycloalkyl group, etc.).

Examples of the above substituted or unsubstituted aminecarbamyl 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, a tertiary butyl group, or the like, or an acetamidine group. An amine carbenyl group such as a fluorenyl group such as a benzyl group or a benzyl group; or an unsubstituted amine carbaryl group or the like. Further, examples of the 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, a tertiary butyl group, or the like. An amine group such as a fluorenyl group such as a benzamidine group; or an unsubstituted amino group or the like.

Examples of the divalent cyclic aliphatic hydrocarbon group include a stretched alkyl group (for example, a ring-like propyl group, a cyclolatene butyl group, a cyclopentylene group, a cyclohexylene group, or the like) having a carbon number of 3 to 20 An alkyl 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 or the like having a carbon number of 3 to 20 a cycloalkenyl group (preferably a C _3-15 cycloalkenyl group), etc., a cycloalkylene group [corresponding to a cycloalkylene group of the above cycloalkyl group, for example, a cyclopentylene group, a cyclohexylene group, etc. a cycloalkylene group (preferably a C _3-15 cycloalkylene group) having a carbon number of 3 to 20, etc., a cycloalkadienylene group [corresponding to a cycloalkane group of the above cycloalkyl group) The alkenyl group is, for example, a cyclopentadienyl group having a carbon number of 4 to 20, such as a cyclopentadienyl group (preferably a C _4-15 cycloalkadienyl group), or the like, and a divalent polycyclic hydrocarbon group. [For example, a divalent spirohydrocarbyl group such as a spirohydrocarbon (for example, spiro[4.4]decane, spiro[4.5]decane, etc.)-diyl or the like; a ring-collecting hydrocarbon (for example, a bicyclopropyl group, etc.)-diyl group or the like a divalent ring-collecting hydrocarbon group; a bridged cyclic hydrocarbon (for example, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, norbornane, descending Ene, adamantane) - diyl divalent bridged cyclic hydrocarbon group, etc.] and the like. The divalent cyclic aliphatic hydrocarbon group may have a substituent, and as the substituent, for example, in addition to the substituent which the above-mentioned divalent linear or branched aliphatic hydrocarbon may have, an alkyl group may be mentioned. (e.g., a C _1-4 alkyl group such as a methyl group or an ethyl group), a monovalent hydrocarbon group such as an alkenyl group or an aryl group (e.g., a phenyl group or a naphthyl group).

Examples of the above-mentioned hetero atom-containing linking group (divalent group) include -CO-, -O-, -CO-O-, -O-CO-O-, -CO-NH-, and -CO-NR ^a. - (substituted amidino group; R ^a represents an alkyl group), -NH-, -NR ^b - (R ^b represents an alkyl group), -SO-, -SO ₂ - or the like containing a hetero atom (oxygen atom, nitrogen atom, A divalent group such as a sulfur atom or the like, a plurality of such linked divalent groups, and the like.

Wherein, as the above R ^1a , a divalent group of (a) is preferred, and more preferably two or more straight or branched alkyl groups having 2 to 6 carbon atoms (especially ethyl or trimethylene) , propyl) a divalent group bonded through -NH- or -O-.

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 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 is directly bonded to a divalent linear or branched aliphatic hydrocarbon group

(e) Removal of an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring (hereinafter, simply referred to as "aromatic heterocyclic ring") Two hydrogen atoms

(f) a divalent group in which a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring is directly bonded to a divalent linear or branched aliphatic hydrocarbon group

(g) a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons having 6 to 12 carbon atoms through a group bonded to a linking group

The divalent group of the above (d) may be a divalent linear or branched aliphatic hydrocarbon group directly bonded to a divalent group of an aromatic hydrocarbon (that is, -(aromatic hydrocarbon)-(aliphatic) The hydrocarbon group)-) may also be a direct bond of two divalent linear or branched aliphatic hydrocarbon groups to the divalent group of the aromatic hydrocarbon (ie, -(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 of the above (f) may be a divalent linear or branched aliphatic hydrocarbon group directly bonded to a divalent group of an aromatic heterocyclic ring (that is, -(aromatic heterocyclic)-( The aliphatic hydrocarbon group)-) may also be a divalent linear or branched aliphatic hydrocarbon group directly bonded to the divalent group of the aromatic heterocyclic ring (that is, -(aliphatic hydrocarbon group)-(aromatic) Family 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, and biphenyl. The aromatic hydrocarbon may have a substituent, and examples of the substituent include, for example, a methyl group (except for a methyl group, in addition to a substituent which the above-mentioned divalent linear or branched aliphatic hydrocarbon may have. A monovalent hydrocarbon group such as a C _1-4 alkyl group such as an ethyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group.

The aromatic heterocyclic ring (an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring) may, for example, be an aromatic group containing an oxygen atom as a hetero atom. Heterocycle (eg, furan ring, 5-membered ring of azole ring, benzofuran ring, a condensed ring such as an anthracene ring or the like), an aromatic heterocyclic ring 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, or a condensed ring such as a benzothiophene ring), An aromatic heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a 5-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, or a triazole ring, a pyridine ring, or a fluorene ring) Ring, pyrimidine ring, pyridyl 6-membered ring, anthracene ring, porphyrin ring, quinoline ring, acridine ring, etc. a condensed ring such as a pyridine ring, a quinazoline ring or an anthracene ring or the like). The aromatic heterocyclic ring may have a substituent, and examples of the substituent include, for example, an alkyl group (for example, A) in addition to the substituent which the divalent linear or branched aliphatic hydrocarbon may have. A monovalent hydrocarbon group such as a C _1-4 alkyl group such as a group or an ethyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group (for example, a phenyl group or a naphthyl group). Further, the nitrogen atom constituting the aromatic heterocyclic ring may be a conventional protecting group (for example, an alkoxy group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an aralkoxycarbonyl group, an aralkyl group, an anthranyl group, an aromatic group). Protected by a sulfonyl group, an alkylsulfonyl group, and the like.

The divalent straight-chain or branched aliphatic hydrocarbon may, for example, be a divalent linear or branched aliphatic hydrocarbon exemplified as R ^1a .

Examples of the above-mentioned linking group (divalent group) include the above-mentioned divalent linear or branched aliphatic hydrocarbon, the above-mentioned divalent cyclic aliphatic hydrocarbon group, -CO-, -O-, -CO- O-, -O-CO-O-, -CO-NH-, -CO-NR ^a - (substituted amidino group; R ^a represents an alkyl group), -NH-, -NR ^b - (R ^b represents 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 plurality of such linked divalent groups.

Wherein, as the above R ^1b , a divalent group of (d), a divalent group of (e), or a divalent group of (g) is more preferably removed from an aromatic hydrocarbon having 6 to 10 carbon atoms; a divalent group (for example, a phenyl group) in which a hydrogen atom is bonded to a divalent group (for example, xylylene group) directly bonded to an alkylene group having 1 to 4 carbon atoms (for example, a methylene group), from aroma A divalent group obtained by removing a hydrogen atom from a heterocyclic ring (for example, a pyridine ring), and an aromatic hydrocarbon (for example, a benzene ring) having two carbon numbers of 6 to 10 (for example, -SO ₂ -, etc.) a divalent group obtained by removing two hydrogen atoms from a bonded group.

More specifically, examples of the amine compound (BI) include a compound represented by the following formula (b-1) (a case referred to as "amine compound (B1)"), and a formula (b-2) below. The compound (in the case of the "amine compound (B2)"), the compound represented by the following formula (b-3) (the case of the "amine compound (B3)"), and the like.

In the above formula (b-1), R ² and R ³ are the same or different, and represent a divalent linear or branched aliphatic hydrocarbon. The divalent straight-chain or branched aliphatic hydrocarbon may, for example, be a divalent linear or branched aliphatic hydrocarbon exemplified as R ^1a .

Wherein, as the above R ² , a linear or branched alkyl group having 2 to 6 carbon atoms is preferred, and a linear or branched alkyl group having 2 to 4 carbon atoms is further preferred (especially Base, trimethylene, propyl).

Wherein, as the above R ³ , a linear or branched alkyl group having 2 to 6 carbon atoms is preferred, and a linear or branched alkyl group having 2 to 4 carbon atoms is further preferred (especially Base, trimethylene, propyl). Further, in the case where q is an integer of 2 or more, R ³ (complex R ³ ) in each parenthesis may be the same or different. Further, in the case of having two or more kinds of R ³ , the addition form (polymerization form) of the structure in the brackets of q may be a random type or a block type.

In the above formula (b-1), q represents an integer of 1 or more. The q is, for example, preferably from 1 to 100, more preferably from 1 to 70, still more preferably from 1 to 30, particularly preferably from 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 of the polymer-based composite (especially the fiber-reinforced composite material) are improved. (Strength, etc.) The tendency to further improve. On the other hand, when the number of q is one or more, the adhesion between the thermoplastic resin and the additive in the polymer-based composite using the epoxy-amine adduct of the present invention tends to be improved.

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

In addition, as the compound represented by the above formula (b-1) (amine compound (B1)), the epoxy-amine adduct of the present invention has adhesion to an additive (especially a reinforcing fiber), wettability, From the viewpoints of heat resistance and water solubility, ethylenediamine (EDA), diethylenetriamine (DETA), triamethylenetetramine (TETA), tetraethyleneamine (TEPA), and more preferably three-stretching are preferred. Ethylenetetramine. Further, as the compound represented by the above formula (b-1), a commercially available product can also be used.

In the above formula (b-2), R ⁴ represents a divalent linear or branched aliphatic hydrocarbon. Examples of the above R ⁴ include a divalent group exemplified as the above R ² and R ³ .

Wherein, as the above R ⁴ , a linear or branched alkyl group having 2 to 6 carbon atoms is preferred, and a linear or branched alkyl group having 2 to 4 carbon atoms is further preferred (especially Base, trimethylene, propyl).

In the above formula (b-2), R ⁵ represents a divalent linear or branched aliphatic hydrocarbon. Examples of the above R ⁵ include a divalent group exemplified as the above R ² and R ³ .

Wherein, as the above R ⁵ , a linear or branched alkyl group having 2 to 6 carbon atoms is preferred, and a linear or branched alkyl group having 2 to 4 carbon atoms is further preferred (especially Base, trimethylene, propyl). Further, in the case where r is an integer of 2 or more, R ⁵ (complex R ⁵ ) in each parenthesis may be the same or different. Further, in the case of having two or more kinds of R ⁵ , the addition form (polymerization form) of the structure in the parentheses attached to r may be a random type or a block type.

In the above formula (b-2), r (the number of repetitions of the structural unit in the parentheses attached to r) represents an integer of 1 or more. R is, for example, preferably from 1 to 100, more preferably from 1 to 70, still more preferably from 1 to 30. When r is 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 of the polymer composite (especially the fiber-reinforced composite material) ( Toughness, etc.) The tendency to further improve. On the other hand, when the number of r is one or more, the adhesion between the thermoplastic resin and the additive in the polymer-based composite using the epoxy-amine adduct of the present invention tends to be improved.

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

Among them, the compound represented by the above formula (b-2) (amine compound (B2)), the adhesion of the epoxy-amine adduct of the present invention to an additive (especially a reinforcing fiber), and a thermoplastic resin From the viewpoint of wettability, an amine terminal (two terminal amino group) polyethylene glycol, an amine terminal polypropylene glycol, an amine terminal polytetramethylene glycol, and more preferably an amine terminal polypropylene glycol are preferable. Further, as the compound represented by the above formula (b-2), a commercially available product (for example, a product name "JEFFAMINE", manufactured by HUNTSMAN Co., Ltd.) may be used.

In the above formula (b-3), R ⁶ and R ⁸ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. Specific examples of R ⁶ and R ⁸ include a methylene group, an exoethyl group, a propyl group, and a butyl group.

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 the same or different represents a monovalent organic group, a monovalent oxygen atom-containing group, and a monovalent group. a sulfur atom-containing group, a monovalent nitrogen atom-containing group, or a halogen atom. Specific examples of R ⁷ include a substituent which the above-mentioned divalent cyclic aliphatic hydrocarbon group may have. Further, in the above formula (b-3), t represents the number of the substituent (R ⁷ ) on the cyclohexane ring represented by the formula, and represents an integer of 0 to 10. In the case where t in the above formula (b-3) is an integer of 2 or more, each R ⁷ may be the same or different.

More specifically, as a group formed by removing two amine groups at both ends from the structural formula represented by the above formula (b-3), for example, 1,2-cyclohexylene-methylene group, 1, 3-cyclohexyl-methylene, 1,4-cyclohexyl-methylene, cyclohexylene-methylene, 1,2-extended cyclohexyl-extended ethyl, 1,3-cyclohexyl- Ethyl, 1,4-cyclohexyl-extended ethyl, cyclohexylene-extended ethyl, methylene-1,5,5-trimethyl-1,3-cyclohexyl (from isophorone) a dicyclohexyl-alkylene group, a methylene-1,2-cyclohexylene-methylene group, a methylene-1,3-extension ring, such as a diamine group formed by removing a diamine from a diamine An alkylene-cyclohexane-alkylene group such as a hexyl-methylene group, a methylene-1,4-cyclohexyl-methylene group or the like.

Among them, the compound represented by the above formula (b-3) (amine compound (B3)) is preferably isophorone diamine from the viewpoint of heat resistance of the epoxy-amine adduct of the present invention. Further, as the compound represented by the above formula (b-3), a commercially available product (for example, a product name "Vestamin IPD" manufactured by Evonik Degussa Japan Co., Ltd.) can be used.

The amine compound (BI) is preferably a formula (see, for example, an effect of improving the adhesion between the thermoplastic resin and the additive material, heat resistance, toughness, etc., by the epoxy-amine adduct of the present invention. The compound represented by b-1) and the compound of the formula (b-3) are more preferably a compound represented by the formula (b-1).

Specific examples of the amine compound (BII) include a compound represented by the following formula (b-5) (a case referred to as "amine compound (B5)"), and a formula (b-6) below. The compound (in the case of the "amine compound (B6)"), the compound represented by the following formula (b-7) (the case of the "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 having 6 to 12 carbon atoms is exemplified by the aromatic hydrocarbon having 6 to 12 carbon atoms exemplified as R ^1b .

In the above formula (b-5), R ¹¹ and R ¹³ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. The alkylene group having 1 to 4 carbon atoms is exemplified by the alkylene group having 1 to 4 carbon atoms exemplified as R ⁶ and R ⁸ in the formula (b-3).

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, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. The monovalent organic group, the oxygen atom-containing group, the sulfur atom-containing group, the nitrogen atom-containing group, and the halogen atom are exemplified as R ⁷ . Further, in the above formula (b-5), w2 represents the number of the substituent (R ¹² ) of A ¹ represented by the formula, and represents an integer of 0 to 4. In the case where 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, as a group formed by removing two amine groups at both ends from the structural formula represented by the above formula (b-5), for example, 1,2-phenylene, 1,3-phenylene a aryl group, a 1,2-phenylene-methylene group, a 1,3-phenylene-methylene group, a 1,4-phenylene-methylene group , 1,2-phenylene-extended ethyl, 1,3-phenylene-extended ethyl, 1,4-phenylene-extended ethyl, etc., aryl-alkylene, methylene- 1,2-phenylene-methylene, methylene-1,3-phenylene-methylene, methylene-1,4-phenylene-methylene, etc. Aryl-alkylene and the like.

In addition, the compound (amine compound (B5)) represented by the above formula (b-5) is a polymer-based composite (for example, a fiber-reinforced composite material) which is excellent in mechanical properties (especially, toughness). The viewpoint is preferably m-xylylenediamine, p-xylylenediamine or o-xylylenediamine. Further, as the compound represented by the above formula (b-5), a commercially available product can also be used.

In the above formula (b-6), B ¹ represents an aromatic heterocyclic ring (aromatic heterocyclic ring) having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. The aromatic heterocyclic ring is exemplified as the aromatic heterocyclic ring 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. The alkylene group having 1 to 4 carbon atoms is exemplified by the alkylene group having 1 to 4 carbon atoms exemplified as R ⁶ and R ⁸ in the formula (b-3).

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. The monovalent organic group, the oxygen atom-containing group, the sulfur atom-containing group, the nitrogen atom-containing group, and the halogen atom are exemplified as R ⁷ . Further, in the above formula (b-6), x2 represents the number of the substituent (R ¹⁵ ) of B ¹ represented by the formula, and represents an integer of 0 to 4. In the case where 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 two amine groups at both ends from the structural formula represented by the above formula (b-6) include pyridine-2,6-diyl and pyridine-2,5. An aromatic heterocyclic ring-diyl group such as a diyl group, a pyridine-2,4-diyl group or a pyridine-2,3-diyl group.

In addition, the compound (the amine compound (B6)) represented by the above formula (b-6) is a polymer-based composite (for example, a fiber-reinforced composite material) which is excellent in mechanical properties (especially, toughness). The viewpoint is preferably 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyridine or 2,3-diaminopyridine. Further, as the compound represented by the above formula (b-6), a commercially available product can also be used.

In the above formula (b-7), A ² and A ³ are the same or different and represent an aromatic hydrocarbon having 6 to 12 carbon atoms. The aromatic hydrocarbon having 6 to 12 carbon atoms is exemplified by the aromatic hydrocarbon having 6 to 12 carbon atoms exemplified as R ^1b .

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

In the above formula (b-7), R ¹⁷ and R ¹⁸ are the same or different and each represent a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. The monovalent organic group, the oxygen atom-containing group, the sulfur atom-containing group, the nitrogen atom-containing group, and the halogen atom are exemplified as R ⁷ . Further, in the above formula (b-7), y1 and y2 represent the formula A shown in substituent group (R ¹⁷⁾ and A ^{3 are} the number of substituent groups (R ^{18) 2,} the same or different and represent 0 An integer of ~4. In the case where y1 in the above formula (b-7) is an integer of 2 or more, each of R ¹⁷ may be the same or different. In the case where y2 in the above formula (b-7) is an integer of 2 or more, each R ¹⁸ may be the same or different.

In addition, the compound (the amine compound (B7)) represented by the above formula (b-7) is a polymer-based composite (for example, a fiber-reinforced composite material) which is excellent in mechanical properties (especially, toughness). The viewpoint is preferably 3,3-diaminodiphenyl hydrazine, 4,4-diaminodiphenyl hydrazine, 2,2-diaminodiphenyl hydrazine. Further, as the compound represented by the above formula (b-7), a commercially available product can also be used.

The amine compound (BII) is preferably a compound (for example, a fiber-reinforced composite material or the like) which is excellent in mechanical properties (especially, toughness), and is preferably represented by the formula (b-5). The compound represented by the formula (b-6) and the compound represented by the formula (b-7) are more preferably a compound represented by the formula (b-7).

The amine compound (BII) may be used alone or in combination of two or more.

 3. Compound [I]  

The compound [I] of the first aspect of the invention is preferably an epoxy-amine adduct represented by the following formula (I) (hereinafter, referred to as "epoxy-amine adduct (I)" "The situation".

Wherein R ^{1 '} is a divalent organic group having a carbon atom at a bonding site to a nitrogen atom represented by the formula, and at least one is selected from the group consisting of the following (a) and (b) At least one divalent group, and at least one other represents at least one divalent group selected from the group consisting of the following (c) to (g). X represents a single bond or a divalent group having one or more atoms. z represents an integer of 1 or more.

(a) a divalent group in which two or more divalent linear or branched aliphatic hydrocarbons are bonded through a linking group containing a hetero atom

(b) a divalent group directly bonded to a divalent linear or branched aliphatic hydrocarbon group and a divalent cyclic aliphatic hydrocarbon group

(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 is directly bonded to a divalent linear or branched aliphatic hydrocarbon group

(e) a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring.

(f) a divalent group and a divalent linear chain obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. Or a divalent group directly bonded to a branched aliphatic hydrocarbon group

(g) a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons having 6 to 12 carbon atoms through a group bonded to a linking group]

The epoxy-amine adduct (I) has a structural unit derived from the epoxy compound (A), a molecular chain alternately arranged with a structural unit derived from the amine compound (B), and an amine at both ends of the molecular chain. An epoxy-amine adduct of a group (-NH ₂ ) (that is, a structural unit derived from the amine compound (B) at both ends). Further, the addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be a random type or a block type.

Further, in the above formula (I), among the carbon atoms constituting the cyclohexane ring, when the carbon atom to which X is bonded is regarded as a carbon atom of "1 position", it is bonded to the formula (I). The bonding position of the nitrogen atom (-NH-) derived from the structural unit of the amine compound (B) of each cyclohexane ring is a carbon atom at the 3-position of the cyclohexane ring or a carbon atom at the 4-position. In the case where the bonding position of the above nitrogen atom is a carbon atom at the 3 position, the bonding position of the hydroxyl group (-OH) bonded to the cyclohexane ring in the formula (I) is a carbon atom at the 4 position. Further, in the case where the bonding position of the nitrogen atom is a carbon atom at the 4-position of the cyclohexane ring, the bonding position of the hydroxyl group (-OH) bonded to the cyclohexane ring in the formula (I) is a 3-position. carbon atom. The bonding position (or the bonding position of the hydroxyl group) of the above nitrogen atom in the plural (2 or more) cyclohexane ring in the above formula (I) may be the same or different. Further, when the above-mentioned position number is added to the carbon atom constituting the cyclohexane ring in the formula (I), the following formula is obtained.

At least one divalent group selected from the group consisting of the above (a) and (b) as at least one of R ^{1 '} constituting the epoxy-amine adduct (I) (hereinafter, referred to as " In the case of the first divalent group, a divalent group selected from the group consisting of (a) and (b) represented by R ^1a in the above formula (bI) can be mentioned.

Wherein, as the first divalent group of R ^{1 ',} a divalent group of (a) is preferred, and more preferably two or more linear or branched alkyl groups having 2 to 6 carbon atoms (especially Ethyl, trimethylene, and propyl) are divalent groups bonded through -NH- or -O-.

At least one divalent group selected from the group consisting of the above (c) to (g) as at least one other of R ^{1 '} constituting the epoxy-amine adduct (I) (hereinafter, referred to as " In the case of the second divalent group, a divalent group selected from the group consisting of (c) to (g) represented by R ^1b in the above formula (b-II) can be mentioned.

Wherein, the second divalent group of R ^{1 '} is preferably a divalent group of (d), a divalent group of (e), or a divalent group of (g), more preferably from 6 to 10 carbon atoms. A divalent group in which an aromatic hydrocarbon removes two hydrogen atoms (for example, a phenyl group) and a alkyl group having a carbon number of 1 to 4 (for example, a methylene group) directly bonded (for example, two a tolyl group, a divalent group obtained by removing two hydrogen atoms from an aromatic hetero ring (for example, a pyridine ring), and an aromatic hydrocarbon (for example, a benzene ring) having two carbon numbers of 6 to 10 (for example, a benzene ring) are transmitted through a linking group (for example, , -SO ₂ -etc.) A divalent group obtained by removing two hydrogen atoms from the bonded group.

Specific examples of the first divalent group of R ^{1 '} include a divalent group represented by the following formula (II), a divalent group represented by the following formula (III), and the following formula (IV). The divalent group shown and the like.

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

Among them, as the divalent group represented by the above formula (II), the viewpoint of adhesion, wettability, heat resistance and water solubility of the epoxy-amine adduct of the present invention to an additive (especially a reinforcing fiber) Preferably, the divalent group of the amine group at both ends of ethylenediamine (EDA), diethylenetriamine (DETA), triamethylenetetramine (TETA), and tetraamethylenetetramine (TEPA) is removed. Preferably, the divalent group of the amine group at both ends of the triamethylenetetramine is removed.

R ⁴ , R ⁵ and r in the above formula (III) are the same as those of R ⁴ , R ⁵ and r in the above formula (b-2).

Among them, as the divalent group represented by the above formula (III), the epoxy-amine adduct of the present invention has an adhesiveness to an additive (especially a reinforcing fiber) and a wettability with a thermoplastic resin. Preferably, the divalent group of the amine group at both ends of the amine terminal (two terminal amino group) polyethylene glycol, the amine terminal polypropylene glycol, and the amine terminal polytetramethylene glycol is removed, and more preferably, both ends of the amine terminal polypropylene glycol are removed. A divalent group of an amino group.

In the above formula ^{(IV) R 6, R 7} , R 8, s and t, as in the illustrated embodiment Department (b-3) R above formula ^{6, R 7, R 8,} s and t are the same.

Here, examples of the divalent group represented by the above formula (IV) include 1,2-cyclohexylene-methylene group, 1,3-cyclohexylene-methylene group, and 1,4-cyclohexylene group-Asia. Methyl, cyclohexylene-methylene, 1,2-extended cyclohexyl-extended ethyl, 1,3-cyclohexyl-extended ethyl, 1,4-cyclohexyl-extended ethyl, cyclohexylene - Stretching of an ethyl group, a methylene-1,5,5-trimethyl-1,3-cyclohexyl group (a divalent group formed by removing two amine groups from isophoronediamine) Alkyl-alkylene, methylene-1,2-cyclohexylene-methylene, methylene-1,3-cyclohexyl-methylene, methylene-1,4-cyclohexyl- An alkylene-cyclohexane-alkylene group such as a methylene group.

Among them, the divalent group represented by the formula (IV) is preferably methylene-1,5,5-trimethyl-1 from the viewpoint of heat resistance of the epoxy-amine adduct of the present invention. 3-cyclohexyl group (a divalent group formed by removing two amine groups from isophorone diamine).

The first divalent group of R ^{1 '} is, in particular, the viewpoint of the adhesion improving effect, heat resistance, and toughness of the thermoplastic resin and the additive due to the epoxy-amine adduct of the present invention. The divalent group represented by the formula (II) and the divalent group represented by the formula (IV) are more preferably a divalent group represented by the formula (II).

Specific examples of the second divalent group of R ^{1 '} include a divalent group represented by the following formula (V), a divalent group represented by the formula (VI), and a formula (VII). Price base, etc.

A ¹ , R ¹¹ , R ¹² , R ¹³ , w1, w2 and w3 in the above formula (V) are exemplified by A ¹ , R ¹¹ , R ¹² , R ¹³ and w1 in the above formula (b-5). , w2 and w3 are the same.

More specifically, examples of the divalent group represented by the above formula (V) include an extended aryl group such as a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group. 1,2-phenylene-methylene, 1,3-phenylene-methylene, 1,4-phenylene-methylene, 1,2-phenyl-ethyl, 1 , 3-phenylene-extended ethyl, 1,4-phenylene-extended ethyl, etc., aryl-alkylene, methylene-1,2-phenylene-methylene, methylene Alkyl-1,3-phenylene-methylene, methylene-1,4-phenylene-methylene, etc., alkylene-arylene-alkylene group and the like.

In the viewpoint of forming a divalent group represented by the above formula (V), a polymer-based composite (for example, a fiber-reinforced composite material) having excellent mechanical properties (especially, a strong toughness) is preferable. a divalent group of an amine group at both ends of xylylenediamine, p-xylylenediamine or o-xylylenediamine.

B ¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ , x1, x2 and x3 in the above formula (VI) are exemplified by B ¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and x1 in the above formula (b-6). , x2 and x3 are the same.

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

In particular, the divalent group represented by the above formula (VI) is preferably removed in view of a polymer-based composite (for example, a fiber-reinforced composite material) which is excellent in mechanical properties (especially, toughness). a divalent group of an amine group at both ends of 6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyridine or 2,3-diaminopyridine.

A ² , A ³ , Y ¹ , R ¹⁷ , R ¹⁸ , y1 and y2 in the above formula (VII) are exemplified by A ² , A ³ , Y ¹ and R ¹⁷ in the above formula (b-7). R ¹⁸ , y1 and y2 are the same.

In addition, as the divalent group represented by the formula (VII), it is preferable to remove 3 from the viewpoint of forming a polymer-based composite (for example, a fiber-reinforced composite material) excellent in mechanical properties (especially, toughness). a divalent group of an amine group at both ends of 3-diaminodiphenyl hydrazine, 4,4-diaminodiphenyl hydrazine, and 2,2-diaminodiphenyl hydrazine.

The second divalent group of the above R ^{1 '} is preferably a formula (V) from the viewpoint of forming a polymer-based composite (for example, a fiber-reinforced composite material) excellent in mechanical properties (especially, toughness). The divalent group shown, the divalent group represented by the formula (VI), and the divalent group represented by the formula (VII) are more preferably a divalent group represented by the formula (VII).

The ratio of the first divalent group to the second divalent group of R ^{1 '} in the epoxy-amine adduct (I) (weight ratio of the first divalent group to the second divalent group) is not particularly limited. Preferably, it is 1.5 to 4.0 (g/g), more preferably 1.7 to 3.0 (g/g). When the ratio is less than 1.5 (g/g), the water solubility tends to decrease, and in the case of more than 4.0 (g/g), the toughness of the epoxy-amine adduct may be insufficient.

X in the above formula (I) represents a single bond or a linking group (having a divalent group of one or more atoms), and is the same as X in the above formula (a). Further, in the case where z is an integer of 2 or more, each X may be the same or different.

z in the above formula (I) (the number of repetitions of the structural unit in the parentheses in z) represents an integer of 1 or more. z is not particularly limited, but is preferably 1 to 200, more preferably 2 to 150, still more preferably 2 to 100. If z exceeds 200, there is a case where the epoxy-amine adduct is difficult to blend with other components. Further, z in the above formula (I) can be controlled, for example, by the ratio of the epoxy compound (A) to the amine compound (B) to be reacted, the reaction conditions, and the like. Further, in the case where z is an integer of 2 or more, each structural unit (X, R ^{1 '} ) in parentheses may be the same or different.

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

 4. A method for producing the compound [I]; a reaction of an epoxy compound (A) with an amine compound (B)  

The compound [I] can be produced by reacting the epoxy compound (A) with the amine compound (B). More specifically, the compound [I] is produced by reacting an alicyclic epoxy group of the epoxy compound (A) with an amine group of the amine compound (B).

The epoxy compound (A) and the amine compound (B) which are the raw materials of the compound [I] are specifically, in particular, adhesion to an additive (strengthening fiber or the like), wettability to a resin, heat resistance, From the viewpoints of workability, water solubility at the time of salt formation, and toughness of a polymer-based composite (for example, a fiber-reinforced composite material), a compound represented by the formula (a) and an amine compound (BI) are used. And the epoxy-amine adduct obtained by the reaction of both (BII). Further, in the epoxy-amine adduct of the present invention, an epoxy compound or an amine compound other than the above-mentioned epoxy compound (A) and the amine compound (B) may be used in combination. For example, as the 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), or an amine other than the amine compound (BII) may be used in combination. Compound.

The ratio of the compound represented by the formula (a) in the total amount (100% by weight) of the epoxy compound (A) of the raw material of the epoxy-amine adduct of the present invention is not particularly limited, and is preferably 80% by weight or more. More preferably, it is 90% by weight or more, and further preferably 98 to 100% by weight. When the ratio of the compound represented by the formula (a) is 80% by weight or more, there is a binder property for an additive (especially a reinforcing fiber such as carbon fiber) or a polymer-based composite (especially a fiber-reinforced composite material). The adhesion between the thermoplastic resin and the additive material (especially the reinforcing fiber) tends to increase 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) of the raw material of the epoxy-amine adduct of the present invention is not particularly limited, and is preferably. It is 10% by weight or more (for example, 10 to 100% by weight), more preferably 20 to 90% by weight, 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) to the above range, the adhesion to the additive (especially the reinforcing fiber such as carbon fiber), the wettability, and the polymer system are further improved. Adhesiveness, water solubility, mechanical properties of polymer-based composites (for example, fiber-reinforced composite materials, etc.) of additives (especially reinforcing fibers) in composites (especially fiber-reinforced composite materials) (especially It is the tendency to be strong and tough.

The above reaction (reaction of the epoxy compound (A) with the amine compound (B)) may be carried out in the presence of a solvent or in the absence of a solvent (that is, in the absence of a solvent). The solvent is not particularly limited, and it is preferred that the epoxy compound (A) and the amine compound (B) are uniformly dissolved or dispersed. 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. Hydrocarbon; halogenated hydrocarbon such as chloroform, dichloromethane, 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, An ether such as an alkane; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ester of methyl acetate, ethyl acetate, isopropyl acetate or butyl acetate; N,N-dimethyl a decylamine such as carbamide or N,N-dimethylacetamide; a nitrile such as acetonitrile, propionitrile or benzonitrile; an alcohol such as methanol, ethanol, isopropanol or butanol; dimethyl hydrazine; water Wait. Further, the solvent may be used singly or in combination of two or more.

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

The ratio of the epoxy compound (A) to the amine compound (B) to be subjected to the above reaction is not particularly limited, and is preferably an alicyclic epoxy group and an amine compound which the epoxy compound (A) in the above reaction has ( B) The ratio of the amine group [alicyclic epoxy group/amino group] (equivalent ratio) is controlled in a manner of 0.05 to 1.00 (more preferably 0.10 to 0.95, further preferably 0.15 to 0.90). When the ratio [alicyclic epoxy group/amino group] is 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/amine group] is 1.00 or less, the unreacted epoxy compound (A) tends not to remain in the product.

The reaction of the above epoxy compound (A) with the amine compound (B) can be carried out, for example, by the method of the following [1], the method of the following [2], or the method of the following [3]. However, the method of carrying out the above reaction is not limited to the following methods [1] to [3].

[1] A method in which an epoxy compound (A) and an amine compound (B) are fed in a batch to a reaction vessel, and the mixture is heated to a reaction temperature to cause a reaction between the two.

[2] A method in which an epoxy compound (A) is fed to a reaction vessel heated to a reaction temperature as needed, and an amine compound (B) is sequentially added to cause a reaction between the two.

[3] A method in which an amine compound (B) is fed to a reaction vessel heated to a reaction temperature as needed, and an epoxy compound (A) is added one by one to cause a reaction between the two.

In addition, the above-mentioned "sequential addition" means continuous addition (a state in which it is added for a certain period of time) or intermittent addition (a state in which division is added in plural times).

Among the above methods [1] to [3], it is easy to control the heat of reaction, and it is easy to produce a compound [I] having a high molecular weight and a high glass transition temperature, preferably the method of the above [2] or [ 3] method. On the other hand, a compound having a lower molecular weight of the compound [I] depending on the use is preferable, but in such a case, it is preferred to carry out the reaction by the method of the above [1].

The rate of addition of the amine compound (B) in the method of the above [2] is not particularly limited. For example, when the total amount of the amine compound (B) to be added is 100 parts by weight, it may be from 0.1 to 20 parts by weight per minute. The range is set as appropriate. Further, the rate of adding the epoxy compound (A) to the method of the above [3] is not particularly limited, and for example, when the total amount of the epoxy compound (A) to be added is 100 parts by weight, the weight may be from 0.1 to 20 parts by weight. The range of parts per minute is set as appropriate. Further, the amine compound (B) or the epoxy compound (A) to be added may be added as it is, or may be added in a state of being dissolved or dispersed in a solution or dispersion of a solvent.

In the case of using the two or more kinds of the amine compounds (B), in the method of the above [2], the respective amine compounds (B) may be dropped or may be dropped in a state in which they are not mixed (each). Further, in the latter case, the respective amine compounds (B) may be dropped at the same time or may be successively dropped. The dropping of the case where two or more kinds of the epoxy compounds (A) are used in the method of the above [3] is also the same.

The temperature (reaction temperature) in the above reaction is not particularly limited, but is preferably 30 to 280 ° C, more preferably 80 to 260 ° C, still more preferably 120 to 250 ° C. When the reaction temperature is 30 ° C or higher, the reaction rate is increased, and the productivity of the compound [I] tends to be further improved. On the other hand, the thermal decomposition of the epoxy compound (A) or the amine compound (B) is suppressed by setting the reaction temperature to 280 ° C or lower, and the yield of the compound [I] tends to be further improved. Further, in the above reaction, the reaction temperature can also be controlled in a manner that is often fixed (substantially fixed), and can also be controlled in a stepwise or continuously varying manner.

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 2 to 8 hours. By setting the reaction time to 0.2 hours or longer, the yield of the compound [I] tends to be more improved. On the other hand, the productivity of the compound [I] tends to be improved by setting the reaction time to 20 hours or shorter.

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 any gas atmosphere such as an inert gas (for example, nitrogen or argon) or air.

The above reaction is not particularly limited, and can be carried out by any of a batch method (batch type), a semi-batch method, and a continuous flow method.

The compound [I] can be obtained by the above reaction (reaction of the epoxy compound (A) with the amine compound (B)). After the above reaction, the obtained compound [I] can be, for example, a known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or the like, a combination of such separation means, and the like. And isolated and purified.

The number of the amine group (-NH ₂ ; unsubstituted amino group) which the compound [I] has is 2 or more, preferably 2 to 10, more preferably 2 to 4, still more preferably 2 or 3. One. Further, the compound [I] does not substantially have an epoxy group (especially an alicyclic epoxy group derived from the epoxy compound (A)).

The amine group (-NH ₂ ; unsubstituted amino group) in the compound [I] is not particularly limited, and is usually located at the end of the molecular chain of the compound [I] (especially in the case of the linear compound [I] is the compound [ I] the two ends of the molecular chain). However, it is not limited to this.

The compound [I] is produced by reacting an alicyclic epoxy group of the epoxy compound (A) with an amine group (-NH ₂ ; an unsubstituted amine group) of the amine compound (B) as described above. It is presumed that the compound [I] lacks the -NH- group (substituted amino group) formed by the reaction of the above alicyclic epoxy group with an amine group (further, in the case of using the amine compound (B1), it is an amine compound ( B1) The reactivity of the -NH- group (m is one or more)) and the alicyclic epoxy group of the epoxy compound (A), usually in the molecule -NH-based system is unreacted The state remains. The number of the -NH- group which the compound [I] has in the molecule is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, 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 lowered, or the thermoplastic resin and the reinforcing fiber in the fiber-reinforced composite material are not sufficiently obtained depending on the use. The situation of the effect of sexual ascension. Further, the water solubility of the epoxy-amine adduct of the present invention is lowered. Further, the number of the -NH- group in the compound [I] can be determined, for example, by using a standard polystyrene-equivalent molecular weight measured by a gel permeation chromatography (GPC) method to obtain a ring constituting the compound [I]. The number of the oxygen compound (A) and the amine compound (B) 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) is obtained by a glycidyl group and an amine group ( The reactivity of the -NH- group formed by the reaction of the unsubstituted amino group with the epoxy propyl group is extremely high, and usually the -NH- group system does not substantially remain.

The number average molecular weight of the compound [I] 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 glass transition temperature of the epoxy-amine adduct of the present invention is increased to some extent, and the contamination of the processing machine (roller or the like) tends to be suppressed. Further, the epoxy-amine adduct of the present invention tends to have higher flexibility and toughness. Further, it is possible to impart excellent texture and workability to the reinforcing fibers (for example, the carbon fibers coated with the sizing agent) to which the epoxy-amine adduct of the present invention is applied. On the other hand, when the number average molecular weight is 40,000 or less, the epoxy-amine adduct of the present invention is easily blended with other components, and the solubility or water solubility of the solvent tends to be further improved. Further, the number average molecular weight of the compound [I] is calculated using a standard polystyrene-equivalent molecular weight measured by a gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the compound [I] is not particularly limited, but is preferably -50 to 200 ° C, more preferably -40 to 190 ° C, still more preferably -30 to 180 ° C, and particularly preferably 20 to 180 ° C. . The heat resistance of the polymer-based composite (especially fiber-reinforced composite material) using the epoxy-amine adduct of the present invention by setting the Tg of the compound [I] to -50 ° C or higher (especially 20 ° C or higher) Sexuality, mechanical properties (strong toughness, etc.) have a tendency to increase. Further, it is possible to suppress the contamination of the processing machine (roller or the like), and to impart excellent texture and workability to the reinforcing fiber (for example, the carbon fiber to which the sizing agent is applied) to which the epoxy-amine adduct of the present invention is applied. . On the other hand, when the Tg of the compound [I] is 200 ° C or lower, the epoxy-amine adduct of the present invention tends to be easily blended with other components. Further, the Tg of the compound [I] can be measured, for example, by differential scanning calorimetry (DSC), dynamic viscoelasticity measurement or the like. More specifically, it can be determined by the method disclosed in the examples.

The 5% weight loss temperature (Td ₅ ) of the compound [I] is not particularly limited, but is preferably 280 ° C or higher, more preferably 300 ° C or higher. By making the 5% weight reduction temperature of the compound [I] 280 ° C or higher (especially 300 ° C or higher), it becomes possible to apply the epoxy-amine adduct of the present invention to processing at a higher temperature (for example) The tendency to produce a carbon fiber coated with a sizing agent. Further, the 5% weight loss temperature of the compound [I] can be determined by TG/DTA. More specifically, it can be determined by the method disclosed in the examples.

The first aspect of the epoxy-amine adduct of the present invention can also be used as it is, or can be used as a solution or a dispersion. For example, the first aspect of the epoxy-amine adduct of the present invention can be dispersed in water under the use of a surfactant as needed, thereby being used as an aqueous dispersion. Further, the first aspect of the epoxy-amine adduct of the present invention can be dissolved in water and used as an aqueous solution. In the first aspect of the epoxy-amine adduct of the present invention, a part or all of the amine group and the -NH- group in the molecule may be protonated as a salt with an anion (for example, a carbonate or a carboxylic acid). A salt, a hydrogencarbonate or the like (that is, a second aspect as the epoxy-amine adduct of the present invention) is used. By forming a salt, the solubility improving effect on water and the like can be obtained. In order to improve the water solubility of the first aspect of the epoxy-amine adduct of the present invention, it is particularly preferable to use a product (for example, an aqueous paint or the like) which uses water or a solvent containing water as a main component as a medium (for example, an aqueous paint). use.

 <Second aspect of the epoxy-amine adduct of the present invention>  

The second aspect of the epoxy-amine adduct of the present invention is a salt of the compound [I] as described above. Hereinafter, the second aspect of the epoxy-amine adduct of the present invention will be referred to 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).

The 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, in the case of the compound [I] using the above epoxy-amine adduct (I) as a raw material of the salt of the epoxy-amine adduct of the present invention, the epoxy-amine adduct becomes a thermal decomposition temperature. Since it is high in heat resistance and excellent in heat resistance, it can be applied to processing at a high temperature, and contributes to productivity improvement of a polymer-based composite. In addition, since it has a glass transition temperature which is high to a certain extent, it is prevented from contamination by a processing machine (roller or the like), and is excellent in workability.

In the total amount (100% by weight) of the epoxy compound (A) which 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 The proportion of the compound represented by the formula (a) is not particularly limited, but is preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 98 to 100% by weight. By the ratio of the compound represented by the formula (a) to 80% by weight or more, the adhesion of the epoxy-amine adduct to the additive (especially a reinforcing fiber such as carbon fiber) or the polymer-based composite (especially The adhesion between the thermoplastic resin in the fiber-reinforced composite material and the additive material (especially the reinforcing fiber) tends to be effectively improved.

 [acid [II]]  

The acid [II] which is a salt constituting the salt of the epoxy-amine adduct of the present invention is an acid which can form a salt by an acid-base reaction with a basic group such as an amine group which the compound [I] has. However, it is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid, carbonic acid, sulfuric acid, nitric acid, and hydrobromic acid; formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, and apple. An organic acid such as acid, lactic acid, maleic acid or fumaric acid. The acid [II] may be used alone or in combination of two or more. Among them, the acid [II] is easily converted into the compound [I] by operability, thermal decomposition by a salt or the like, preferably carbonic acid, organic acid, more preferably carbonic acid, acetic acid (especially carbonic acid). ). That is, the salt of the epoxy-amine adduct of the present invention is preferably a carbonate, a hydrogencarbonate or an organic acid salt, more preferably a carbonate or an acetate (particularly a 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 method of producing a well-known or conventional salt. Specifically, for example, the present invention can be obtained by a method of reacting a compound [I] (specifically, a basic group such as an amine group of the compound [I]) with an acid [II] (acid-base reaction). a salt of an epoxy-amine adduct.

The above reaction can be carried out in the presence of a solvent or in the absence of a solvent (i.e., without a solvent). The solvent is not particularly limited. For example, those exemplified in the reaction of the epoxy compound (A) with the amine compound (B) can be used, and it is particularly preferred to use at least water. Further, the solvent may be used singly or in combination of two or more. Moreover, the amount of the solvent used in the above reaction is not particularly limited and can be appropriately set.

The ratio of the compound [I] to the acid [II] to be subjected to the above reaction (the reaction of the compound [I] with the acid [II]) is not particularly limited, and may be based on the basic group (for example, an amine) of the compound [I]. The ratio of the conversion to the salt is required in the group, the -NH- group, etc. (this ratio can be determined, for example, depending on the desired water solubility, etc.), and is appropriately selected.

The operation for carrying out the above reaction is not particularly limited. For example, the compound [I] and the acid [II] may be fed to the reaction vessel in batches for reaction, or the compound [I] and the acid [II] may be used. Either one of the materials is pre-advanced to the reaction vessel, and the other (for example, the above-described sequential addition) is added to cause the reaction.

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

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 any gas atmosphere such as an inert gas (for example, nitrogen or argon) or air.

The above reaction is not particularly limited, and can be carried out by any of a batch method (batch type), a semi-batch method, and a continuous flow method.

The salt of the epoxy-amine adduct of the present invention is produced by the above reaction. After the above reaction, the salt of the epoxy-amine of the present invention can be, for example, a known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or the like, or a combination thereof. Separation and purification are carried out by means of separation or the like. Further, since the salt of the epoxy-amine of the present invention is particularly excellent in water solubility, it can be preferably used in the form of an aqueous solution.

The salt of the epoxy-amine adduct of the present invention has at least part or all of the basic group (especially an amine group, -NH- group) possessed by the compound [I] by at least the acid of the acid [II] Since the base reacts to form a salt, it has excellent water solubility, and can be preferably used in an aqueous solution. Moreover, since it can be easily converted into a basic group (especially an amine group, an -NH- group) by thermal decomposition or other treatment (for example, treatment with a strong base, etc.), it can be converted into an amine group, -NH Since the compound [I] is a base, the adhesion improving effect of the resin and the additive in the polymer-based composite exhibited by the compound [I] can be exhibited. Further, it is a matter of course that the salt of the epoxy-amine adduct of the present invention has a structure in which only one of the basic groups of the compound [I] is a salt (that is, has an amine group, a -NH- group). In the case of the compound [I], it does not particularly convert into the compound [I], and it has an effect of improving the adhesion between the thermoplastic resin and the additive in the polymer-based composite such as the fiber-reinforced composite material or the nano-composite.

The salt of the epoxy-amine adduct of the present invention can also be used as it is, and can also be used as a solution or a dispersion. In particular, since the salt of the epoxy-amine adduct of the present invention is excellent in water solubility, it can be preferably used in the form of an aqueous solution (containing the epoxy-amine adduct of the present invention (the epoxy-amine addition of the present invention) The aqueous solution which is an essential component of the first and second aspects of the product is referred to as "the aqueous solution of the present invention"). In particular, even when the concentration of the aqueous solution (the aqueous solution of the present invention) is low, the salt of the epoxy-amine adduct of the present invention is likely to be precipitated due to the precipitation of the dissolved matter, so that various states can be obtained. Use. The aqueous solution of the present invention can be used for various purposes (for example, water-based paints, sizing agents, etc.) to be described later. Further, the concentration of the epoxy-amine adduct of the present invention in the aqueous solution of the present invention is not particularly limited and may be appropriately selected.

The use of the epoxy-amine adduct of the present invention (the first and second aspects of the epoxy-amine adduct of the present invention) is not particularly limited. For example, the epoxy-amine adduct of the present invention can be used for an adhesion improver (adhesive improver) for improving the adhesion between a thermoplastic resin and an additive in a polymer-based composite. A compatibilizing enhancer (enhancement improver) for improving adhesion to an adherend, and a compatibilizing enhancer for enhancing solubility of two or more different components (especially polymers) Various additives such as a dispersibility enhancer, a fluidity enhancer, a fluidity inhibitor, a plasticizer, an epoxy resin, etc., which are used for improving the dispersibility of the additive in the polymer-based composite. Adhesives; coatings; sealants; sizing agents and the like. Moreover, it can also be preferably used for the use of a product (for example, an aqueous coating material) which uses water or a solvent which has water as a main component as a medium. Further, the water-based paint is a paint containing water or a solvent containing water as a main component (generally including a binder component, a pigment, etc.). By using the epoxy-amine adduct of the present invention, an aqueous coating material containing the epoxy-amine adduct as an essential component can be obtained.

 <Thermoplastic resin composition>  

A thermoplastic resin composition can be obtained by blending (mixing) the epoxy-amine adduct of the present invention (the first and second aspects of the epoxy-amine adduct of the present invention) with a well-known or conventional thermoplastic resin. (the case of "the thermoplastic resin composition of the present invention"). The thermoplastic resin is not particularly limited, and examples thereof include polyolefin (for example, polyethylene, polypropylene, polybutadiene, etc.), vinyl polymer (for example, acrylic resin, polystyrene, etc.), and 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 Diester, polybutylene terephthalate), polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyacetal, polyphenylene ether, polyphenylene sulfide, polyether oxime, polyether ether ketone, etc. Thermoplastic resin. However, the above-mentioned "thermoplastic resin" does not include the epoxy-amine adduct of the present invention. Further, in the thermoplastic resin composition of the present invention, the thermoplastic resin may be used singly or in combination of two or more.

The thermoplastic resin composition of the present invention [containing at least the thermoplastic resin composition of the epoxy-amine adduct of the present invention and a thermoplastic resin], in particular, a curable resin composition (for example, a thermosetting resin composition, photohardening) Compared with a resin composition or the like, it has an advantage that it can be formed in a short time. Therefore, the thermoplastic resin composition of the present invention can be particularly preferably used for applications requiring a reduction in molding time (for example, for automotive parts and the like).

The content (mixing amount) of the thermoplastic resin in the thermoplastic resin composition of the present invention is not particularly limited, and is preferably from 0.1 to 99.9% by weight, more preferably from 1 to 99% by weight based on the total amount (100% by weight) of the thermoplastic resin composition. 99% by weight, further preferably 2 to 98% by weight. When the content is 0.1% by weight or more, the heat resistance and mechanical properties (such as toughness) of the polymer-based composite (especially 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 thermoplastic resin in the polymer-based composite (especially the fiber-reinforced composite material) and the additive (especially the reinforcing fiber) is further improved. tendency.

In the thermoplastic resin composition of the present invention, the epoxy-amine adducts of the present invention may be used singly or in combination of two or more.

The content (doping amount) of the epoxy-amine adduct of the present invention in the thermoplastic resin composition of the present invention is not particularly limited, and is preferably 0.1 to 200 parts by weight, more preferably 100 parts by weight, based on the thermoplastic resin. 1 to 100 parts by weight, further preferably 2 to 50 parts by weight. The content of the epoxy-amine adduct of the present invention is 0.1 part by weight or more, and the thermoplastic resin in the polymer-based composite (especially the fiber-reinforced composite material) is densely bonded to the additive (especially the reinforcing fiber). There is a tendency for improvement in terms of consistency. On the other hand, when the content of the epoxy-amine adduct of the present invention is 200 parts by weight or less, heat resistance and mechanical properties (toughness, etc.) of the polymer-based composite (especially, fiber-reinforced composite material) are obtained. There is a tendency to improve.

The thermoplastic resin composition of the present invention may contain, in addition to the thermoplastic resin and the epoxy-amine adduct of the present invention, a polymerization initiator (a thermal polymerization initiator, a photopolymerization initiator, etc.), a curing agent, and the like. Hardening accelerator, antifoaming agent, leveling agent, coupling agent (decane coupling agent, etc.), surfactant, inorganic filler ( vermiculite, alumina, etc.), flame retardant, colorant, antioxidant, ultraviolet absorber Conventional additives such as ion adsorbents, pigments, phosphors, mold release agents, and the like.

The thermoplastic resin composition of the present invention is not particularly limited as long as it contains at least the epoxy-amine adduct of the present invention and a thermoplastic resin. Specifically, for example, each component constituting the thermoplastic resin composition can be stirred at a predetermined ratio. Mix and modulate. In addition, the mixing of the ingredients. In the mixing, well-known apparatuses such as a self-rotating public-transition mixer, a planetary mixer, a kneader, a dissolver, and the like can be used.

The epoxy-amine adduct of the present invention in the thermoplastic resin composition of the present invention can improve the thermoplastic resin in the composite material (fiber-reinforced composite material) of the reinforcing fiber and the thermoplastic resin such as carbon fiber due to high reactivity. Since the adhesion of the reinforcing fibers is enhanced, it is particularly preferably used as a resin composition (resin composition for a fiber-reinforced composite material) for forming a fiber-reinforced composite material. Specifically, the fiber-reinforced composite material is formed by impregnating or applying a thermoplastic resin composition of the present invention to a prepreg obtained by reinforcing fibers. More specifically, for example, the thermoplastic resin composition of the present invention is impregnated or coated with a reinforcing fiber in a molten state or in a state of being dissolved in a suitable solvent to obtain a prepreg (particularly a thermoplastic prepreg; The epoxy-amine adduct of the invention, a thermoplastic resin, and a prepreg of reinforcing fibers (especially carbon fibers) are further molded into the prepreg, whereby a fiber-reinforced composite material (including the thermoplastic resin of the invention) can be obtained a fiber reinforced composite of a composition and reinforcing fibers (especially carbon fibers). In particular, the thermoplastic resin composition (thermoplastic prepreg) of the present invention can be preferably used for applications requiring a reduction in molding time (for example, automotive parts and the like).

As the reinforcing fiber, a well-known or conventional reinforcing fiber can be used, and it is not particularly limited, and examples thereof include carbon fiber, glass fiber, polyarylene fiber, boron fiber, graphite fiber, tantalum carbide fiber, high-strength polyethylene fiber, and carbonization. Tungsten fiber, polyparaphenylene benzophenone 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 fiber, glass fiber, and polyamidamide fiber are preferred from the viewpoint of mechanical properties (strength and toughness). Further, the reinforcing fibers may be used singly or in combination of two or more.

Further, the reinforcing fiber may be a well-known or conventional surface treatment agent to which a coupling treatment, an oxidation treatment, a coating treatment, or the like is applied.

The form of the reinforcing fiber is not particularly limited, and examples thereof include a form of a filament (long fiber), a form of a tow, a form of a unidirectional material in which a tow is arranged in a single direction, a form of a woven fabric, and a form of a non-woven fabric. Wait. Examples of the woven fabric of the reinforced fiber include plain weave, twill weave, satin woven fabric, or a sheet in which the fiber bundle is unidirectionally woven or represented by a non-twist fabric (Non-Crimp Fabric). A suture piece or the like that is sewn without loosening.

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

The method of impregnating or applying the thermoplastic resin composition of the present invention to the reinforcing fibers is not particularly limited, and it can be carried out by a method of impregnation or coating in a method for producing a well-known or conventional prepreg.

The fiber-reinforced composite material of the present invention is formed of the prepreg of the present invention as described above, and the production method thereof is not particularly limited, and it can be produced by a well-known or conventional method, for example, a hand lamination method, a prepreg method, RTM method, pultrusion method, filament winding method, spray method, pultrusion method, melt impregnation method, powder method, and the like.

The fiber reinforced composite material of the present invention can be used as a material of various structures, and is not particularly limited. For example, it is preferably used as an aircraft fuselage, a main wing, a tail wing, a rotating blade, a fairing, a hood, a door, etc.; Motor shell, main wing, etc.; body structure of artificial satellite; automobile parts such as chassis of automobile; body structure of railway vehicle; body structure of bicycle; body structure of ship; blade of wind power generation; The material of the structure such as a fishing rod; a tennis racket; a golf club; a robot arm; a cable (for example, a core material of a cable, etc.).

 <Sizing agent>  

The epoxy-amine adduct of the present invention (the first and second aspects of the epoxy-amine adduct of the present invention) is as described above, and a hydroxyl group, a carboxyl group, an epoxy group, or the like is present on the surface of the reinforcing fiber. Since the functional group has high reactivity and can effectively improve the adhesion between the thermoplastic resin and the reinforcing fiber in the fiber-reinforced composite material, it can be preferably used as a sizing agent (especially a sizing agent for carbon fibers). Further, the so-called sizing agent is applied (coated) to the reinforcing fiber in order to improve the workability in the manufacturing step of the reinforcing fiber, the high-order processing step (fabric step, prepreg step, other forming step). Treatment agents are also known as bolsters. In the present specification, a sizing agent containing the epoxy-amine adduct of the present invention is referred to as "the sizing agent of the present invention".

The sizing agent of the present invention may contain an epoxy-amine adduct of the present invention as an essential component, and may contain a solvent, other additives, etc. in addition to the epoxy-amine adduct of the present invention. It may also be composed only of the epoxy-amine adduct of the present invention (the epoxy-amine adduct itself of the present invention). Further, the epoxy-amine adduct of the present invention in the sizing agent of the present invention may be in the form of a salt, for example, a salt of the epoxy-amine adduct of the present invention, or an aqueous solution or dispersion containing the salt. Liquid, etc. In the sizing agent of the present invention (especially, a sizing agent for carbon fibers), a water-soluble one can be used as the epoxy-amine adduct of the present invention.

The solvent to be contained in the sizing agent of the present invention is not particularly limited, and examples thereof include water; aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; and benzene, toluene, and xylene. An aromatic hydrocarbon such as ethylbenzene; a halogenated hydrocarbon such as chloroform, dichloromethane or 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, and An ether such as an alkane; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ester of methyl acetate, ethyl acetate, isopropyl acetate or butyl acetate; N,N-dimethyl A guanamine such as formamide or N,N-dimethylacetamide; a nitrile such as acetonitrile, propionitrile or benzonitrile; an alcohol such as methanol, ethanol, isopropanol or butanol; and dimethyl hydrazine. Among them, water and alcohol (especially water) are preferred in that the load on the environment and the working environment is small. That is, the sizing agent of the present invention may be a solution (especially an aqueous solution) or a dispersion of the epoxy-amine adduct of the present invention containing water and/or an alcohol (either or both of water and alcohol). (especially aqueous dispersion). Further, the solvent may be used singly or in combination of two or more. Wherein, in the case where the epoxy-amine adduct of the present invention is a salt (for example, the second aspect of the epoxy-amine adduct of the present invention), the sizing agent of the present invention is easily prepared to a low concentration. The point of the aqueous solution is very beneficial.

The sizing agent of the present invention may further contain various additives such as a lubricant such as a fatty acid, a guanamine or an ester; a coupling agent such as a decane coupling agent or a titanium coupling agent.

The content (mixing amount) of the epoxy-amine adduct, the solvent, and the additive of the present invention in the sizing agent of the present invention is not particularly limited, and may be appropriately adjusted.

The sizing agent of the present invention (for example, a sizing agent for carbon fibers) can be preferably used for a product (for example, an aqueous paint or the like) which uses water or a solvent containing water as a main component as a medium. For example, using the sizing agent of the present invention, an aqueous solution or an aqueous coating material containing the sizing agent as an essential component can be obtained.

 <carbon fiber coated with sizing agent>  

The sizing agent-coated carbon fiber (carbon fiber to which the sizing agent is attached) can be obtained by coating (coating) the sizing agent (carbon fiber sizing agent) of the present invention on carbon fibers (referred to as "coating of the present invention" The case of the carbon fiber of the slurry). That is, the sizing agent-coated carbon fiber of the present invention is a carbon fiber coated with a sizing agent for carbon fibers.

The method of applying the sizing agent of the present invention to carbon fibers is not particularly limited, and examples thereof include a method of immersing carbon fibers in the sizing agent of the present invention, and a method of contacting the rolls to which the sizing agent of the present invention is attached, with carbon fibers. A well-known or conventional method of a method in which a sizing agent of the invention is sprayed into a carbon fiber in a mist form. Further, the application of the sizing agent of the present invention may be carried out for the entire carbon fiber or for a part of the surface. Further, the coating thickness and the coating amount can be appropriately adjusted, and are not particularly limited.

After the sizing agent of the present invention is applied, heat treatment may be performed as needed. The conditions of the above heat treatment are not particularly limited, and the heating temperature is preferably 40 to 300 ° C, more preferably 60 to 250 ° C. Further, the heating time is 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 carried out continuously in one stage, or may be carried out intermittently in two or more stages. Further, the above heat treatment is generally carried out in order to promote impregnation of the sizing agent while drying the solvent. The above heat treatment can be carried out by a well-known or conventional method (for example, heating using a hot air oven, etc.).

The sizing agent-coated carbon fiber of the present invention may be one which is further coated with the above thermoplastic resin after the sizing agent of the present invention is applied and heat-treated. According to the type of the thermoplastic resin described above, the viscosity of the carbon fiber to which the sizing agent is applied is reduced, and the handleability (handleability) is improved. The method of the above coating is not particularly limited, and for example, it can be carried out in the same manner as the application of the above-mentioned slurry to the carbon fiber of the present invention. Further, the above coating may be performed on the entire surface of the carbon fiber to which the sizing agent is applied, or on a part of the surface. Further, the coating thickness and the coating amount can be appropriately adjusted, and are not particularly limited.

Since the sizing agent-coated carbon fiber of the present invention is coated with the epoxy-amine adduct of the present invention in the slurry of the present invention, it is excellent in adhesion to the resin. Further, the epoxy-amine adduct of the present invention as the sizing agent of the present invention can be suitably used for processing at a high temperature (for example, a carbon fiber coated with a sizing agent), especially when it is excellent in heat resistance. Manufactured) can also contribute to the productivity improvement of fiber reinforced composites. Further, as the epoxy-amine adduct of the present invention in the sizing agent of the present invention, the use of a glass transition temperature of a certain degree is used to prevent contamination of the processing machine (roller, etc.), and also The reinforcing fiber coated with the sizing agent (for example, the carbon fiber coated with the sizing agent) imparts excellent texture and workability. In addition, since the sizing agent of the present invention has an excellent function as a general sizing agent, such as a function of converging carbon fibers and a function of imparting flexibility to carbon fibers, the sizing agent-coated carbon fiber of the present invention Good workability and excellent high-order workability.

Since the sizing agent-coated carbon fiber of the present invention has the above characteristics, the fiber reinforced composite material containing the carbon fiber coated with the sizing agent and various matrix resins (thermoplastic resin) (fiber reinforced with the carbon fiber coated with the sizing agent of the present invention) Composite material), has excellent heat resistance and mechanical strength, and has high productivity. Further, the fiber-reinforced composite material can be produced by a well-known or conventional method such as the above-described method for producing a fiber-reinforced composite material. Further, as the fiber-reinforced composite material, a material which is various structures as described above can be preferably used.

In the sizing agent-coated carbon fiber of the present invention, for example, a sizing agent (carbon fiber sizing agent) containing the water-dispersed resin composition of the present invention described later may be used instead of the above-mentioned sizing agent (carbon fiber for the present invention). Sizing agent), and obtained in the same manner.

 <Water-dispersed resin composition>  

The epoxy-amine adduct of the present invention (the first and second aspects of the epoxy-amine adduct of the present invention) can be used to obtain a water-dispersed resin composition. The water-dispersed resin composition preferably contains the epoxy-amine adduct of the present invention (particularly, the first aspect of the epoxy-amine adduct of the present invention), and a urethane resin. A water-dispersible resin composition (an aqueous dispersion containing the epoxy-amine adduct of the present invention and a urethane resin; and a case of the "water-dispersed resin composition of the present invention").

In addition, the "water-dispersible type" in the water-dispersible resin composition of the present invention means that at least a part of the epoxy-amine adduct and the urethane resin of the present invention are not dissolved in the aqueous medium. Further, it includes a state of being suspended and dispersed, a state of being emulsified and dispersed, and the like. In the water-dispersed resin composition of the present invention, at least the epoxy-amine adduct of the present invention is preferably emulsified and dispersed in an aqueous medium.

The epoxy-amine adduct of the present invention which is a constituent component of the water-dispersed resin composition of the present invention is as described above. Among them, the first aspect of the epoxy-amine adduct of the present invention is preferably used. Further, in the water-dispersible resin composition of the present invention, the epoxy-amine adduct of the present invention may be used alone or in combination of two or more.

The content (doping amount) of the epoxy-amine adduct of the present invention in the water-dispersible resin composition of the present invention is not particularly limited, and is relative 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, particularly preferably 20 to 80% by weight.

 [urethane resin]  

In the water-dispersible resin composition of the present invention, the urethane resin is not particularly limited, and a resin having a polyurethane structure obtained by reacting a polyfunctional isocyanate with a polyol can be used. Further, the urethane resin may be used alone or in combination of two or more.

The polyfunctional isocyanate is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule. The polyfunctional isocyanate includes, for example, an aliphatic polyfunctional isocyanate, an alicyclic polyfunctional isocyanate, an aromatic polyfunctional isocyanate, an aromatic aliphatic polyfunctional isocyanate, and the like. The polyfunctional isocyanate may be used alone or in combination of two or more.

Examples of the aliphatic polyfunctional isocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, and 1,6-hexamethylene group. Diisocyanate, 1,2-propylidene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1, An aliphatic diisocyanate having 2 to 12 carbon atoms such as 5-pentamethylene diisocyanate, dodecamethylene diisocyanate, and lysine diisocyanate (excluding carbon in NCO).

Examples of the alicyclic polyfunctional isocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 3-isocyanatomethyl group. 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(isocyanatomethyl)cyclohexane, norbornane diisocyanate An alicyclic diisocyanate having 4 to 18 carbon atoms (excluding carbon in NCO).

Examples of the aromatic polyfunctional isocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-toluene diisocyanate. Naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 4,4'-diphenyldiisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane Diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'- An aromatic diisocyanate having 6 to 15 carbon atoms such as dimethyldiphenylmethane-4,4'-diisocyanate or 4,4'-diphenylpropane diisocyanate (excluding carbon in NCO).

Examples of the aromatic aliphatic polyfunctional isocyanate include 1,3-xylylene diisocyanate, 1,4-benzyldimethylisocyanate, and ω,ω'-diisocyanate. 1,4-1,4-diethylbenzene, 1,3-bis(1-isocyanato-1-methylethyl)benzene, 1,4-bis(1-isocyanato-1-methyl Aromatic aliphatic diisocyanate having 8 to 15 carbon atoms (excluding carbon in NCO) such as ethyl)benzene or 1,3-bis(α,α-dimethylisocyanatomethyl)benzene.

As the polyfunctional isocyanate, 1,6-hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-bis(isocyanatomethyl)cyclohexane are preferably used. Alkane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane Diisocyanate, 1,3-benzenedimethyl diisocyanate, 1,4-benzyldimethylisocyanate, norbornane diisocyanate, 1,3-bis(α,α-dimethylisocyanatomethyl )benzene.

Further, as the polyfunctional isocyanate, a dimer or a trimer derived from the above-exemplified aliphatic polyfunctional isocyanate, alicyclic polyfunctional isocyanate, aromatic polyfunctional isocyanate or aromatic aliphatic polyfunctional isocyanate may be used. Reaction product, modified substance or polymer (for example, dimer or trimer of diphenylmethane diisocyanate, reaction product of trimethylolpropane and toluene diisocyanate, trimethylolpropane and hexamethylene A reaction product of a bis-isocyanate, a polymethylene polyphenyl isocyanate, a polyether polyisocyanate, a polyester polyfunctional isocyanate or the like).

Examples of the polyhydric alcohol 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 6,000, still more preferably 800 to 4,000. Each of the low molecular weight polyol and the long-chain polyol may 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-butylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,2-pentane. Glycol, 2,3-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,4- Polyol (especially diol) such as cyclohexanedimethanol, glycerol, trimethylolpropane, bisphenol A or the like.

As the polyether polyol, for example, in addition to polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol (PTMG), etc., a plurality of alkylene oxides may be cited as ethylene oxide. a monomer component (alkylene oxide-other alkylene oxide) copolymer or the like such as a propylene oxide copolymer.

As the polyester polyol, for example, a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a ring-opening polymer of a cyclic ester (lactone); and three components of a polyhydric alcohol, a polyvalent carboxylic acid, and a cyclic ester can be used. Reactions, etc. In the condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid, as the polyhydric alcohol, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, or 1, can be used. 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-nonanediol, glycerol, trimethylolpropane, trimethylolethane, Cyclohexanediol (such as 1,4-cyclohexanediol), cyclohexanedimethanol (such as 1,4-cyclohexanedimethanol), bisphenols (such as bisphenol A), and sugar alcohols ( Xylitol or sorbitol, etc.). On the other hand, examples of the polyvalent carboxylic acid include malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, sebacic acid, and dodecanedioic acid. Aliphatic dicarboxylic acid; alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, p-phenylene An aromatic dicarboxylic acid such as formic acid or trimellitic acid. Further, 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. The above-exemplified person or the like can be used as the polyol, the polyvalent carboxylic acid or the cyclic ester in the reaction product composed of the three components.

Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol with phosgene, a chloroformate, a dialkyl carbonate or a diaryl carbonate; and a ring-opening polymer of a cyclic carbonate (alkylene carbonate or the like). Wait. Specifically, in the reactant of a polyol and phosgene, as the polyol, the above-exemplified polyol (for example, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol) can be used. , neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, etc.). Further, examples of the alkylene carbonate in the ring-opening polymer of the cyclic carbonate include ethyl carbonate, methyl trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. Further, the polycarbonate polyol may be a compound having a carbonate bond in the molecule and a terminal hydroxyl group, and may have both a carbonate bond and an ester bond. Typical examples of the polycarbonate polyol include polyhexamethylene carbonate diol, a diol obtained by subjecting a lactone to ring-opening addition polymerization to polyhexamethylene carbonate diol, and polyhexamethylene a cocondensate of a carbonate diol with a polyester diol or a polyether diol, and the like.

The polyolefin polyol is a polyol having an olefin as a component of a skeleton (or main chain) of a polymer or a copolymer and having at least two hydroxyl groups in a molecule (particularly, a 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 site other than the terminal (for example, Isobutene, etc.), and may also be a diene (for example, butadiene, isoprene, etc.). Typical examples of the polyolefin polyol include butadiene homopolymer, isoprene homopolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer, butadiene- The end of the butadiene or isoprene polymer is changed by an acrylonitrile copolymer, a butadiene-2-ethylhexyl acrylate copolymer, a butadiene-n-octadecyl acrylate copolymer or the like. The quality is hydroxyl.

The polyacrylic polyol is a polyol having a (meth) acrylate as a component of a skeleton (or main chain) of a polymer or a copolymer and having at least two hydroxyl groups in a molecule (particularly, a terminal). As the (meth) acrylate, an alkyl (meth) acrylate [for example, a C _1-20 alkyl (meth) acrylate or the like] is preferably used. Further, as the polyol, all materials other than those listed herein can be used.

Further, as the chain extender, a polyamine can be used as the above urethane resin. The molecular weight of the polyamine is usually less than 500, preferably 300 or less. Typical examples of the polyamine include hexamethylenediamine, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 4,4'-methylenebis-2. a polyamine (especially a diamine) such as chloroaniline.

In the water-dispersed resin composition of the present invention, as the urethane resin, an emulsion type urethane resin is preferably used. The emulsion type urethane resin may be a forced emulsified urethane resin using a surfactant as an emulsifier or a self-emulsifying urethane resin having a hydrophilic group introduced into the resin. One. Among them, as the emulsion type urethane resin, a self-emulsifiable urethane resin is particularly preferred. Examples of the hydrophilic group of the self-emulsifiable urethane resin include a sulfonic acid group, a carboxyl group, a hydroxyl group, a polyethylene group, an amine group, and a mono- or disubstituted amine group. Among these, the hydrophilic group is preferably a sulfonic acid group, a carboxyl group, a hydroxyl group or a polyethylene group.

As a commercial item of the emulsion type urethane resin [polyurethane emulsion (urethane resin emulsion)], for example, the trade name "UCOAT UX-150" of Sanyo Chemical Industry Co., Ltd. is mentioned. "UCOAT UX-200", "UCOAT UX-300", "UCOAT UX-310", "UCOAT UWS-145", "PERMARIN UA-150", "PERMARIN UA-300", "PERMARIN UA-310", "PERMARIN UA-368", "UPRENE UXA-307"; the trade name "KP-2820" of Matsumoto Oil & Fats Co., Ltd.; the product name "Superflex 150HS" of the first industrial pharmaceutical company (shares); Names "HYDRAN AP-20", "HYDRAN AP-30F", "HYDRAN AP-40F", "HYDRAN WLS-213"; TAISEI FINE CHEMICAL's trade name "ACRIT WBR-2018", "ACRIT WBR-016U" ", "ACRIT WEM-3008" and so on.

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

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

 [Surfactant]  

The water-dispersed resin composition of the present invention may contain a surfactant. As the surfactant, a well-known or conventional surfactant can be used, and it is not particularly limited, and examples thereof include a well-known anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a high surfactant. Molecular dispersants, etc. The surfactant mainly has a function of stably dispersing the epoxy-amine adduct of the present invention in the water-dispersed resin composition of the present invention.

Examples of the anionic surfactant include dodecylbenzenesulfonate, alkylenedisulfonate, sodium dialkyl succinate sulfonate, and disodium salt of monoalkyl succinate sulfonate. a sulfonate type such as a sodium salt of a naphthalenesulfonic acid condensate condensate or an α-olefin sulfonate; a polyoxyethylene methyl polycyclic phenyl ether sulfate salt, a polyoxyethylene ethyl aryl ether sulfate salt, a poly Sulfate type such as oxygen-extended ethyl alkyl ether sulfate salt, polyoxy-extension ethyl castor oil ether sulfate salt; phosphate type such as polyoxyalkylene alkyl alkyl ether phosphate; sodium polyacrylate salt, etc. . In particular, the anionic surfactant is preferably a sulfate salt type surfactant, and specifically, the brand names "NEWCOL707SF", "NEWCOL707SFC", "NEWCOL707SN", and "NEWCOL780SF" (above, Japanese emulsifier ( Commercial products such as shares).

In addition to the above, as the anionic surfactant, for example, a reactive surfactant having a radically polymerizable polymerizable functional group can be used, and for example, it can be exemplified by a sulfate salt of polyoxyethylene ethyl phenyl ether. 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, examples of the former include "AQUALON KH-10" and "AQUALON HS-10" (above, the first industrial pharmaceutical company); and the product name "ADEKA REASOAP SE-10N" (ADEKA). (share) system, etc. In addition, examples of the latter include the trade names "Eleminol JS2" and "Eleminol RN-30" (above, Sanyo Chemical Industry Co., Ltd.); the trade names "Latemul S-180" and "Latemul S-180A" ( Above, Kao (share) system, etc.

Examples of the nonionic surfactant include polyoxyethylene ethyl 2-ethylhexyl ether, polyoxyethyl oleyl ether, polyoxyethylidene tridecyl ether, and polyoxyethyl ether castor oil. Ether, polyoxyethylene ethyl cetyl ether, polyoxyethylene ethyl stearyl ether, polyoxyalkylene 2-ethylhexyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl a polyoxyalkylene alkyl ether type such as an alkyl ether; a polyoxyalkylene polycyclic phenyl ether type (polycyclic phenyl ether type) such as polyoxyethylidene polyphenylene ether; sorbitan Laurate, sorbitan stearate, sorbitan oleate, sorbitan trioleate, polyoxyethyl sorbitan laurate, polyoxyethyl sorbitan stearate A sorbitan derivative of ester, polyoxyethylene ethyl sorbate oleate, polyoxyethylene ethyl sorbate trioleate, polyoxyalkylene sorbitan fatty acid ester, etc. Polyoxyalkylene fats such as ethyl aryl ether, polyoxyethylene ethyl cumyl phenyl ether, polyoxyethylene ethyl oxypropyl block polymer, polyoxyethyl oleate Acid ester, polyoxyalkylene ethyl alkylamine ether Alkylene oxide adduct 2-butyl-hydroxy -1,3-β- oxide, fatty acyl derivatives, polyhydric alcohol derivatives and the like. Among them, a polyoxyalkylene ether type nonionic surfactant is preferable, and specifically, the trade names "Noigen EA-197D", "Noigen XL", "Noigen ET-B", and " Noigen TDS" (above, the first industrial pharmaceutical company). Further, a polyoxyalkylene fatty acid ester such as polyoxyethylidene oleate is preferably used, and specifically, the trade names "NEWCOL150", "NEWCOL170", "NEWCOL180", "NEWCOL180T" (above) can be used. , Japan emulsifier (stock) system, etc.

In addition to the above, examples of the nonionic surfactant include a surfactant in which a radically polymerizable unsaturated double bond is introduced into a molecule of polyoxyethylidene ethyl phenyl ether, and specifically, The product name "AQUALON RN-20", "AQUALON RN-50" (above, the first industrial pharmaceutical company); trade name "ADEKA REASOAP NE-20", "ADEKA REASOAP NE-40" (above) , ADEKA system (shares) and so on.

Examples of the cationic surfactant include a tetramethylammonium salt (for example, tetramethylammonium chloride or tetramethylammonium hydroxide), an alkyltrimethylammonium salt, and a dialkyldimethylammonium salt. a quaternary ammonium salt type such as an alkyl dimethyl benzyl ammonium salt, a pyridinium salt, an alkyl isoquinolinium salt, a benzothonium chloride or the like; an alkylamine salt (for example, Amine salt type of monomethylamine hydrochloride, dimethylamine hydrochloride, etc., amino alcohol fatty acid derivative, polyamine fatty acid derivative, imidazolium, etc.; butylpyridinium chloride, chlorinated 12 A pyridinium salt type such as an alkylpyridinium or the like.

Examples of the amphoteric surfactant include alanine, dodecyl bis(aminoethyl)glycine, bis(octylaminoethyl)glycine, and N-alkyl-N,N-di Methylammonium 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-maleic acid copolymer, etc.) and Various metal salts or ammonium salts, acrylic polymers (polyacrylic acid, copolymer of acrylic acid, etc.) and various metal salts or ammonium salts thereof, maleic acid monoester copolymers, acrylonitrile methylpropane sulfonic acid copolymers, poly Ester system, CMC (carboxymethyl cellulose), HEC (hydroxyethyl cellulose), hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl starch, alginic acid, pectic acid and the like.

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-dispersible resin composition of the present invention is not particularly limited, and is preferably 0.01 to 500 parts by weight based on 100 parts by weight of the epoxy-amine adduct of the present invention. More preferably, it is 0.1 to 200 parts by weight, further preferably 0.5 to 100 parts by weight, particularly preferably 5 to 80 parts by weight. When the content of the surfactant is 0.01 parts by weight or more, the epoxy-amine adduct of the present invention tends to be more stably dispersed. On the other hand, when the content of the surfactant is 500 parts by weight or less, it is economically advantageous, or the heat resistance and 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 as the surfactant, the ratio of the amount of the surfactant used [anionic surfactant/nonionic surfactant] (weight ratio) is not particularly The limit is preferably 95/5 to 10/90, more preferably 90/10 to 30/70, still more preferably 85/15 to 50/50.

The water-dispersed resin composition of the present invention contains a composition of 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, and may contain 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. a halogenated hydrocarbon such as chloroform, dichloromethane or 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, An ether such as an alkane; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ester of methyl acetate, ethyl acetate, isopropyl acetate or butyl acetate; N,N-dimethyl A guanamine such as formamide 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 and environmental protection. The content (mixing amount) of the organic solvent in the water-dispersible resin composition of the present invention is not particularly limited, and is preferably 10% by weight or less based on the total amount (100% by weight) of the water-dispersed 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 (the case may be referred to as "other components"). Examples of the other component include various additives such as a lubricant such as a fatty acid, a guanamine or an ester; a coupling agent such as a decane coupling agent or a titanium coupling agent.

The preparation method (manufacturing method) of the water-dispersed resin composition of the present invention may be, for example, (i) mixing the aqueous dispersion containing the epoxy-amine adduct of the present invention with the urethane resin emulsion. a method, (ii) a method of emulsification after mixing an epoxy-amine adduct of the present invention with a urethane resin, and (iii) adding to an aqueous dispersion containing an epoxy-amine adduct of the present invention a method of mixing a urethane resin, (iv) a method of adding an epoxy-amine adduct of the present invention and a surfactant (if necessary) to a urethane resin emulsion, and mixing the same Either. Among these, from the viewpoint of easily obtaining a stable emulsion, the method of the above (i) or (ii) is preferred.

For the "mixing" in each of the above methods, for example, a dispersing machine, a homomixer, a bead mill, a jet mill, a roll mill, a hammer mill, a vibration mill, a ball mill, a sand mill (sand can be used) Mill), pearl mill, SPIKE MILL, agitator mill, coball mill, etc. (especially medium agitating disperser) .

The above aqueous dispersion containing an epoxy-amine adduct of the present invention can be prepared, for example, by mixing the epoxy-amine adduct of the present invention, a surfactant, an aqueous medium, and other components as needed. The epoxy-amine adduct of the invention is dispersed (for example, suspension-dispersed, 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, a mixture containing the epoxy-amine adduct of the present invention, a surfactant, and an aqueous medium can be prepared by using the above dispersing machine. In addition, in order to reduce the content of the organic solvent in the water-dispersed resin composition of the present invention, it may be further subjected to a treatment such as drying under reduced pressure.

The water-dispersed resin composition of the present invention can also be obtained by using the above-described sizing agent of the present invention (for example, a sizing agent for carbon fibers) instead of the epoxy-amine adduct of the present invention. In this case, a water-dispersed resin composition containing at least the sizing agent of the present invention (for example, a sizing agent for carbon fibers), a urethane resin, and a surfactant or the like as needed (the present invention) can be obtained. Water-dispersed resin composition).

 [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 respect to a functional group such as a hydroxyl group, a carboxyl group or an epoxy group which is present on the surface of the reinforcing fiber, and contains Since the urethane resin is formed, the formed film is excellent in flexibility. Therefore, the adhesion of the resin (especially thermoplastic resin) in the fiber-reinforced composite material to the reinforcing fibers (especially glass fibers, carbon fibers) can be effectively improved.

As a more specific method of using the prepreg for obtaining a fiber-reinforced composite material, for example, in the case where the resin composition of the present invention is a resin composition containing at least the epoxy-amine adduct of the present invention and a thermoplastic resin, The resin composition is impregnated or coated with a reinforcing fiber in a molten state or dissolved in a suitable solvent to obtain a prepreg (thermoplastic prepreg), and the prepreg is further molded. Fiber reinforced composites. On the other hand, when the resin composition of the present invention is a resin composition containing at least the epoxy-amine adduct of the present invention and a curable resin, the resin composition is impregnated or coated with a reinforcing fiber. The prepreg (curable prepreg) further hardens and forms the curable resin in the prepreg, whereby a fiber-reinforced composite material can be obtained.

In particular, the above thermoplastic prepreg can be preferably used for applications requiring a reduction in forming time (for example, automotive parts and the like). Further, in the thermoplastic prepreg, the water-dispersed resin composition of the present invention is in the form of a water-dispersible resin composition (aqueous dispersion), and therefore 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 (especially a sizing agent for glass fibers, 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.

By using the water-dispersed resin composition of the present invention as a sizing agent, impregnating or coating the resin composition on the reinforcing fiber, a prepreg of the fiber-reinforced composite material precursor material can be obtained (also referred to as a sizing material) It is the case of "prepreg of the present invention").

As the reinforcing fiber, a known or conventional reinforcing fiber can be used, and it is not particularly limited. For example, the above-exemplified reinforcing fiber can be used. Among them, carbon fiber, glass fiber, and polyamidamide fiber are preferred from the viewpoint of mechanical properties (strength and toughness). Further, the reinforcing fibers may be used singly or in combination of two or more. Further, the reinforcing fiber may be a well-known or conventional surface treatment to which a coupling treatment, an oxidation treatment, a coating treatment, or the like is applied. Further, the form of the reinforcing fiber is not particularly limited, and for example, a reinforcing fiber of the above-exemplified form can be used.

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 applying the water-dispersed resin composition of the present invention to the reinforcing fiber is not particularly limited, and may be impregnated or dried by a known method or a conventional method for producing a prepreg as described above. The method of coating is carried out. 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 roll of the water-dispersed resin composition of the present invention into contact with the reinforced fiber, and dispersing the water of the present invention A well-known or conventional method in which a resin composition is sprayed in a mist form and sprayed on a reinforced fiber. Further, the application of the water-dispersed resin composition of the present invention may be carried out for the entire surface of the reinforcing fibers or for a part of the surface. Further, the coating thickness or the coating amount and the amount of impregnation thereof can be appropriately adjusted, and are not particularly limited.

The prepreg of the present invention may be obtained by subjecting the water-dispersed resin composition of the present invention to a reinforced fiber after being impregnated or coated with a reinforcing fiber. The conditions of the above heat treatment are not particularly limited, and the heating temperature is preferably 40 to 300 ° C, more preferably 60 to 250 ° C. Further, the heating time is 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 carried out continuously in one stage, or may be carried out intermittently in two or more stages. Further, the heat treatment is generally carried out in order to promote impregnation of the reinforcing fibers with the water-dispersible resin composition of the present invention, and to dry and remove volatile matter (aqueous medium or the like). The above heat treatment can be carried out by a well-known or conventional method (for example, heating using a hot air oven, etc.).

The prepreg of the present invention may be one in which a thermoplastic resin is further applied after impregnating or applying the water-dispersed resin composition of the present invention to a reinforcing fiber. According to the type of the thermoplastic resin, the prepreg of the present invention has a reduced viscosity and improved handleability (handleability). The method of the above coating 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 a reinforced fiber. Further, the above coating may be carried out comprehensively on the prepreg (when no thermoplastic resin is applied), or on a part of the surface. Further, the coating thickness and the coating amount can be appropriately adjusted, and are not particularly limited. Thereby, the prepreg of the present invention comprising the epoxy-amine adduct of the present invention, a thermoplastic resin, and reinforcing fibers (especially carbon fibers) can be obtained.

The thermoplastic resin is not particularly limited, and for example, a thermoplastic resin exemplified as a constituent component of the thermoplastic resin composition of the present invention can be used. Further, the thermoplastic resins may be used alone or in combination of two or more.

Among the prepregs of the present invention, the thermoplastic prepreg system is particularly effective, and can be shorter than a usual curable prepreg (for example, a thermosetting prepreg or a photocurable prepreg). The advantage of time shaping. Therefore, the thermoplastic prepreg of the present invention can be preferably used for applications requiring a reduction in molding time (for example, for automobile parts and the like).

The content (mixing amount) of the thermoplastic resin or the like in the prepreg of the present invention (especially, the prepreg using the water-dispersible resin composition of the present invention) is not particularly limited, and is a prepreg excluding the reinforcing fibers. The total amount (100% by weight) is preferably 0.1 to 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 and mechanical properties (strength and 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 thermoplastic resin and the reinforcing fibers in the fiber-reinforced composite material tends to be improved.

The content (doping amount) of the epoxy-amine adduct of the present invention in the prepreg of the present invention (especially the prepreg using the water-dispersible resin composition of the present invention) is not particularly limited, as opposed to thermoplastic 100 parts by weight of the resin or the like is preferably 0.1 to 200 parts by weight, more preferably 1 to 100 parts by weight, still more preferably 2 to 50 parts by weight. When the content of the epoxy-amine adduct of the present invention is 0.1 part by weight or more, the adhesion between the thermoplastic resin and the reinforcing fiber in the fiber-reinforced composite material tends to be 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 (strength and toughness) of the fiber-reinforced composite material tend to be high.

The prepreg of the present invention may additionally contain, 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 coupler). Mixtures, etc., surfactants, inorganic fillers (such as vermiculite, alumina, etc.), flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, pigments, phosphors, mold release agents, etc. Additives. The amount of such additives is not particularly limited.

A fiber-reinforced composite material (also referred to as "the fiber-reinforced composite material of the present invention") is formed from the prepreg of the present invention. More specifically, for example, the prepreg system of the present invention produces a fiber-reinforced composite material by molding the prepreg.

 [Fiber reinforced composite material]  

The fiber-reinforced composite material of the present invention is formed of the prepreg of the present invention (especially a prepreg using the water-dispersed resin composition of the present invention) as described above, and the production method thereof is not particularly limited and can be known by Or a conventional method, such as the method exemplified above. The fiber-reinforced composite material of the present invention is excellent in adhesion to a reinforcing fiber 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. For example, a material which is the above-exemplified structure can be preferably used.

The epoxy-amine adduct of the present invention (the first and second aspects of the epoxy-amine adduct of the present invention) is not particularly limited to the above-mentioned use, and can be widely used, for example, in papermaking. Paper processing field; followed by industrial field; ink, photographic industry; fiber industry; as a coagulant, clarifier, float; as a chelating resin, ion exchange resin, separation membrane, adsorbent; cosmetics, cosmetics (toiletery ); as a lubricant, rust inhibitor, dispersant; as a plating agent; in the field of biological and medical enzymes; as a cement additive, as a petroleum, and in various fields.

The epoxy-amine adduct of the invention is in papermaking. In the field of paper processing, for example, it can be used as a moist paper strength enhancer; to promote water removal in the papermaking step, to improve water repellency; as a yield improving agent for fine fibers, sizing agents, various fillers, pigments, dyes, and the like; Use of clarification of white water, papermaking and drainage treatment. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for the treatment of an epoxy-amine adduct of the present invention with an acid dye by the epoxy-amine adduct of the present invention. An ink jet recording paper prepared by improving the water resistance of a water-based ink; an oil-resistant paper treated with a reactant of a phosphate ester and an epoxy-amine adduct of the present invention; using a quaternized or ethoxylated a dyed paper of the epoxy-amine adduct of the present invention; an alkaline or neutral sizing agent using an anionic sizing agent and an epoxy-amine adduct (a yield agent) of the present invention; The softening, sizing, and wetting strength of the paper of the reaction product of the epoxy-amine adduct, the fatty acid, and the epichlorohydrin; the use of the polyphosphoric acid-based flame retardant and the epoxy-amine adduct of the present invention Heat-resistant paper; a deinking agent or the like of waste paper using an alkoxylated epoxy-amine adduct of the present invention. use.

The epoxy-amine adduct of the present invention can be used, for example, in the industrial field as a water-soluble adhesion promoter (layering. anchoring agent). More specifically, the epoxy-amine adduct of the present invention can be used, for example, for: an FRP article treated with the epoxy-amine adduct of the present invention; comprising the epoxy-amine adduct of the present invention and a polycyclic ring a water-dispersible composition of a reactant of an oxygen compound; a composition comprising a diene polymer and an epoxy-amine adduct of the present invention, and an adhesive composition for a masking tape; a rubber/metal adhesion promoter of a metal complex composed of an epoxy-amine adduct and a nickel or cobalt salt; a water-soluble vinyl acetate copolymer emulsion modified by the epoxy-amine adduct of the present invention a two-component type quick-curing aqueous adhesive for wood, tile, etc. comprising the epoxy-amine adduct of the present invention and ethyl acetylated polyvinyl alcohol; comprising the epoxy-amine adduct of the present invention A moisture-activated hot melt adhesive with a hydroxy-substituted organic compound and a compatible adhesive. use.

The epoxy-amine adduct of the present invention can be used, for example, in the field of ink and photographic industry to improve the storage stability and color contamination of a color developing solution, and antistatic in a silver halide photographic light-sensitive material. Sexual imparting; use of water fastening properties in inkjet compositions. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for a color development processing liquid containing diethylhydroxylamine and the epoxy-amine adduct of the present invention; A silver halide photographic light-sensitive material of an ion-conductive polymer complex composed of an epoxy-amine adduct and a metal salt; comprising the hydroxyethylated epoxy-amine adduct of the present invention and a water-soluble dye The aspect of the ink jet composition and the like. use.

In the field of the fiber industry, the epoxy-amine adduct of the present invention can be used, for example, for dyeing properties, shrinkage prevention, flameproof processing, and antistatic treatment of various fibers including cellulose fibers. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for an antistatic polyamine composition treated with a hydrazine of the epoxy-amine adduct of the present invention; An antistatic agent for synthesizing fibers of an amphoteric polymer obtained by adding an alkylene oxide adduct to an alkylene oxide and an ethylenically unsaturated monomer; adding the epoxy-amine adduct of the present invention to the fiber slurry and a fibrous sheet of an anionic latex; a functional fiber obtained by mixing the epoxy-amine adduct of the present invention and polyvinyl alcohol, dry spinning, and crosslinking by glutaraldehyde or the like; and the epoxy-amine addition of the present invention The appearance of the product and the hyaluronic acid treated flame retardant fiber. use.

The epoxy-amine adduct of the present invention can be used as a coagulant, a clarifier or a float as described above, and can be used, for example, as an exchanger for wastewater purification; as an aggregating agent for activated sludge; and for agglomeration of pulp wastewater a water treatment agent for removing organic and inorganic substances dispersed and emulsified in water; treatment of water containing waste paint in circulating water of a wet coating chamber; agglomeration and recovery of vermiculite dissolved in geothermal water; coal Aggregation with minerals; collection of harmful heavy metals contained in wastewater; use of oil for recovery from wastewater from petroleum recovery. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for an exchange agent for wastewater purification using a modified product of the epoxy-amine adduct of the present invention using cellulose or a derivative thereof. a flocculating agent for pulp wastewater comprising the epoxy-amine adduct and inorganic salt of the present invention; a porous water-treating material composed of polyethylene, vermiculite and the epoxy-amine adduct of the present invention; Aggregation of coal and minerals of an adduct of xanthogenate and an epoxy-amine adduct of the present invention; recovery from petroleum by using the reaction product of the epoxy-amine adduct of the present invention and epichlorohydrin The state of waste water and oil recovery. use.

The epoxy-amine adduct of the present invention can be used as a chelating resin, an ion exchange resin, a separation membrane or an adsorbent as described above, and can be used for: anion exchange resin; heavy metal adsorbent; chelate resin; uranium adsorption Adsorbent for low molecular metal chelate; composite membrane for high performance reverse osmosis; controlled release of microcapsule separation membrane using high electrolyte; ion selective electrode; acid gas adsorbent; separation membrane made of high concentration sugar liquid The use of etc. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for an anion exchange resin formed from the epoxy-amine adduct of the present invention and epihalohydrin or the like; The reaction product of the epoxy-amine adduct and carbon disulfide is added to the heavy metal adsorbent attached to the activated carbon; the epoxy-amine adduct of the present invention and the epichlorohydrin are grafted to the chloromethylated bridge. a chelating resin for styrene; a uranium adsorbent for forming a polyionic complex from a carboxyl group-containing polymer and an epoxy-amine adduct of the present invention; using an active group having an epoxy-amine adduct from the present invention An adsorbent for a low molecular metal chelate of an ion exchanger; an ion selective electrode using a membrane containing the epoxy-amine adduct of the present invention or a derivative thereof; and an epoxy-amine adduct of the present invention An acid gas adsorbent which adheres or reacts to the surface of the porous material; a separation membrane made of a high-concentration sugar liquid formed by the reaction product of the epoxy-amine adduct of the present invention and dialdehyde. use.

The epoxy-amine adduct of the present invention can be used, for example, in the field of cosmetics and cosmetics, for: solid soap for skin cleansing; hair cosmetic (shampoo, conditioner, hair conditioner, etc.); nail polish Composition; use of sludge removal and prevention of recontamination. More specifically, the epoxy-amine adduct of the present invention can be used for: a skin-cleaning solid soap containing the epoxy-amine adduct of the present invention or a modified substance thereof; blended with the ring of the present invention a cosmetic for hair of an oxy-amine adduct or a derivative thereof; a nail formed by blending a polyion complex synthesized by reacting an anionic polymeric salt with the epoxy-amine adduct of the present invention Oil composition; use of the ethoxylated epoxy-amine adduct of the present invention to remove sludge and prevent re-contamination. use.

The epoxy-amine adduct of the present invention can be used as a lubricant, a rust preventive or a dispersant as described above, and can be used, for example, for a metalworking oil composition; a metal rolling lubricant; a ceramic dispersant; a dispersing agent in a magnetic layer of a magnetic recording medium; a dispersing agent for coal-water slurry; preventing adhesion of ash in a fine carbon-oil mixture to a metal; a high-concentration low-viscosity water slurry of a fine powder of vermiculite use. More specifically, the epoxy-amine adduct of the present invention can be used, for example, as a metalworking oil composition containing a condensate of a carboxylic acid and an epoxy-amine adduct of the present invention as an active ingredient; a lubricant for metal rolling of a component and a dispersant of an epoxy-additive of an epoxy-amine adduct of the present invention; and a magnetic layer containing the epoxy-amine adduct of the present invention and a carboxyl group-containing polyester a magnetic recording medium containing a reaction product as a dispersing agent; a dispersing agent for a coal-water slurry comprising a polyoxoalkyl ether of the epoxy-amine adduct of the present invention and a formalin condensate of an aromatic sulfonate; An aspect of the use of an alkylene oxide adduct of the epoxy-amine adduct of the present invention in a fine powder carbon-oil mixture to prevent adhesion of ash to metals and the like. use.

The epoxy-amine adduct of the present invention can be used as a plating agent as described above, and can be used, for example, for gloss improvement; electrodeposition of glossy copper for electronic circuit printed substrates; acid zinc plating; high-speed copper plating The use of an electroless plating film or the like. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for gloss improvement by addition to an electroplating bath (for example, a black enamel plating bath, etc.); the epoxy-amine addition of the present invention The material activates the transparent electroconductive film to form an electroless plating film. use.

The epoxy-amine adduct of the present invention can be used, for example, in the fields of biology, medicine, and enzymes for immobilization of enzymes (for example, production of saponin using α-glucosyltransferase, sucrose displacement) Immobilization of sucrose-mutase, immobilization of alcohol oxidase, glucose oxidase, cholesterol oxidase, etc., using 7-β-acylamidocephalosporanic acid (7-β-acylamidocephalosporanic acid) - Immobilization of Bacillus subtilis of acetamidine detachment product, production of L-phenylalanine from trans-cinnamic acid by immobilized Sporobolomyces roseus cells; Purification from cell-free extract of coliform DNA polymerase III; analyte detection by antibody immunofluorescence; purification of human interferon-β; purification of single-body, single-source antibody; synthesis of anti-blood coagulant; use of enzyme immobilization membrane, etc. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for the use of the epoxy-amine adduct of the present invention or a derivative thereof, and an enzyme of glutaraldehyde, alginic acid, citric acid or the like. Immobilization by immobilization; analyte detection by antibody immunofluorescence using a reactant of the epoxy-amine adduct of the present invention and a functional fluorescent dye molecule; using an epoxy-amine adduct loaded with the present invention Purification of single-body, single-source antibody of tannin; synthesis of anti-blood coagulant using sulfonated epoxy-amine adduct of the present invention; utilization of epoxy-amine adduct of the present invention and dialdehyde Cross-linked enzyme immobilization film and other aspects. use.

The epoxy-amine adduct of the present invention can be used as a cement additive or a petroleum additive as described above, for example, it can be used for: a water reducing agent for cement; a water reducing agent for cementing under petroleum exploitation ( Fluid loss agent); use of concrete mixtures, etc. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for: a cement water reducing agent using the hydroxyalkylated epoxy-amine adduct of the present invention; using carboxyethylation The aspect of the concrete mixture of the epoxy-amine adduct of the present invention. use.

The epoxy-amine adduct of the present invention can also be used as a primer for metals, steel sheets, resins, and the like in order to improve the adhesion between the metal and the resin or the resin.

The epoxy-amine adduct of the present invention can be used, for example, for: a solid electrolyte composition; bonding of metal ions; accumulation of a monomolecular film (accumulation method); production of sustained release microcapsules; Use of bacteria, etc. More specifically, the epoxy-amine adduct of the present invention can be used, for example, for a solid electrolyte composition using a crosslinked body of an epoxy-amine adduct of the present invention and a polyfunctional epoxy compound; Bonding of metal ions of the epoxy-amine adduct of the present invention or a derivative thereof; accumulation of a monomolecular film which has been previously treated with the epoxy-amine adduct of the present invention on the surface of the solid substrate (accumulation method) Production of sustained release microcapsules by interfacial polymerization of an epoxy-amine adduct of the present invention with a diisocyanate compound; using water in polystyrene grafted with the epoxy-amine adduct of the present invention Antibacterial, sterilization and other aspects. use.

 <Processing agent for carbon fiber>  

A treatment agent for carbon fibers can be obtained by using the epoxy-amine adduct of the present invention. The "treatment agent for carbon fibers" means a coating agent used for coating (coating) carbon fibers. In other words, the treating agent for carbon fibers of the present invention contains a coating agent for carbon fibers containing an epoxy-amine adduct of the present invention as an essential component. This carbon fiber treating agent can be used as a binder applied to carbon fibers and used to maintain a nonwoven fabric. Further, the matrix resin is impregnated into a structure comprising carbon fibers treated with the treating agent for carbon fibers of the present invention, and can be used as a fiber-reinforced composite material.

The treatment agent for carbon fibers of the present invention may contain an epoxy-amine adduct of the present invention as an essential component, and may contain a solvent, other additives, etc. in addition to the epoxy-amine adduct of the present invention. Further, it may be composed only of the epoxy-amine adduct of the present invention (the epoxy-amine adduct itself of the present invention). However, as described above, it is different from the matrix resin which is a main component of the fiber-reinforced composite material. The treatment agent for carbon fibers of the present invention may be in the form of a solution (for example, an aqueous solution) or a dispersion (for example, an aqueous dispersion). The solvent exemplified above may be used as the solvent to be used in the form of a solution or a dispersion. The other additives are not particularly limited, and examples thereof include a lubricant such as a fatty acid, a guanamine or an ester; a coupling agent such as a decane coupling agent or a titanium coupling agent; and the like.

The content (doping amount) of the epoxy-amine adduct, the solvent, and other additives of the present invention in the treatment agent for carbon fibers of the present invention is not particularly limited, and may be appropriately adjusted.

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

 [Examples]  

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

 Example 1    [Manufacture of epoxy-amine adduct]  

3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylic acid [manufactured by DAICEL Co., Ltd., trade name "Celloxide 2021P") was used as the epoxy compound (A), and An amine [trade name "TETA" manufactured by HUNTSMAN Co., Ltd.) and 3,3-diaminodiphenyl hydrazine [Tokyo Chemicals Sales Co., Ltd.] are used as the amine compound (B).

In a 1 L stainless steel reaction vessel, 250.0 g of triamethylenetetramine and 87.5 g of 3,3-diaminodiphenyl hydrazine were added, and 60 of them were consumed at 160 ° C under a nitrogen atmosphere. 512.5 g of the epoxy compound (A) was dropped in minutes. Then, the mixture was stirred at 200 ° C for 3 hours, and further stirred at 220 ° C for 2 hours to cause a reaction, thereby obtaining an epoxy-amine adduct (amine addition product).

After cooling, after the content has fluidity (130 to 150 ° C), it flows out from the reaction vessel onto the release paper, and after further cooling and solidifying it, 850 g of epoxy-amine is obtained by pulverization. Adult.

Then, 800 g of the epoxy-amine adduct obtained above was dissolved in 1200 g of water in a 3 L flask (reaction container) to obtain 2 kg of a 40% aqueous solution.

 Example 2    [Manufacture of epoxy-amine adduct]  

3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylic acid [manufactured by DAICEL Co., Ltd., trade name "Celloxide 2021P") was used as the epoxy compound (A), and An amine [trade name "TETA" manufactured by HUNTSMAN Co., Ltd.) and m-xylylenediamine [Tokyo Chemicals Sales Co., Ltd.] are used as the amine compound (B).

Into a 1 L stainless steel reaction vessel, 205.0 g of triamethylenetetramine and 123.0 g of m-xylylenediamine were added, and 569.9 g of the mixture was dropped at 160 ° C for 60 minutes under a nitrogen atmosphere. Epoxy compound (A). Then, the mixture was stirred at 200 ° C for 3 hours, and further stirred at 220 ° C for 2 hours to cause a reaction, thereby obtaining an epoxy-amine adduct (amine addition product).

After cooling, after the content has fluidity (130 to 150 ° C), it flows out from the reaction vessel onto the release paper, and after further cooling and solidifying it, 850 g of epoxy-amine is obtained by pulverization. Adult.

Then, 800 g of the epoxy-amine adduct obtained above was dissolved in 1200 g of water in a 3 L flask (reaction container) to obtain 2 kg of a 40% aqueous solution.

 Example 3    [Manufacture of epoxy-amine adduct]  

3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylic acid [manufactured by DAICEL Co., Ltd., trade name "Celloxide 2021P") was used as the epoxy compound (A), and An amine [trade name "TETA" manufactured by HUNTSMAN Co., Ltd.) and 2,6-diaminopyridine [sold by Sigma-Aldrich] were used as the amine compound (B).

In a 1 L stainless steel reaction vessel, 210.0 g of triamethylenetetramine and 105.0 g of 2,6-diaminopyridine were added, and it was dropped in a nitrogen atmosphere at 160 ° C for 60 minutes. 546.0 g of the epoxy compound (A). Then, the mixture was stirred at 200 ° C for 3 hours, and further stirred at 220 ° C for 2 hours to cause a reaction, thereby obtaining an epoxy-amine adduct (amine addition product).

After cooling, after the content has fluidity (130 to 150 ° C), it flows out from the reaction vessel onto the release paper, and after further cooling and solidifying it, 850 g of epoxy-amine is obtained by pulverization. Adult.

Then, 800 g of the epoxy-amine adduct obtained above was dissolved in 1200 g of water in a 3 L flask (reaction container) to obtain 2 kg of a 40% aqueous solution.

 Comparative example 1    [Manufacture of epoxy-amine adduct]  

3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylic acid [manufactured by DAICEL Co., Ltd., trade name "Celloxide 2021P") was used as the epoxy compound (A), and An amine [trade name "TETA" manufactured by HUNTSMAN Co., Ltd.) and isophorone diamine [manufactured by Evonik Degussa Japan Co., Ltd., trade name "Vestamin IPD"] are used as the amine compound (B).

In a 1 L stainless steel reaction vessel, 228.0 g of triamethylenetetramine and 171.0 g of isophorone diamine were added, and 632.5 g of 632.5 g was dropped in a nitrogen atmosphere at 160 ° C for 60 minutes. Epoxy compound (A). Then, the mixture was stirred at 200 ° C for 3 hours, and further stirred at 220 ° C for 2 hours to cause a reaction, thereby obtaining an epoxy-amine adduct (amine addition product).

After cooling, after the content has fluidity (130 to 150 ° C), it flows out from the reaction vessel onto the release paper, and after further cooling and solidifying, 1000 g of epoxy-amine is obtained by pulverization. Adult.

Then, 800 g of the epoxy-amine adduct obtained above was dissolved in 1200 g of water in a 3 L flask (reaction container) to obtain 2 kg of a 40% aqueous solution.

 . Subsequent evaluation (checkerboard test)  

40% aqueous solution of the epoxy-amine adduct prepared in the above examples and comparative examples was applied to a film made of polypropylene (PP) and nylon 6 (NY6) using a bar coater (No. 6). After the surface was not treated, the solvent (water) was removed by drying in a dryer (40 ° C × 12 hours + 80 ° C × 2 hours) to obtain a coating film (thickness) in which an epoxy-amine adduct was formed on the substrate film. : 6 μm) test piece. The obtained test piece was subjected to the adhesion evaluation (100 square checkerboard test) in accordance with the old JIS-K-5400 (year of development: February 17, 1959). The results are shown in the "Checkerboard Test" column of Table 1. In addition, the above checkerboard test was carried out in a glove box.

The numerical values in Table 1 indicate the number of squares which were not peeled off from the base film before and after peeling of the tape. In other words, the maximum value of 100 is the highest, and the larger the value, the better the adhesion.

 . Flexibility evaluation (mandrel test)  

The coating was carried out in the same manner as the above checkerboard test. After drying, the obtained test piece was subjected to a mandrel tester (diameter: 2, 3, 4, 6, 8, 10 mm) in accordance with the old JIS-K-5600-5-1, in such a manner that the coating film side became a convex side. Evaluate the bendability. The bending diameter (mm) in which the coating film was not broken was shown in Table 1. The smaller the bending diameter (mm), the higher the bendability (toughness). In addition, the mandrel test described above was carried out in a glove box.

 . Wettability evaluation    1) Drying step  

A 40% aqueous solution of the epoxy-amine adduct prepared in the above Examples and Comparative Examples was added to an aluminum cup (diameter: 55 mm) to make the weight of the dried epoxy-amine adduct 1.5 g. The mixture was dried by heating at 105 ° C for 2 hours under reduced pressure.

 2) heating furnace (muffle furnace) heating step  

In the aluminum cup obtained in the above 1), 10 pieces of nylon 6 (UBE MYLON, manufactured by Ube Industries, Ltd.) selected to be 11.5 ± 5 mg were placed in a reheating furnace (manufactured by Yamato Scientific Co., Ltd.). The nylon 6 was melted by heating at 290 ° C for 5 minutes under an argon atmosphere.

 3) Wettability evaluation  

The aluminum cup obtained in the above 2) was measured for the area (mm ² ) of each of the melted nylon 6 and its central value using a microscope. The results are shown in Table 2. The wider the area (mm ² ) of the molten nylon 6 is, the higher the wettability is.

The variations of the invention described above are noted below.

[1] An epoxy-amine adduct selected from the group consisting of a compound [I] having two or more amine groups in a molecule, and a salt of the compound [I], characterized in that a compound [I] is an addition product of an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule, and an amine compound (B) having two or more amine groups in the molecule, and an epoxy compound ( A) a compound represented by the following formula (a), wherein the amine compound (B) contains at least one compound selected from the group consisting of the following formula (bI) (hereinafter, referred to as "amine compound (BI)" And at least one compound selected from the following formula (b-II) (hereinafter, referred to as "amine compound (BII)"), and the epoxy-amine adduct is two A compound having an amine group at the end.

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

R ^1a (NH ₂ ) ₂ (bI) 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 through a linking group containing a hetero atom

(b) a divalent group in which a divalent linear or branched aliphatic hydrocarbon group is directly bonded to a divalent cyclic aliphatic hydrocarbon group]

R ^1b (NH ₂ ) ₂ (b-II)

[wherein R ^1b represents a divalent group selected from the group consisting of the following (c) to (g).

(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 is directly bonded to a divalent linear or branched aliphatic hydrocarbon group

(e) a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring.

(f) a divalent group and a divalent linear chain obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. Or a divalent group directly bonded to a branched aliphatic hydrocarbon group

(g) a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons having 6 to 12 carbon atoms through a group bonded to a linking group]

[2] The epoxy-amine adduct of the above [1], wherein the compound represented by the above formula (a) is selected from the group consisting of 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) ring Oxyethane (=1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane), and bis(3,4-epoxycyclohexylmethyl) At least one of the groups of ethers.

[l and m in the formulas (a-5) and (a-7) each represent an integer of 1 to 30. R' in the formula (a-5) represents an alkylene group having 1 to 8 carbon atoms. N1 to n6 in the formulas (a-9) and (a-10) each represent an integer of 1 to 30]

[3] The epoxy-amine adduct of the above [1] or [2], wherein the epoxy compound (A) is a compound represented by the above formula (a-1) [(3,4-epoxy)) 3,4-epoxycyclohexylmethyl cyclohexanecarboxylate].

[4] The epoxy-amine adduct according to any one of the above [1] to [3], wherein the ratio of the amine compound (BI) to the amine compound (BII) in the aforementioned amine compound (B) (amine compound) The weight ratio of (BI) / amine compound (BII) is from 1.5 to 4.0 (g/g) (preferably from 1.7 to 3.0 (g/g)).

[5] The epoxy-amine adduct according to any one of [1] to [4] wherein the molecular weight of the amine compound (B) is from 80 to 10,000 (preferably from 100 to 5,000, more preferably 200). ~1000).

[6] The epoxy-amine adduct according to any one of [1] to [5] wherein R ^1a is a divalent group of (a) (preferably 2 or more carbon atoms 2 to 6) A linear or branched alkyl group (especially an ethyl group, a trimethylene group, a propyl group) is bonded to a divalent group bonded by -NH- or -O-).

[7] The epoxy-amine adduct according to any one of [1] to [6] wherein R ^1b is a divalent group selected from the group consisting of (d), a divalent group (e), and (g) At least one of the groups of divalent groups.

[8] The epoxy-amine adduct according to any one of [1] to [7] wherein the R ^1b is selected from the group consisting of removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 10 carbon atoms. a divalent group (preferably a phenyl group) and a divalent group (preferably a xylyl group) directly bonded to an alkylene group (preferably a methylene group) having 1 to 4 carbon atoms; a divalent group obtained by removing two hydrogen atoms from a ring (preferably a pyridine ring); and a linking group (preferably -SO ₂ ) from two aromatic hydrocarbons having 6 to 10 carbon atoms (preferably a benzene ring) -etc.) At least one group of divalent groups obtained by removing two hydrogen atoms from the bonded group.

[9] The epoxy-amine adduct according to any one of [1] to [8] wherein the amine compound (BI) is selected from the group consisting of compounds represented by the following formula (b-1) (below) There is a compound called "amine compound (B1)", a compound represented by the following formula (b-2) (hereinafter, referred to as "amine compound (B2)"), and the following formula (b) -3) At least one of the groups of the compounds shown (in the case of "amine compound (B3)").

[wherein R ² and R ³ represent the same or different divalent linear or branched aliphatic hydrocarbons. q represents an integer of 1 or more. ]

[wherein R ⁴ and R ⁵ are the same or different and represent a divalent linear or branched aliphatic hydrocarbon. r represents an integer of 1 or more. ]

[wherein R ⁶ and R ⁸ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. s means 0 or 1. R ⁷ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. t represents an integer from 0 to 10. ]

[10] The epoxy-amine adduct according to the above [9], wherein the amine compound (BI) is at least one selected from the group consisting of the amine compound (B1) and the amine compound (B3). The aforementioned amine compound (B1)) is preferred.

[11] The epoxy-amine adduct according to any one of [1] to [10] wherein the amine compound (BII) is selected from the group consisting of compounds represented by the following formula (b-5) (below) There is a compound called "amine compound (B5)", a compound represented by the following formula (b-6) (hereinafter, referred to as "amine compound (B6)"), and the following formula (b) -7) At least one of the group of the compounds (hereinafter referred to as "amine compound (B7)").

[In the formula, A ¹ represents an aromatic hydrocarbon having 6 to 12 carbon atoms. R ¹¹ and R ¹³ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. R ¹² represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. W1 and w3 are the same or differently representing 0 or 1. W2 represents an integer from 0 to 4. ]

[wherein, B ¹ represents an aromatic heterocyclic ring having 1 or 2 hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. R ¹⁴ and R ¹⁶ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. 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. X1 and x3 are the same or differently representing 0 or 1. X2 represents an integer from 0 to 4. ]

[In the formula, A ² and A ³ represent the same or different aromatic hydrocarbons having 6 to 12 carbon atoms. Y ¹ represents a linking group. R ¹⁷ and R ¹⁸ are the same or different and each represent a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. Y1 and y2 represent the same or different integers from 0 to 4. ]

[12] The epoxy-amine adduct according to [11] above, wherein the aforementioned amine compound (BII) is the aforementioned amine compound (B7).

[13] The epoxy-amine adduct according to any one of the above [1], wherein the compound [I] having two or more amine groups in the molecule is represented by the following (I). A compound having two or more amine groups in its molecule.

Wherein R ^{1 '} is a divalent organic group having a carbon atom at a bonding site to a nitrogen atom represented by the formula, and at least one is selected from the group consisting of the following (a) and (b) At least one divalent group (hereinafter referred to as "the first divalent group"), and at least one other one selected from at least one of the groups including the following (c) to (g) Price base (hereinafter, there is a case called "the second divalent base"). X represents a single bond or a divalent group having one or more atoms. z represents an integer of 1 or more.

(a) a divalent group in which two or more divalent linear or branched aliphatic hydrocarbons are bonded through a linking group containing a hetero atom

(b) a divalent group directly bonded to a divalent linear or branched aliphatic hydrocarbon group and a divalent cyclic aliphatic hydrocarbon group

(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 is directly bonded to a divalent linear or branched aliphatic hydrocarbon group

(e) a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring.

(f) a divalent group and a divalent linear chain obtained by removing two hydrogen atoms from an aromatic heterocyclic ring having one or two hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. Or a divalent group directly bonded to a branched aliphatic hydrocarbon group

(g) a divalent group obtained by removing two hydrogen atoms from two or more aromatic hydrocarbons having 6 to 12 carbon atoms through a group bonded to a linking group]

[14] The epoxy-amine adduct of the above [13], wherein the first divalent group of the R ^{1 ' is} a divalent group of (a) (preferably two or more carbon atoms of 2 to 6) A linear or branched alkyl group (especially an ethyl group, a trimethylene group, a propyl group) is a divalent group bonded through -NH- or -O-).

[15] The epoxy-amine adduct of the above [13] or [14], wherein the second divalent group of the aforementioned R ^{1 '} is selected from the divalent group containing (d), and the divalent group of (e) At least one of a group of divalent groups of a group and (g).

[16] The epoxy-amine adduct according to any one of [13] to [15] wherein the second divalent group of the aforementioned R ^{1 '} is selected from aromatic hydrocarbons having a carbon number of 6 to 10 a divalent group (preferably a phenyl group) obtained by removing two hydrogen atoms and a divalent group directly bonded to an alkylene group (preferably a methylene group) having 1 to 4 carbon atoms (preferably xylene) a divalent group obtained by removing two hydrogen atoms from an aromatic heterocyclic ring (preferably a pyridine ring); and a linking group derived from two aromatic hydrocarbons having 6 to 10 carbon atoms (preferably a benzene ring) (preferably, -SO ₂ - or the like) at least one of a group of divalent groups obtained by removing two hydrogen atoms from a bonded group.

The epoxy-amine adduct according to any one of the above-mentioned [13], wherein the divalent group of the above (a) is a divalent group represented by the following formula (II) or the following The divalent group represented by the formula (III), and the divalent group of the above (b) are a divalent group represented by the following formula (IV).

[wherein R ² and R ³ represent the same or different divalent linear or branched aliphatic hydrocarbons. q represents an integer of 1 or more. ]

[wherein R ⁴ and R ⁵ are the same or different and represent a divalent linear or branched aliphatic hydrocarbon. r represents an integer of 1 or more. ]

[wherein R ⁶ and R ⁸ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. s means 0 or 1. R ⁷ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. t represents an integer from 0 to 10. ]

[18] The epoxy-amine adduct according to any one of [13] to [17] wherein the divalent group of the above (c) or the divalent group of the above (d) is the following formula (V) In the divalent group shown, the divalent group of the above (e) or the divalent group of the above (f) is a divalent group represented by the following formula (VI), and the divalent group of the above (g) is a formula The divalent group shown in (VII).

[In the formula, A ¹ represents an aromatic hydrocarbon having 6 to 12 carbon atoms. R ¹¹ and R ¹³ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. R ¹² represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. W1 and w3 are the same or differently representing 0 or 1. W2 represents an integer from 0 to 4. ]

[wherein, B ¹ represents an aromatic heterocyclic ring having 1 or 2 hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring. R ¹⁴ and R ¹⁶ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. 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. X1 and x3 are the same or differently representing 0 or 1. X2 represents an integer from 0 to 4. ]

[In the formula, A ² and A ³ represent the same or different aromatic hydrocarbons having 6 to 12 carbon atoms. Y ¹ represents a group of a linking group. R ¹⁷ and R ¹⁸ are the same or different and each represent a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. Y1 and y2 represent the same or different integers from 0 to 4. ]

[19] The epoxy-amine adduct according to any one of [13] to [18] wherein the first divalent group of the aforementioned R ^{1 '} is selected from the group consisting of the divalent group represented by the above formula (II) At least one of the group of the divalent groups represented by the above formula (IV) (preferably a divalent group represented by the formula (II)).

[20] The epoxy-amine adduct according to any one of [13] to [19] wherein the second divalent group of the above R ^{1 ' is} a divalent group represented by the above formula (VII).

[21] The epoxy-amine adduct according to any one of [13] to [20] wherein the ratio of the first divalent group to the second divalent group of the aforementioned R ^{1 '} (the first divalent group) / Weight ratio of the second divalent group) is 1.5 to 4.0 (g/g) (preferably 1.7 to 3.0 (g/g)).

[22] The epoxy-amine adduct according to any one of [1] to [21] wherein the compound [I] has a number average molecular weight of from 200 to 40,000 (preferably from 300 to 30,000, more preferably 400~20000).

[23] The epoxy-amine adduct according to any one of [1] to [22] wherein the compound [I] has a glass transition temperature (Tg) of -50 to 200 ° C (preferably -40). ~190 ° C, more preferably -30 ~ 180 ° C, especially good 20 ~ 180 ° C).

[24] The epoxy-amine adduct according to any one of [1] to [23] wherein the compound [I] has a 5% weight loss temperature (Td ₅ ) of 280 ° C or higher (preferably 300). °C or more).

[25] The epoxy-amine adduct according to any one of the above [1] to [24] which is a salt of the compound [I] having two or more amine groups in the molecule, and is a compound [I] ] salt with acid [II].

[26] An epoxy-amine adduct according to the above [25], which is a carbonate or an organic acid salt (preferably a carbonate, an acetate, particularly preferably a carbonate).

[27] A thermoplastic resin composition comprising the epoxy-amine adduct according to any one of [1] to [26] above, and a thermoplastic resin.

[28] The thermoplastic resin composition according to [27] above, wherein the thermoplastic resin is selected from the group consisting of polyolefins (for example, polyethylene, polypropylene, polybutadiene, etc.), vinyl polymers (for example, acrylic resins, 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 At least one of the group of polyether oxime and polyetheretherketone.

[29] The thermoplastic resin composition according to the above [27] or [28] wherein the content (the blending amount) of the thermoplastic resin is 0.1 to 99.9 by weight based on the total amount (100% by weight) of the thermoplastic resin composition. % (preferably 1 to 99% by weight, more preferably 2 to 98% by weight).

[30] The thermoplastic resin composition according to any one of [27] to [29] wherein the content (the blending amount) of the epoxy-amine adduct is 0.1 based on 100 parts by weight of the thermoplastic resin. ~200 parts by weight (preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight).

[31] The thermoplastic resin composition according to any one of [27] to [30] which is a resin composition for a fiber-reinforced composite material.

[32] An aqueous coating comprising the epoxy-amine adduct according to any one of [1] to [26] above.

[33] An aqueous solution containing the epoxy-amine adduct according to any one of [1] to [26] above.

[34] A water-dispersible resin composition comprising the epoxy-amine adduct according to any one of [1] to [26], and a urethane resin.

[35] The water-dispersed resin composition according to [34] above, which further contains a surfactant.

[36] The water-dispersible resin composition according to the above [35], wherein the surfactant is at least one selected from the group consisting of an anionic surfactant and a nonionic surfactant.

[37] A method for producing a water-dispersible resin composition, characterized by mixing an aqueous dispersion containing the epoxy-amine adduct according to any one of [1] to [26], and an aminocarboxylic acid. Ester resin emulsion.

[38] The method for producing a water-dispersed resin composition according to the above [37], wherein the aqueous dispersion containing the epoxy-amine adduct contains a surfactant.

[39] The method for producing a water-dispersed resin composition according to the above [38], wherein the surfactant is at least one selected from the group consisting of an anionic surfactant and a nonionic surfactant. .

[40] A sizing agent for carbon fibers, which comprises the epoxy-amine adduct according to any one of [1] to [26] above.

[41] An aqueous coating comprising the sizing agent for carbon fibers according to [40] above.

[42] An aqueous solution containing the sizing agent for carbon fibers according to [40] above.

[43] A water-dispersible resin composition comprising the sizing agent for carbon fibers according to [40] above, and a urethane resin.

[44] The water-dispersed resin composition according to [43] above, which further contains a surfactant.

[45] The water-dispersible resin composition according to [44] above, wherein the surfactant is at least one selected from the group consisting of an anionic surfactant and a nonionic surfactant.

[46] The sizing agent for carbon fibers according to the above [40], wherein the aforementioned epoxy-amine adduct is water-soluble.

[47] A sizing agent for carbon fibers, which comprises the water-dispersed resin composition according to any one of [34] to [36] above.

[48] A carbon fiber coated with a sizing agent for carbon fibers, which is coated with a sizing agent for carbon fibers according to any one of the above [40], [46], and [47].

[49] A fiber-reinforced composite material comprising the carbon fiber for coating a carbon fiber sizing agent according to [48] above.

[50] A fiber-reinforced composite material comprising the thermoplastic resin composition according to any one of the above [27] to [31] and a carbon fiber.

[51] A treatment agent for carbon fibers, which comprises the epoxy-amine adduct according to any one of [1] to [26] above.

[52] A carbon fiber bundle coated with a sizing agent for carbon fibers according to any one of the above [40], [46], or [47].

[53] A prepreg obtained by coating a carbon fiber for a sizing agent for carbon fibers as described in [48] above.

[54] A prepreg comprising the epoxy-amine adduct according to any one of [1] to [26], a thermoplastic resin, and a carbon fiber.

[55] A fiber-reinforced composite material formed from the prepreg according to the above [54].

[56] A fiber-reinforced composite material comprising the carbon fiber coated with a sizing agent for carbon fibers according to [48] above, and a thermoplastic resin.

Industrial availability

The epoxy-amine adduct of the present invention can be used, for example, for an adhesion improver (adhesive improver) for improving the adhesion between a resin and an additive in a polymer-based composite, and for improving An adhesion enhancer (adhesive improver) for adhesion to an adherend, and a compatibility enhancer (compatibilizer) for improving the solubility of two or more different components (especially polymers) Various additives such as a dispersibility enhancer, a fluidity enhancer, a fluidity inhibitor, a plasticizer, and a crosslinking agent such as an epoxy resin for improving the dispersibility of the additive in the polymer composite; Various uses of coatings, sealants, sizing agents, and the like.

Claims (35)

An epoxy-amine adduct selected from the group consisting of a compound [I] having two or more amine groups in a molecule, and a salt of the compound [I], characterized in that the compound [I] An addition product of an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule, and an amine compound (B) having two or more amine groups in the molecule, and the epoxy compound (A) is contained The compound represented by the following formula (a), the amine compound (B) contains at least one compound selected from the group consisting of the following formula (bI), and a compound selected from the group consisting of the following formula (b-II). At least one, and the epoxy-amine adduct is a compound having an amine group at both ends; [wherein, X represents a single bond or a divalent group having one or more atoms] R ^1a (NH ₂ ) ₂ (bI) [wherein R ^1a represents a selected from the group consisting of the following (a) and (b) a divalent group of a group; (a) a divalent linear group of two or more divalent linear or branched aliphatic hydrocarbons bonded through a hetero atom-containing linking group (b) Or a divalent group in which a branched aliphatic hydrocarbon group is directly bonded to a divalent cyclic aliphatic hydrocarbon group]R ^1b (NH ₂ ) ₂ (b-II) wherein R ^1b is selected from the group consisting of the following (c) a divalent group of the group of (g); (c) a divalent group (d) obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms (d) from a carbon number of 6 to 12 a divalent group in which a divalent group obtained by removing a hydrogen atom from a hydrocarbon and a divalent linear or branched aliphatic hydrocarbon group directly bonded to each other has a divalent group (e) having 1 or 2 selected from a ring containing a nitrogen atom. An aromatic heterocyclic ring of a hetero atom of a group of a sulfur atom and an oxygen atom, wherein a divalent group (f) obtained by removing two hydrogen atoms has one or two selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom. A divalent group formed by removing a hydrogen atom from an aromatic heterocycle of a hetero atom of a group and a divalent straight or branched chain The aliphatic hydrocarbon group is directly bonded to the divalent group (g) from two or more of the carbon atoms of an aromatic hydrocarbon having 6 to 12 removing two hydrogen through a linking group are bonded group of atoms formed by the divalent group]. The epoxy-amine adduct of claim 1, wherein the compound represented by the formula (bI) is selected from the group consisting of a compound represented by the following formula (b-1) and represented by the following formula (b-2) At least one of a group of the compound and a compound represented by the following formula (b-3); [wherein R ² and R ³ are the same or different, respectively represent a divalent straight or branched aliphatic hydrocarbon; q represents an integer of 1 or more] Wherein R ⁴ and R ⁵ are the same or different, and represent a divalent linear or branched aliphatic hydrocarbon; r represents an integer of 1 or more] Wherein R ⁶ and R ⁸ are the same or different represent an alkylene group having 1 to 4 carbon atoms; s represents 0 or 1; and R ⁷ represents a monovalent organic group, an oxygen atom-containing group, and a sulfur atom-containing group. a group, a nitrogen atom-containing group, or a halogen atom; t represents an integer of 0 to 10]. The epoxy-amine adduct of claim 1 or 2, wherein the compound represented by the formula (b-II) is selected from the group consisting of a compound represented by the following formula (b-5), and the following formula (b- 6) at least one selected from the group consisting of a compound represented by the following formula (b-7); [wherein, A ¹ represents an aromatic hydrocarbon having 6 to 12 carbon atoms; and R ¹¹ and R ¹³ are the same or differently represented by an alkylene group having 1 to 4 carbon atoms; and R ¹² represents a monovalent organic group or an oxygen-containing atom; a base, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom; w1 and w3 are the same or differently represented by 0 or 1; w2 represents an integer of 0 to 4] Wherein B ¹ represents an aromatic heterocyclic ring having 1 or 2 hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom; and R ¹⁴ and R ¹⁶ are the same or different carbon numbers. 1 to 4 alkylene; 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; and x1 and x3 are the same or differently represented by 0 or 1; x2 represents an integer from 0 to 4] [In the formula, A ² and A ³ are the same or different, and represent an aromatic hydrocarbon having 6 to 12 carbon atoms; Y ¹ represents a linking group; and R ¹⁷ and R ¹⁸ are the same or different, and represent a monovalent organic group and oxygen. An atomic group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom; y1 and y2 are the same or different integers of 0 to 4]. The epoxy-amine adduct of claim 1, wherein the compound [I] having two or more amine groups in the molecule is a compound having two or more amine groups in the molecule represented by the following (I); Wherein R ^{1 '} is a divalent organic group having a carbon atom at a bonding site to a nitrogen atom represented by the formula, and at least one is selected from the group consisting of the following (a) and (b) At least one divalent group, and at least one other represents at least one divalent group selected from the group consisting of (c) to (g) below; X represents a single bond, or two having one or more atoms a valence group; z represents an integer of 1 or more; (a) a divalent group of two or more divalent linear or branched aliphatic hydrocarbons bonded through a hetero atom-containing linking group (b) a divalent group in which a linear or branched aliphatic hydrocarbon group is directly bonded to a divalent cyclic aliphatic hydrocarbon group (c), and a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms a divalent group (e) in which a divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6 to 12 carbon atoms is directly bonded to a divalent linear or branched aliphatic hydrocarbon group (e) An aromatic heterocyclic ring having one or two aromatic heterocyclic rings selected from a group consisting of a nitrogen atom, a sulfur atom and an oxygen atom in the ring, and having two hydrogen atoms (f) having 1 or 2 from the ring One selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom A divalent group in which an aromatic heterocyclic ring of a hetero atom is removed by removing two hydrogen atoms and a divalent group directly bonded to a divalent linear or branched aliphatic hydrocarbon group (g) from two or more carbon numbers A divalent group obtained by removing two hydrogen atoms from an aromatic hydrocarbon of ~12 through a bond group of a linking group. The epoxy-amine adduct of claim 4, wherein the divalent group of (a) is a divalent group represented by the following formula (II) or a divalent group represented by the following formula (III), The divalent group of (b) is a divalent group represented by the following formula (IV); [wherein R ² and R ³ are the same or different, respectively represent a divalent straight or branched aliphatic hydrocarbon; q represents an integer of 1 or more] Wherein R ⁴ and R ⁵ are the same or different, and represent a divalent linear or branched aliphatic hydrocarbon; r represents an integer of 1 or more] Wherein R ⁶ and R ⁸ are the same or different represent an alkylene group having 1 to 4 carbon atoms; s represents 0 or 1; and R ⁷ represents a monovalent organic group, an oxygen atom-containing group, and a sulfur atom-containing group. a group, a nitrogen atom-containing group, or a halogen atom; t represents an integer of 0 to 10]. The epoxy-amine adduct of claim 4 or 5, wherein the divalent group of (c) or the divalent group of (d) is a divalent group represented by the following formula (V), The divalent group of the (f) or the divalent group of the formula (f) is a divalent group represented by the following formula (VI), and the divalent group of the (g) is a divalent group represented by the following formula (VII); [wherein, A ¹ represents an aromatic hydrocarbon having 6 to 12 carbon atoms; and R ¹¹ and R ¹³ are the same or differently represented by an alkylene group having 1 to 4 carbon atoms; and R ¹² represents a monovalent organic group or an oxygen-containing atom; a base, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom; w1 and w3 are the same or differently represented by 0 or 1; w2 represents an integer of 0 to 4] Wherein B ¹ represents an aromatic heterocyclic ring having 1 or 2 hetero atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom; and R ¹⁴ and R ¹⁶ are the same or different carbon numbers. 1 to 4 alkylene; 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; and x1 and x3 are the same or differently represented by 0 or 1; x2 represents an integer from 0 to 4] [In the formula, A ² and A ³ are the same or different, and represent an aromatic hydrocarbon having 6 to 12 carbon atoms; Y ¹ represents a group of a linking group; and R ¹⁷ and R ¹⁸ are the same or different, and represent a monovalent organic group, An oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom; y1 and y2 are the same or different integers of 0 to 4].  The epoxy-amine adduct according to any one of claims 1 to 6, which is a salt of the compound [I] having two or more amine groups in the molecule, and is a compound [I] and an acid [II] Salt.    An epoxy-amine adduct of claim 7, which is a carbonate or an organic acid salt.    A thermoplastic resin composition comprising the epoxy-amine adduct according to any one of claims 1 to 8, and a thermoplastic resin.    The thermoplastic resin composition of claim 9, which is a resin composition for a fiber-reinforced composite material.    An aqueous coating comprising the epoxy-amine adduct of any one of claims 1 to 8.    An aqueous solution containing the epoxy-amine adduct of any one of claims 1 to 8.    A water-dispersed resin composition containing the epoxy-amine adduct according to any one of claims 1 to 8, and a urethane resin.    The water-dispersed resin composition of claim 13, which further contains a surfactant.    The water-dispersible resin composition of claim 14, wherein the surfactant is selected from at least one surfactant comprising a group of an anionic surfactant and a nonionic surfactant.    A method for producing a water-dispersed resin composition characterized by mixing an aqueous dispersion containing the epoxy-amine adduct according to any one of claims 1 to 8, and a urethane resin emulsion.    The method for producing a water-dispersed resin composition according to claim 16, wherein the aqueous dispersion containing the epoxy-amine adduct contains a surfactant.    The method for producing a water-dispersed resin composition according to claim 17, wherein the surfactant is at least one selected from the group consisting of an anionic surfactant and a nonionic surfactant.    A sizing agent for carbon fibers, which comprises the epoxy-amine adduct according to any one of claims 1 to 8.    An aqueous coating comprising the sizing agent for carbon fibers according to claim 19.    An aqueous solution containing the sizing agent for carbon fibers as claimed in claim 19.    A water-dispersed resin composition containing the sizing agent for carbon fibers according to claim 19, and a urethane resin.    The water-dispersed resin composition of claim 22, which further contains a surfactant.    The water-dispersed resin composition according to claim 23, wherein the surfactant is selected from at least one surfactant comprising a group of an anionic surfactant and a nonionic surfactant.    A carbon fiber sizing agent according to claim 19, wherein the epoxy-amine adduct is water-soluble.    A sizing agent for carbon fibers, which comprises the water-dispersed resin composition according to any one of claims 13 to 15.    A carbon fiber coated with a sizing agent for carbon fibers, which is coated with a sizing agent for carbon fibers according to any one of claims 19, 25, and 26.    A fiber-reinforced composite material comprising the carbon fiber for coating a carbon fiber sizing agent according to claim 27.    A fiber-reinforced composite material comprising the thermoplastic resin composition of claim 9 or 10 and carbon fibers.    A treatment agent for carbon fibers, which comprises the epoxy-amine adduct according to any one of claims 1 to 8.    A carbon fiber bundle coated with a sizing agent for carbon fibers according to any one of claims 19, 25 and 26.    A prepreg obtained by the carbon fiber of a coated carbon fiber sizing agent according to claim 27.    A prepreg comprising the epoxy-amine adduct according to any one of claims 1 to 8, a thermoplastic resin, and a carbon fiber.    A fiber reinforced composite material formed by the prepreg of claim 33.    A fiber-reinforced composite material comprising the carbon fiber for coating a carbon fiber sizing agent according to claim 27, and a thermoplastic resin.