JP7083641B2 - Sizing agents for organic fibers, organic fibers, textiles, and laminates - Google Patents

Description

The present invention relates to a sizing agent for organic fibers, a sizing agent-coated organic fiber coated with the organic fiber sizing agent, a woven fabric using the sizing agent-coated organic fiber, and the woven fabric and a fiber-reinforced composite material. Regarding laminates.

A sizing agent (converging agent) is generally used as a fiber-reinforced composite material which is a composite material of a reinforcing fiber such as carbon fiber or glass fiber and a resin. The sizing agent is applied as a glue to reinforcing fibers such as carbon fibers, and is used for the purpose of improving the higher workability of the reinforcing fibers having poor convergence.

Examples of the sizing agent include aromatics such as diglycidyl ether of bisphenol A (see Patent Documents 1 and 2) and an epoxy group added to a polyalkylene oxide adduct of bisphenol A (see Patent Documents 3 and 4). Those containing epoxy compounds, urethane emulsions and the like are known.

Japanese Unexamined Patent Publication No. 50-059589 Japanese Unexamined Patent Publication No. 57-171767 Japanese Unexamined Patent Publication No. 61-028074 Japanese Unexamined Patent Publication No. 01-272867

However, for organic fibers other than reinforcing fibers, since there was no sizing agent having good wettability, it was usual that no sizing agent was used. Therefore, when the fiber-reinforced composite material using the reinforcing fiber is bonded to the woven fabric of the organic fiber, there is a problem that the adhesion between the fiber-reinforced composite material and the woven fabric of the organic fiber is poor. When the sizing agent used for the reinforcing fiber such as the sizing agent described in Patent Documents 1 to 4 is used for the organic fiber, the wettability to the organic fiber is poor, and the fiber-reinforced composite material and the woven fabric of the organic fiber are used. The adhesion was also inferior.

Therefore, an object of the present invention is an organic fiber sizing agent capable of forming an organic fiber woven fabric having excellent wettability to organic fibers and excellent adhesion to a fiber-reinforced composite material using reinforcing fibers (particularly carbon fibers). To provide.
Further, another object of the present invention is to provide a woven fabric having excellent adhesion to a fiber-reinforced composite material and an organic fiber coated with a sizing agent for forming the woven fabric.
Further, another object of the present invention is to provide a laminate of an organic fiber woven fabric and a fiber reinforced composite material, which has excellent adhesion between the fiber reinforced composite material and the organic fiber woven fabric.

As a result of diligent studies to solve the above problems, the present inventor has found that among epoxy compounds, specific epoxy compounds, more specifically, specific epoxy-amine adducts, aliphatic epoxy compounds, and derivatives thereof. In common, they have found that it is possible to form an organic fiber woven fabric having excellent wettability to organic fibers and excellent adhesion to a fiber-reinforced composite material, and completed the present invention.

That is, the present invention has an epoxy having a structure in which an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule are added. -Organic characterized by containing at least one selected from the group consisting of a component [I] which is an amine adduct or a derivative thereof, and a component [II] which is an aliphatic epoxy compound (E) or a derivative thereof. A sizing agent for fibers is provided.

The component [I] is preferably at least one selected from the group consisting of the following components [I-1], component [I-2], and component [I-3].
Component [I-1]: An epoxy-amine adduct component [I-2]: which has a structure in which an epoxy compound (A) and an amine compound (B) are added and has two or more amino groups in the molecule. A lactone-modified epoxy-amine adduct having a structure in which the lactone compound (C) is ring-opened and added to the component [I-1]. Meta) Polyfunctional urethane (meth) acrylate-modified epoxy-amine adduct having a structure to which a polyfunctional urethane (meth) acrylate (D) having an acryloyl group is added.

［式中、Ｘは単結合、又は１以上の原子を有する二価の基を示す。］ The epoxy compound (A) is preferably a compound represented by the following formula (a).

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

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

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

［式（ｂ－３）中、Ｒ⁶及びＲ⁸は、同一又は異なって、炭素数１～４のアルキレン基、又は炭素数６～１２のアリーレン基を示す。ｓは、０又は１を示す。Ｒ⁷は、一価の有機基、一価の酸素原子含有基、一価の硫黄原子含有基、一価の窒素原子含有基、又はハロゲン原子を示す。ｔは、０～１０の整数を示す。］
で表されるアミン化合物（Ｂ３）からなる群より選択される少なくとも一種であることが好ましい。 The amine compound (B) has the following formula (b-1).

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

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

[In the formula (b-3), R ⁶ and R ⁸ represent the same or different alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. s indicates 0 or 1. R ⁷ represents a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom-containing group, a monovalent nitrogen atom-containing group, or a halogen atom. t represents an integer from 0 to 10. ]
It is preferable that it is at least one selected from the group consisting of the amine compound (B3) represented by.

The component [II] is preferably an aliphatic epoxy compound derivative having a structure in which the aliphatic epoxy compound (E) and the ethylenically unsaturated monomer (F) are added.

In the sizing agent for organic fibers, the component [II] is an aliphatic epoxy compound (E), and further, (iii) a surfactant, (iv) a polymer dispersant, and (v) polymerizable on a side chain. It may contain one or more water-based components (G) selected from the group consisting of water-soluble or water-dispersible vinyl polymers having no unsaturated group, and an aqueous medium (H).

The aliphatic epoxy compound (E) is preferably epoxidized polybutadiene.

The present invention also provides a sizing agent-coated organic fiber in which the organic fiber is coated with the above-mentioned organic fiber sizing agent.

The present invention also provides a woven fabric containing the above-mentioned sizing agent-coated organic fiber.

The present invention also provides a laminate in which the above-mentioned woven fabric and a fiber-reinforced composite material are laminated.

The sizing agent for organic fibers of the present invention is excellent in wettability to organic fibers by containing a specific epoxy compound or a derivative thereof. Further, the woven fabric of the organic fiber (sizing agent-coated organic fiber) coated with the sizing agent for organic fiber of the present invention has excellent adhesion to the fiber-reinforced composite material using the reinforcing fiber (particularly carbon fiber). Further, by using the sizing-coated organic fiber, a woven fabric and a laminate having high mechanical characteristics (particularly toughness) can be obtained with high productivity.

In the sizing agent for organic fibers of the present invention, an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule are added. A component [I] which is an epoxy-amine adduct having a structure or a derivative thereof (hereinafter, may be simply referred to as “component [I]”), or a component [II] which is an aliphatic epoxy compound or a derivative thereof. Hereinafter, it is a composition (composition used for strengthening organic fibers) containing (may be simply referred to as “component [II]”) as an essential component. The sizing agent for organic fibers of the present invention has good wettability to organic fibers by containing such a component [I] or a component [II] as an essential component. Therefore, by using the sizing agent-coated organic fiber in which the organic fiber is coated with the sizing agent for organic fiber of the present invention, it is possible to obtain an organic fiber capable of forming a woven fabric having excellent adhesion to the fiber-reinforced composite material. The sizing agent for organic fibers of the present invention may contain other optional components other than the component [I] and the component [II].

[Ingredient [I]]
The epoxy-amine adduct or its derivative, which is the component [I] in the sizing agent for organic fibers of the present invention, is an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule (hereinafter, simply "epoxide". Compound (A) ”) and an amine compound (B) having two or more amino groups in the molecule (hereinafter, may be simply referred to as“ amine compound (B) ”) are added. Has. That is, the component [I] is an epoxy-amine adduct or a derivative thereof obtained by reacting the epoxy compound (A) with the amine compound (B).

The component [I] is not particularly limited, but is preferably at least one selected from the group consisting of the following components [I-1], component [I-2], and component [I-3]. ..
Component [I-1]: An epoxy-amine adduct component [I-2]: which has a structure in which an epoxy compound (A) and an amine compound (B) are added and has two or more amino groups in the molecule. A lactone-modified epoxy-amine adduct having a structure in which the lactone compound (C) is ring-opened and added to the component [I-1]. Meta) Polyfunctional urethane (meth) acrylate-modified epoxy-amine adduct having a structure to which a polyfunctional urethane (meth) acrylate (D) having an acryloyl group is added.

1. 1. Ingredient [I-1]
The component [I-1] is an epoxy-amine adduct having two or more amino groups in the molecule, and has an epoxy-amine adduct having a structure in which the epoxy compound (A) and the amine compound (B) are added. A substance (that is, an epoxy-amine adduct obtained by reacting an epoxy compound (A) with an amine compound (B)). More specifically, the epoxy-amine adduct is one or more molecules of the epoxy compound produced by reacting the alicyclic epoxy group of the epoxy compound (A) with the amino group of the amine compound (B). It is an adduct of (A) and an amine compound (B) having one or more molecules (particularly two or more molecules). In the present specification, the term "amino group" simply means -NH ₂ (unsubstituted amino group), and the term "-NH- group" means the unsubstituted amino group (-NH ₂ ). Is not included.

1-1. Epoxy compound (A)
The epoxy compound (A) is a polyepoxy compound (alicyclic epoxy compound) having two or more alicyclic epoxy groups in the molecule. In addition, the "alicyclic epoxy group" in this specification means an epoxy group composed of two adjacent carbon atoms constituting an alicyclic (aliphatic ring) and an oxygen atom.

The alicyclic epoxy group contained in the epoxy compound (A) is not particularly limited, and is, for example, an aliphatic ring (aliphatic hydrocarbon) having 4 to 16 carbon atoms such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. Examples thereof include an epoxy group composed of two adjacent carbon atoms constituting the ring) and an oxygen atom. Among them, as the alicyclic epoxy group, an epoxy group (cyclohexene oxide group) composed of two carbon atoms constituting a cyclohexane ring and an oxygen atom is preferable.

The number of alicyclic epoxy groups contained in the molecule of the epoxy compound (A) may be 2 or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, and even more preferably 2. One or three. By setting the number of alicyclic epoxy groups to 6 or less, the water solubility or water dispersibility of the component [I] tends to be improved, and the stability of the sizing agent for organic fibers tends to be further improved.

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

X in the above formula (a) represents a divalent group (linking group) having a single bond or one or more atoms. Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. Examples thereof include a group in which two or more of the groups are linked. A substituent such as an alkyl group may be bonded to one or more of the carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (a).

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

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 ethylene group, a propylene group, a trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group and 1,3-. Examples thereof include a divalent cycloalkylene group (including a cycloalkylidene group) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group.

Examples of the alkenylene group in the alkenylene group in which a part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include a vinylene group, a propenylene group, and a 1-butenylene group. , 2-Butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like, such as a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, as the epoxidized alkenylene group, an alkenylene group in which the entire carbon-carbon double bond is epoxidized is preferable, and more preferably, the entire carbon-carbon double bond is epoxidized and has 2 to 4 carbon atoms. It is an alkenylene group.

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

Typical examples of the compound represented by the above formula (a) are the compounds represented by the following formulas (a-1) to (a-10), 2,2-bis (3,4-epoxycyclohexyl). Examples thereof include propane, 1,2-bis (3,4-epoxycyclohexyl) ethane, 2,3-bis (3,4-epoxycyclohexyl) oxylane, and bis (3,4-epoxycyclohexylmethyl) ether. In addition, l and m in the following formulas (a-5) and (a-7) represent integers of 1 to 30, respectively. R'in the following formula (a-5) represents an alkylene group having 1 to 8 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, an s-butylene group, or a pentylene. Examples thereof include a linear or branched alkylene group such as a group, a hexylene group, a heptylene group and an octylene group. Among them, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group and an isopropylene group is preferable. N1 to n6 in the following formulas (a-9) and (a-10) represent integers of 1 to 30, respectively.

As the epoxy compound (A), the compound represented by the above formula (a) is preferable, and in particular, from the viewpoint of heat resistance and handleability, the compound represented by the above formula (a-1) [3,4-epoxy]. Cyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; trade name "Selokiside 2021P" (manufactured by Daicel Corporation), etc.] is preferable.

1-2. Amine compound (B)
The amine compound (B) is a polyamine compound having two or more amino groups (-NH ₂ ; unsubstituted amino group) in the molecule. The number of amino groups contained in the molecule of the amine compound (B) may be 2 or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, still more preferably 2 or 3. It is an individual. By setting the number of amino groups to 6 or less, the water solubility or water dispersibility of the component [I] tends to be improved, and the stability of the sizing agent for organic fibers tends to be further improved.

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

P in the above equation (b) represents an integer of 2 or more. p may be an integer of 2 or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, and even more preferably 2 or 3.

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

Examples of the linear or branched p-valent aliphatic hydrocarbon group include a linear or branched divalent aliphatic hydrocarbon group and a linear or branched trivalent aliphatic hydrocarbon. Examples thereof include hydrogen groups, linear or branched tetravalent aliphatic hydrocarbon groups. Examples of the linear or branched divalent aliphatic hydrocarbon group include an alkylene group [for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Nonylene group, _decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, etc. Alkylene group (preferably C _1-18 alkylene group), etc.], alkenylene group [Alkenylene group corresponding to the above alkylene group, for example, a linear or branched alkaneylene group having 2 to 30 carbon atoms such as a vinylene group and an allylene group. (Preferably C _2-18 alkenylene group), etc.] and the like. Examples of the linear or branched trivalent aliphatic hydrocarbon group include an alkane-triyl group [for example, a propane-triyl group, a 1,1,1-trimethylpropane-triyl group, etc., having 3 to 3 carbon atoms. 30 linear or branched alkane-triyl groups (preferably C _3-18 alkane-triyl groups)] and the like can be mentioned. Examples of the linear or branched tetravalent aliphatic hydrocarbon group include an alkane-tetrayl group [for example, a butane-tetrayl group, a 2,2-dimethylpropane-tetrayl group, etc., having 4 to 30 carbon atoms. A linear or branched alkane-tetrayl group (preferably a C _4-18 alkane-tetrayl group)] and the like can be mentioned.

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

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

The heterocycles constituting the above heterocyclic group include aromatic heterocycles and non-aromatic heterocycles. Examples of such a heterocycle include a heterocycle containing an oxygen atom as a heteroatom (for example, a 3-membered ring such as an oxylan ring, a 4-membered ring such as an oxetane ring, a furan ring, a tetrahydrofuran ring, an oxazole ring, and a γ-butyrolactone. 5-membered ring such as a ring, 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholin ring, benzofuran ring, 4-oxo-4H-chromen ring, fused ring such as chroman ring, 3-oxa Cross-linking rings such as tricyclo [4.3.1.1 ^4,8 ] undecane-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring, etc. ), A heterocycle containing a sulfur atom as a heteroatom (for example, a 5-membered ring such as a thiophene ring, a thiazole ring, a thiadiazole ring, a 6-membered ring such as a 4-oxo-4H-thiopyran ring, a fused ring such as a benzothiophene ring, etc. ), Heterocycle containing a nitrogen atom as a heteroatom (for example, 5-membered ring such as pyrrol ring, pyrrolidine ring, pyrazole ring, imidazole ring, triazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine). 6-membered rings such as rings, indole rings, indolin rings, quinoline rings, aclysine rings, naphthylidine rings, quinazoline rings, fused rings such as purine rings, etc.) and the like can be mentioned. The heterocyclic group may be a heterocyclic group having a substituent, and the substituent may be, for example, the linear or branched p-valent aliphatic hydrocarbon group. In addition to good substituents, alkyl groups (eg, C _1-4 alkyl groups such as methyl and ethyl groups), alkenyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups (eg, phenyl groups, naphthyl groups, etc.) Examples thereof include monovalent hydrocarbon groups such as. Further, the nitrogen atom constituting the heterocyclic group in the above heterocyclic group is a conventional protective group (for example, an alkoxy group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group, an aralkyl group, an acyl group, an arylsulfonyl group). , Alkylsulfonyl group, etc.).

Examples of the cyclic p-valent aliphatic hydrocarbon group include a cyclic divalent aliphatic hydrocarbon group, a cyclic trivalent aliphatic hydrocarbon group, and a cyclic tetravalent aliphatic hydrocarbon group. .. Examples of the cyclic divalent aliphatic hydrocarbon group include a cycloalkylene group [for example, a cycloalkylene group having 3 to 20 carbon atoms such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group (for example, a cycloalkylene group having 3 to 20 carbon atoms. Preferably C _3-15 cycloalkylene group)], cycloalkenylene group [cycloalkenylene group corresponding to the above cycloalkylene group, for example, cycloalkenylene group having 3 to 20 carbon atoms such as cyclohexenylene group (preferably C ₃ ). _-15 Cycloalkenylene group), etc.], Cycloalkylidene group [Cycloalkylidene group corresponding to the above cycloalkylene group, for example, cycloalkylidene group having 3 to 20 carbon atoms such as cyclopentylidene group and cyclohexylidene group (preferably C). _3-15 cycloalkylidene group), etc.], cycloalkazienylene group [cycloalkazienylene group corresponding to the above cycloalkylene group, for example, cycloalkazienylene group having 4 to 20 carbon atoms such as cyclopentadienylene group ( Preferred are C _4-15 cycloalkadienylene groups), etc.], divalent polycyclic hydrocarbon groups [eg, spiro hydrocarbons (eg, spiro [4.4] nonane, spiro [4.5] decane, etc.)). -Divalent spirohydrocarbon groups such as diyl groups; ring-aggregated hydrocarbons (eg, bicyclopropyl, etc.)-Divalent ring-aggregated hydrocarbon groups such as diyl groups; bridging ring hydrocarbons (eg, bicyclo [2. 1.0] Pentan, bicyclo [3.2.1] octane, norbornan, norbornen, adamantan, etc.)-Divalent bridging ring hydrocarbon groups such as diyl groups] and the like. Examples of the cyclic trivalent aliphatic hydrocarbon group include a cycloalkane-triyl group and a polycyclic hydrocarbon-triyl group. Examples of the cyclic tetravalent aliphatic hydrocarbon group include a cycloalkane-tetrayl group and a polycyclic hydrocarbon-tetrayl group. The cyclic p-valent aliphatic hydrocarbon group may have a substituent, and the substituent includes, for example, the linear or branched p-valent aliphatic hydrocarbon group. In addition to the substituents which may be used, monovalent groups such as alkyl groups (for example, C _1-4 alkyl groups such as methyl group and ethyl group), alkenyl groups and aryl groups (for example, phenyl group and naphthyl group). Examples include the hydrocarbon group of.

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

Examples of the linking group (divalent group) containing the heteroatom include -CO-, -O-, -CO-O-, -O-CO-O-, -CO-NH-, and -CO-NR. Heteroatoms such as ^a- (substituted amide group; R ^a indicates an alkyl group), -NH-, -NR ^b- (R ^b indicates an alkyl group), -SO-, -SO _2- , etc. (oxygen atom, Examples thereof include a divalent group containing a nitrogen atom, a sulfur atom, etc., and a divalent group in which a plurality of these are linked.

More specifically, the amine compound (B) includes an amine compound (B1) represented by the following formula (b-1), an amine compound (B2) represented by the following formula (b-2), and the following formula. Examples thereof include the amine compound (B3) represented by (b-3) and the amine compound (B4) represented by the following formula (b-4).

In the above formula (b-1), R ² and R ³ are the same or different, a linear, branched, or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic group. A divalent group in which one or more hydrocarbon groups and one or more cyclic aliphatic hydrocarbon groups are bonded directly or via a linking group containing a heteroatom (divalent group) is shown. Examples of the linear, branched, or cyclic divalent aliphatic hydrocarbon group include the substituted or unsubstituted linear, branched, or cyclic divalent aliphatic hydrocarbon group exemplified as ^R1 . Can be mentioned. Further, as a divalent group in which one or more of the above-mentioned linear or branched aliphatic hydrocarbon groups and one or more of the cyclic aliphatic hydrocarbon groups are directly bonded, for example, the following formula (b-). Examples of the group formed by removing the two amino groups at both ends from the structural formula represented by 3) include an exemplary group (for example, cyclohexylene-alkylene group, alkylene-cyclohexylene-alkylene group, etc.). .. Further, as the linking group containing a heteroatom, for example, a group exemplified as a linking group containing a heteroatom in R ¹ can be mentioned.

Among them, as the R ² , a linear or branched divalent aliphatic hydrocarbon group is preferable, a linear or branched alkylene group having 2 to 6 carbon atoms is more preferable, and a linear or branched alkylene group having 2 to 6 carbon atoms is more preferable. ~ 4 linear or branched alkylene groups (particularly ethylene group, trimethylene group, propylene group).

Among them, as the above R ³ , a linear or branched divalent aliphatic hydrocarbon group is preferable, a linear or branched alkylene group having 2 to 6 carbon atoms is more preferable, and a linear or branched alkylene group having 2 to 6 carbon atoms is more preferable. ~ 4 linear or branched alkylene groups (particularly ethylene group, trimethylene group, propylene group). When q is an integer of 2 or more, R ³ (plurality of R ³ ) in each parenthesis may be the same or different. Further, when having two or more kinds of R ³ , the additional form (polymerization form) of the structure in parentheses with q may be a random type or a block type.

In the above equation (b-1), q represents 0 or an integer of 1 or more. The q is, for example, preferably 0 to 100, more preferably 0 to 70, still more preferably 1 to 30, and particularly preferably 1 to 8. By setting q to 100 or less, the water solubility or water dispersibility of the component [I] tends to be improved, and the stability of the sizing agent for organic fibers tends to be further improved. Further, the heat resistance of the component [I] and the adhesion between the organic fiber woven fabric and the fiber-reinforced composite material tend to be further improved. On the other hand, when q is 1 or more, the adhesion between the organic fiber woven fabric and the fiber-reinforced composite material tends to be further improved.

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

Among them, the compounds represented by the above formula (b-1) include ethylenediamine (EDA) and diethylenetriamine (EDA) and diethylenetriamine from the viewpoints of water solubility of the component [I], wettability of the sizing agent for organic fibers to organic fibers, and heat resistance. DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) are preferable, and triethylenetetramine is more preferable. Further, as the compound represented by the above formula (b-1), a commercially available product can also be used.

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

Among them, as the R ⁴ , a linear or branched divalent aliphatic hydrocarbon group is preferable, a linear or branched alkylene group having 2 to 6 carbon atoms is more preferable, and a linear or branched alkylene group having 2 to 6 carbon atoms is more preferable. ~ 4 linear or branched alkylene groups (particularly ethylene group, trimethylene group, propylene group).

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

Among them, as R5, a linear or branched divalent aliphatic hydrocarbon group is preferable, a linear or branched alkylene group having 2 to ⁶ carbon atoms is more preferable, and a linear or branched alkylene group having 2 to 6 carbon atoms is more preferable. ~ 4 linear or branched alkylene groups (particularly ethylene group, trimethylene group, propylene group). When r is an integer of 2 or more, R ⁵ (plurality of R ⁵ ) in each parenthesis may be the same or different. Further, when having two or more kinds of R ⁵ , the additional form (polymerization form) of the structure in parentheses with r may be a random type or a block type.

In the above equation (b-2), r (the number of repetitions of the structural unit in parentheses with r) indicates an integer of 1 or more. The r is, for example, preferably 1 to 100, more preferably 1 to 70, and even more preferably 1 to 30. By setting r to 100 or less, the water solubility of the component [I] is improved, and the heat resistance of the component [I] and the adhesion between the organic fiber woven fabric and the fiber-reinforced composite material tend to be further improved. On the other hand, when r is 1 or more, the adhesion between the organic fiber woven fabric and the fiber-reinforced composite material tends to be further improved.

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

Among them, the compounds represented by the above formula (b-2) include amine-terminated (both-terminal amino groups) polyethylene glycol, amine-terminated polypropylene glycol, and amine-terminated from the viewpoint of wettability of the sizing agent for organic fibers to organic fibers. Polybutylene glycol is preferable, and amine-terminated polypropylene glycol is more preferable. Further, as the compound represented by the above formula (b-2), a commercially available product (for example, manufactured by HUNTSMAN, trade name "JEFFAMIN" series, etc.) can also be used.

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

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

R ⁷ in the above formula (b-3) indicates a substituent on the cyclohexane ring shown in the formula, and is the same or different, a monovalent organic group, a monovalent oxygen atom-containing group, and a monovalent sulfur atom. Indicates a containing group, a monovalent nitrogen atom-containing group, or a halogen atom. Specific examples of R ⁷ include an alkyl group, a halogen atom (fluorine atom, chlorine atom, etc.), a hydroxy group, a carboxy group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, and an acyloxy group. Mercapto group, alkylthio group, alkenylthio group, arylthio group, aralkylthio group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group, nitro group, mono or dialkylamino group, acylamino group, epoxy group, glycidyl Examples thereof include a group, an acyl group, a cyano group, an isocyanato group, an isothiocyanate group, a carbamoyl group, a sulfo group and the like. Further, t in the above formula (b-3) indicates the number of substituents (R ⁷ ) on the cyclohexane ring shown in the formula, and indicates an integer of 0 to 10. When t in the above equation (b-3) is an integer of 2 or more, each R ⁷ may be the same or different.

More specifically, examples of the group formed by removing the two amino groups at both ends from the structural formula represented by the above formula (b-3) include 1,2-cyclohexylene-methylene group, 1, 3-Cyclohexylene-methylene group, 1,4-cyclohexylene-methylene group, cyclohexylidene-methylene group, 1,2-cyclohexylene-ethylene group, 1,3-cyclohexylene-ethylene group, 1,4-cyclohexyl Silen-ethylene group, cyclohexylidene-ethylene group, methylene-1,5,5-trimethyl-1,3-cyclohexylene group (divalent group formed by removing two amino groups from isophorone diamine), etc. Cyclohexylene-alkylene group; 1,2-cyclohexylene-phenylene group, 1,3-cyclohexylene-phenylene group, 1,4-cyclohexylene-phenylene group and other cyclohexylene-allylen groups; methylene-1,2-cyclohexyl Alkylene-cyclohexylene-alkylene group such as methylene-methylene group, methylene-1,3-cyclohexylene-methylene group, methylene-1,4-cyclohexylene-methylene group; methylene-1,2-cyclohexylene-phenylene group, Methylene-1,3-cyclohexylene-phenylene group, alkylene-cyclohexylene-phenylene group such as methylene-1,4-cyclohexylene-phenylene group; phenylene-1,2-cyclohexylene-phenylene group, phenylene-1,3 Examples thereof include an arylene-cyclohexylene-arylene group such as a cyclohexylene-phenylene group and a phenylene-1,4-cyclohexylene-phenylene group.

Among them, as the compound represented by the above formula (b-3), isophorone diamine is preferable from the viewpoint of heat resistance of the component [I]. Further, as the compound represented by the above formula (b-3), a commercially available product (for example, manufactured by Evonik Japan Co., Ltd., trade name “Vestamine IPD”) can also be used.

In the above formula (b-4), u (the number of repetitions of the structural unit in parentheses with u) represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 70, and even more preferably 1. ~ 30. Further, v (the number of structures in parentheses with v bonded to R ⁹ ) in the above formula (b-4) indicates an integer of 3 or more, preferably 3 to 6, and more preferably 3 to 5. , More preferably 3 or 4.

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

As the compound represented by the above formula (b-4), a commercially available product (for example, manufactured by HUNTSMAN, trade name "JEFFAMIN" series, etc.) can be used.

The amine compound (B) is a compound represented by the formula (b-1), the formula (b-1), particularly from the viewpoint of the effect of the sizing agent for organic fibers on improving the wettability of the organic fiber, the heat resistance of the component [I], and the like. The compound represented by b-2) and the compound represented by the formula (b-3) are preferable, and the compound represented by the formula (b-1) and the compound represented by the formula (b-3) are more preferable. Is.

1-3. Method for Producing Epoxy-Amine Adduct; Reaction of Epoxy Compound (A) and Amine Compound (B) The epoxy-amine adduct (that is, component [I-1]) is an epoxy compound (A) and an amine compound (B). ) And can be produced. More specifically, the epoxy-amine adduct is produced by reacting the alicyclic epoxy group of the epoxy compound (A) with the amino group of the amine compound (B).

The epoxy compound (A) and the amine compound (B) as raw materials for the epoxy-amine adduct can be appropriately selected depending on the characteristics to be imparted to the sizing agent for organic fibers. The epoxy-amine adduct is described in the formula (a), for example, when the water solubility or water dispersibility of the component [I], the wettability of the sizing agent for organic fibers with respect to the organic fibers, the heat resistance, and the handleability are emphasized. ) Is reacted with the amine compound (B1) (more preferably both the amine compounds (B1) and (B3)) to obtain an epoxy-amine adduct (“epoxy-amine adduct (“epoxy-amine adduct (”). i) ”) is preferable. Further, for example, when heat resistance is particularly important, an epoxy-amine adduct obtained by reacting the compound represented by the formula (a) with the amine compound (B2) and the amine compound (B3). (Refered to be "epoxy-amine adduct (ii)"). In the epoxy-amine adducts (i) and (ii), epoxy compounds and amine compounds other than the above-mentioned essential epoxy compounds (A) and amine compounds (B) can also be used in combination. For example, an amine compound other than the amine compound (B1) (for example, an amine compound (B2), an amine compound (B3), an amine compound (B4), etc.) can be used in combination as a raw material for the epoxy-amine adduct (i). Further, as a raw material for the epoxy-amine adduct (ii), an amine compound other than the amine compound (B2) and the amine compound (B3) (for example, the amine compound (B1), the amine compound (B4), etc.) can be used in combination. ..

When the above-mentioned epoxy-amine adduct (i) or epoxy-amine adduct (ii) is used as the epoxy-amine adduct, the component [I] has a high thermal decomposition temperature and excellent heat resistance. It can be applied to processing at high temperatures and can contribute to improving the productivity of sizing agent-coated organic fibers. Further, since the glass transition temperature is high to some extent, contamination of the processing machine (roll, etc.) is prevented, and the handleability is excellent.

The compound represented by the formula (a) in the total amount (100% by weight) of the epoxy compound (A) which is the raw material of the component [I-1] (for example, the epoxy-amine adducts (i) and (ii)). The ratio is not particularly limited, but is preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 98 to 100% by weight. By setting the proportion of the compound represented by the formula (a) to 80% by weight or more, the wettability of the sizing agent for organic fibers to organic fibers and the adhesion between the woven fabric of organic fibers and the fiber-reinforced composite material tend to be further improved. There is.

The ratio of the amine compound (B1) to the total amount (100% by weight) of the amine compound (B) which is the raw material of the epoxy-amine adduct (i) is not particularly limited, but is 10% by weight or more (for example, 10 to 100% by weight). % By weight), more preferably 20 to 90% by weight, still more preferably 50 to 80% by weight. By controlling the ratio of the amine compound (B1) to the above range, the water-soluble or water-dispersible component [I], the wettability of the sizing agent for organic fibers to organic fibers, and the woven fabric of organic fibers and the fiber-reinforced composite material. Adhesion tends to be improved.

The ratio of the amine compound (B3) to the total amount (100% by weight) of the amine compound (B) which is the raw material of the epoxy-amine adduct (i) is not particularly limited, but is preferably 10 to 70% by weight, more preferably. Is 20 to 60% by weight, more preferably 30 to 50% by weight. By controlling the ratio of the amine compound (B3) within the above range, the wettability of the sizing agent for organic fibers to the organic fibers and the adhesion between the woven fabric of the organic fibers and the fiber-reinforced composite material tend to be efficiently improved.

The ratio of the amine compound (B2) to the total amount (100% by weight) of the amine compound (B) which is the raw material of the epoxy-amine adduct (ii) is not particularly limited, but is preferably 10 to 90% by weight, more preferably. Is 20 to 80% by weight, more preferably 30 to 70% by weight. By controlling the ratio of the amine compound (B2) within the above range, the wettability of the sizing agent for organic fibers to the organic fibers and the adhesion between the woven fabric of the organic fibers and the fiber-reinforced composite material tend to be efficiently improved.

The ratio of the amine compound (B3) to the total amount (100% by weight) of the amine compound (B) which is the raw material of the epoxy-amine adduct (ii) is not particularly limited, but is preferably 10 to 90% by weight, more preferably. Is 20 to 80% by weight, more preferably 30 to 70% by weight. By controlling the ratio of the amine compound (B3) within the above range, the wettability of the sizing agent for organic fibers to the organic fibers and the adhesion between the woven fabric of the organic fibers and the fiber-reinforced composite material tend to be efficiently improved.

The above reaction (reaction of the epoxy compound (A) and the amine compound (B)) can 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, but a solvent capable of uniformly dissolving or dispersing the epoxy compound (A) and the amine compound (B) is preferable. More specifically, examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, and the like. Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate and the like. Esters; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol; dimethylsulfoxide and the like. .. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination.

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) and the amine compound (B) to be subjected to the above reaction is not particularly limited, but the alicyclic epoxy group of the epoxy compound (A) and the amino group of the amine compound (B) in the above reaction are used. [Alicyclic epoxy group / amino group] (equivalent ratio) is 0.05 to 1.00 (more preferably 0.10 to 0.95, still more preferably 0.15 to 0.90). It is preferable to control such a method. By setting the above ratio [alicyclic epoxy group / amino group] to 0.05 (particularly 0.5) or more, the unreacted amine compound (B) tends to be less likely to remain in the product. On the other hand, by setting the above ratio [alicyclic epoxy group / amino group] to 1.00 or less, the unreacted epoxy compound (A) tends to be less likely to remain in the product.

The reaction between the epoxy compound (A) and the amine compound (B) described above can be allowed to proceed, 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 for advancing 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 collectively charged in a reaction vessel and heated to a reaction temperature as necessary to react them.
[2] A method in which an amine compound (B) is sequentially added to a reaction vessel in which an epoxy compound (A) is charged and heated to a reaction temperature as needed, and both are reacted.
[3] A method in which the epoxy compound (A) is sequentially added to a reaction vessel in which the amine compound (B) is charged and heated to a reaction temperature as needed, and the two are reacted.

The above-mentioned "sequential addition" means continuous addition (a mode of addition over a certain period of time) or intermittent addition (a mode of partial addition in a plurality of times).

Among the above methods [1] to [3], the method of the above [2] or the above method [2] is easy to control the heat of reaction and easily generate an epoxy-amine adduct having a high molecular weight and a high glass transition temperature. The method of [3] is preferable. On the other hand, depending on the application, it may be convenient to have a low molecular weight of the epoxy-amine adduct. In such a case, it is preferable to react by the method of the above [1].

The rate at which the amine compound (B) is added in the above method [2] is not particularly limited, but for example, when the total amount of the amine compound (B) to be added is 100 parts by weight, 0.1 to 20 parts by weight / part. It can be set appropriately from the range of minutes. The speed at which the epoxy compound (A) is added in the method of the above [3] is not particularly limited, but for example, when the total amount of the epoxy compound (A) to be added is 100 parts by weight, the weight is 0.1 to 20 parts by weight. It can be set appropriately from the range of parts / minutes. The amine compound (B) or epoxy compound (A) to be added can be added as it is, or can be added in the state of a solution or a dispersion liquid dissolved or dispersed in a solvent.

When two or more kinds of amine compounds (B) are used, in the method of the above [2], each amine compound (B) may be dropped in a mixed state or dropped in a non-mixed state (each). You may. In the latter case, each amine compound (B) can be dropped simultaneously or sequentially. The same applies to the dropping when two or more kinds of epoxy compounds (A) are used in the method of the above [3].

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, and even more preferably 120 to 250 ° C. By setting the reaction temperature to 30 ° C. or higher, the reaction rate tends to be high and the productivity of the epoxy-amine adduct tends to be further improved. On the other hand, when the reaction temperature is 280 ° C. or lower, the thermal decomposition of the epoxy compound (A) and the amine compound (B) is suppressed, and the yield of the epoxy-amine adduct tends to be further improved. During the above reaction, the reaction temperature can be controlled to be always constant (substantially constant), or can be controlled to change stepwise or continuously.

The time (reaction time) for carrying out the above reaction is not particularly limited, but is preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours, and even more preferably 2 to 8 hours. By setting the reaction time to 0.2 hours or more, the yield of the epoxy-amine adduct tends to be further improved. On the other hand, when the reaction time is 20 hours or less, the productivity of the epoxy-amine adduct tends to be improved.

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

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

The above reaction (reaction of epoxy compound (A) and amine compound (B)) gives an epoxy-amine adduct. After the above reaction, the obtained epoxy-amine adduct is obtained from known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these. It can be separated and purified by such means.

The number of amino groups (-NH ₂ ; unsubstituted amino groups) contained in the molecule of the component [I-1] is 2 or more, preferably 2 to 10, more preferably 2 to 4, and even more preferably. Is 2 or 3. Further, the component [I-1] has substantially no epoxy group (particularly, an alicyclic epoxy group derived from the epoxy compound (A)).

The amino group (-NH ₂ ; unsubstituted amino group) in the component [I-1] is not particularly limited, but usually, the molecular chain terminal (particularly, linear chain) of the component [I-1] (epoxy-amine adduct) is used. In the case of an epoxy-amine adduct in the form of an epoxy-amine adduct, it is located at both ends of the molecular chain of the epoxy-amine adduct). However, the present invention is not limited to this.

As described above, the component [I-1] is produced by the reaction of the alicyclic epoxy group of the epoxy compound (A) with the amino group (-NH ₂ ; unsubstituted amino group) of the amine compound (B). .. The component [I-1] is a -NH- group (substituted amino group) generated by the reaction of the alicyclic epoxy group and the amino group (furthermore, when the amine compound (B1) is used, the amine compound (B1) is used. ) Has a poor reactivity with the alicyclic epoxy group of the epoxy compound (A) (when q is 1 or more), but usually -NH- is contained in the molecule. The group remains unreacted. The number of -NH- groups contained in the molecule of the component [I-1] is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, and even more preferably 2 to 100. When the component [I-1] does not have a -NH- group, the reactivity of the epoxy-amine adduct is lowered, and the effect of improving the adhesion between the organic fiber woven fabric and the fiber-reinforced composite material cannot be sufficiently obtained. In some cases. Further, the water solubility or water dispersibility of the component [I-1] may decrease. The number of -NH- groups possessed by the component [I-1] is, for example, the molecular weight of the component [I-1] in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method. It can be calculated by determining the number of the constituent epoxy compound (A) and amine compound (B).

In contrast to the above, for example, a compound (epoxy-amine adduct) obtained by reacting an epoxy compound having a glycidyl group with an amine compound (B) is prepared by reacting a glycidyl group with an amino group (unsubstituted amino group). Since the reaction between the generated -NH- group and the glycidyl group is very high, a crosslinked structure is usually formed, and when the equivalent of the epoxy compound is large, the -NH- group does not substantially remain.

The number average molecular weight of the epoxy-amine adduct is not particularly limited, but is preferably 200 to 40,000, more preferably 300 to 30,000, and even more preferably 400 to 20,000. By setting the number average molecular weight to 200 or more, the glass transition temperature of the epoxy-amine adduct becomes high to some extent, and contamination of the processing machine (roll or the like) tends to be suppressed. In addition, there is a tendency to impart excellent texture and handleability to organic fibers coated with a sizing agent. On the other hand, when the number average molecular weight is 40,000 or less, the water solubility or water dispersibility of the component [I-1] tends to be further improved. The number average molecular weight of the epoxy-amine adduct can be calculated using the molecular weight in terms of standard polystyrene measured by the gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the epoxy-amine adduct 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 20 to. It is 180 ° C. By setting the Tg of the epoxy-amine adduct to −50 ° C. or higher (particularly 20 ° C. or higher), the heat resistance and mechanical characteristics (toughness, etc.) of the organic fiber coated with the sizing agent and the woven fabric tend to be further improved. In addition, contamination of processing machines (rolls and the like) is suppressed, and there is a tendency that excellent texture and handleability can be imparted to organic fibers coated with a sizing agent. On the other hand, by setting the Tg of the epoxy-amine adduct to 200 ° C. or lower, it may be easy to blend the component [I-1] with other components. The Tg of the epoxy-amine adduct can be heated from 25 ° C. to 20 ° C./min under a nitrogen flow using a differential scanning calorimeter (DSC) [for example, an apparatus manufactured by Seiko Instruments Co., Ltd.]. The temperature was raised to 200-230 ° C at a rate, then cooled to -100 ° C at a cooling rate of 20 ° C / min (this is the first scan), and then at a heating rate of 10 ° C / min. The temperature was raised to 350 ° C, and then cooled to 25 ° C at a cooling rate of 20 ° C / min (the second scan is from the end of the first scan to this point), and then the second measurement was performed. It is obtained from the DSC curve at the time of temperature rise in the scan of.

The 5% weight loss temperature (Td ₅ ) of the epoxy-amine adduct is not particularly limited, but is preferably 280 ° C. or higher, more preferably 300 ° C. or higher. By setting the 5% weight loss temperature of the epoxy-amine adduct to 280 ° C. or higher (particularly 300 ° C. or higher), the component [I-1] can be processed at a higher temperature (for example, production of organic fiber coated with a sizing agent). Tends to be applicable. The 5% weight loss temperature of the epoxy-amine adduct was 25 ° C. under nitrogen flow using a differential thermal weight simultaneous measurement device (TG / DTA) [for example, Seiko Instruments Co., Ltd. device, etc.]. It is obtained by raising the temperature to 400 ° C. at a heating rate of 10 ° C./min.

［式（Ｉ）中、Ｘは、上記式（ａ）におけるものと同じ。］

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

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

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

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

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

The epoxy-amine adduct (i) is a structural unit derived from the epoxy compound (A) (for example, a structural unit represented by the formula (I)) and a structural unit derived from the amine compound (B) (for example, the formula). It has a molecular chain in which the structural units represented by (II) and the structural units represented by the formula (III) are alternately arranged. An amino group, an epoxy group, a hydroxyl group and the like are present at both ends of the molecular chain. The addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be a random type or a block type.

In the above formula (I), if the carbon atom to which X is bonded is the "1-position" carbon atom among the carbon atoms constituting the cyclohexane ring, each cyclohexane ring of the constituent unit represented by the formula (I) is used. The bond position of the nitrogen atom (-NH-) of the constituent unit derived from the amine compound (B) bonded to is the carbon atom at the 3-position or the carbon atom at the 4-position of the cyclohexane ring. When the bond position of the nitrogen atom is the carbon atom at the 3-position, the bond position of the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is the carbon atom at the 4-position. When the bond position of the nitrogen atom is the carbon atom at the 4-position of the cyclohexane ring, the bond position of the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is the carbon atom at the 3-position. The bond positions of the nitrogen atoms (or the bond positions of the hydroxy groups) in the plurality of (two or more) cyclohexane rings in the above formula (I) may be the same or different. If the carbon atoms constituting the cyclohexane ring in the formula (I) are given the above-mentioned position numbers, the following formula is obtained. This also applies to the epoxy-amine adduct (ii).

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

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

The epoxy-amine adduct (ii) is a structural unit derived from the epoxy compound (A) (for example, a structural unit represented by the formula (I)) and a structural unit derived from the amine compound (B) (for example, the formula). It has a molecular chain in which the structural units represented by (III) and the structural units represented by the formula (IV) are alternately arranged. An amino group, an epoxy group, a hydroxyl group and the like are present at both ends of the molecular chain. The addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be a random type or a block type.

When X in the formula (a) contains an ester bond, or when R ¹ (particularly, R ² to R ¹⁰ ) in the formula (b) contains an ester bond, the ester bond is combined with these ester bonds. An amide bond or a hydroxyl group terminal may be formed by an exchange reaction of the amine compound (B) with an amino group. As described above, even if the epoxy-amine adduct (for example, the epoxy-amine adduct (i) and the epoxy-amine adduct (ii)) has a structural unit different from the above-mentioned structural unit in part. good.

The epoxy-amine adduct (that is, the component [I-1]) can be used as it is, or can be used as a solution (for example, an aqueous solution) or a dispersion. For example, the component [I-1] may be used as an aqueous dispersion by using a surfactant as necessary and then dispersing it in water. In addition, the component [I-1] should be used as a salt with an anion (for example, carbonate, carboxylate, etc.) by protonating a part or all of the amino group and -NH- group in the molecule with an acid. You can also. By using a salt, the water solubility or water dispersibility of the component [I-1] tends to be further improved.

When the component [I-1] is used as a salt, the acid constituting the salt causes an acid-base reaction with a basic group such as an amino group possessed by the component [I-1] to form a salt. Any acid that can be produced is not particularly limited, and is not particularly limited. For example, inorganic acids such as hydrochloric acid, phosphoric acid, carbonic acid, sulfuric acid, nitrate, hydrobromic acid; formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include organic acids such as citric acid, tartaric acid, malic acid, lactic acid, maleic acid and fumaric acid. The acid used to form the salt may be used alone or in combination of two or more. Among them, as the acid, carbonic acid and organic acids are preferable, and carbonic acid and acetic acid (particularly carbonic acid) are more preferable in terms of handleability and ease of production. That is, the salt of the component [I-1] is preferably a carbonate or an organic acid salt, more preferably a carbonate or an acetate (particularly preferably a carbonate).

The salt of the component [I-1] can be produced by a known or conventional salt production method. Specifically, for example, the component [I-1] (specifically, a basic group such as an amino group possessed by the component [I-1]) is reacted with an acid (acid-base reaction). -1] salt can be obtained.

The reaction can be carried out in the presence of a solvent or in the absence of a solvent (ie, in the absence of a solvent). The solvent is not particularly limited, and for example, those exemplified in the reaction between the epoxy compound (A) and the amine compound (B) can be used, but at least water is particularly preferable. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination. Further, the amount of the solvent used in the above reaction is not particularly limited and can be appropriately set.

The ratio of the component [I-1] to the acid to be subjected to the above reaction (reaction between the component [I-1] and the acid) is not particularly limited, and the basic group (for example, amino group) contained in the component [I-1] is not particularly limited. , -NH- group, etc.) to be converted to a salt (this ratio can be determined, for example, depending on the desired water solubility or the like), and can be appropriately selected.

The operation for carrying out the above reaction is not particularly limited, and for example, the component [I-1] and the acid can be collectively charged into the reaction vessel and reacted, or either the component [I-1] or the acid can be reacted. It is also possible to charge one of them in a reaction vessel and add the other (for example, the above-mentioned sequential addition) to react.

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

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

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

The above reaction produces a salt of the component [I-1]. After the above reaction, the salt of the component [I-1] is subjected to known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these. It can be separated and purified by such means. Further, since the salt of the component [I-1] has a characteristic of being particularly excellent in water solubility, it can be preferably used in the state of an aqueous solution.

The salt of the component [I-1] has a structure in which a part or all of the basic groups (particularly amino groups and -NH- groups) of the epoxy-amine adduct are formed into salts by at least an acid-base reaction with an acid. Since it has, it has excellent water solubility and can be particularly preferably used in the state of an aqueous solution. Therefore, when the salt of the component [I-1] is used, in addition to the effects of the wettability to the organic fiber and the adhesion between the woven fabric of the organic fiber and the fiber-reinforced composite material, the sizing agent for the organic fiber is used. There is also a tendency to obtain a stabilizing effect on the fiber. The salt of the component [I-1] can be easily converted into a basic group (particularly an amino group or an -NH- group) by thermal decomposition or other treatment (for example, treatment with a strong base), and the amino group can be obtained. Since it can be converted into a component [I-1] having a -NH- group, it exerts the effect of improving the wettability of the epoxy-amine adduct on organic fibers and the adhesion between the organic fiber woven fabric and the fiber-reinforced composite material. be able to. Needless to say, when the salt of the component [I-1] has a structure in which only a part of the basic group of the component [I-1] is a salt (that is, an amino group or The (in the case of having an -NH- group) has an effect of improving the adhesion of the coating film to the object to be coated by itself even if it is not converted into the component [I-1].

The salt of the component [I-1] can be used as it is, or can be used as a solution, a dispersion liquid, or the like. The salt of the component [I-1] can be used in various embodiments because the precipitation of the dissolved substance is unlikely to occur even when the concentration of the aqueous solution is low.

2. 2. Ingredient [I-2]
The component [I-2] is a lactone-modified epoxy-amine adduct having a structure in which the lactone compound (C) is cycloadded to the component [I-1]. More specifically, an epoxy-amine adduct having two or more amino groups in the molecule obtained by the reaction of the epoxy compound (A) and the amine compound (B) (that is, component [I-1]; molecule. It is a lactone-modified epoxy-amine adduct (lactone adduct) obtained by subjecting a lactone compound (C) to a ring-opening addition reaction with a compound having an active hydrogen atom inside. Specifically, the component [I-2] is one molecule of the above, which is produced by the ring-opening addition reaction of the lactone compound (C) starting from the active hydrogen atom contained in the molecule of the epoxy-amine adduct. It is an adduct of an epoxy-amine adduct and one or more molecules of the lactone compound (C). The "ring-opening addition reaction" in the present specification includes both the meanings of the ring-opening addition reaction by one molecule of the lactone compound (C) and the ring-opening addition polymerization by two or more molecules of the lactone compound (C). Will be done.

The epoxy-amine adduct as a raw material for the component [I-2] is a compound having two or more amino groups in the molecule obtained by the reaction of the epoxy compound (A) and the amine compound (B). The epoxy-amine adduct has at least a hydroxy group and two or more amino groups in the molecule, and a hydrogen atom in these amino groups and / or hydroxy groups (either one or both of amino groups and hydroxy groups). Acts as an active hydrogen atom for the ring-opening addition reaction of the lactone compound (C). That is, the component [I-2] is produced by the ring-opening addition reaction of the lactone compound (C) starting from the amino group and / or the hydroxy group contained in the molecule of the epoxy-amine adduct. It is an adduct of one molecule of epoxy-amine adduct and one or more molecules of lactone compound (C).

2-1. Epoxy-amine adduct The epoxy-amine adduct as a raw material for the component [I-2] is the component [I-1]. In addition to the two or more amino groups, the component [I-1] has two or more hydroxy groups in the molecule generated by the reaction between the alicyclic epoxy group and the amino group described above.

2-2. Lactone compound (C)
As the lactone compound (C) as a raw material for the component [I-2], a known or commonly used lactone can be used, and is not particularly limited, but for example, β-propiolactone, β-butyrolactone, and γ-butyrolactone. , Δ-Valerolactone, γ-Valerolactone, ε-caprolactone, γ-caprolactone, δ-caprolactone, ζ-enant lactone, η-caprolactone, these lactones are substituted with one or more alkyl groups such as methyl groups. (For example, 4-methylcaprolactone, etc.) and the like. As the raw material of the component [I-2], the lactone compound (C) may be used alone or in combination of two or more. Among them, ε-caprolactone is preferable as the lactone compound (C). The component [I-2] has a structure formed by the ring-opening addition reaction of the lactone compound (C), so that the adhesion between the woven fabric of the organic fiber and the fiber-reinforced composite material is excellent, and the organic fiber coated with the sizing agent is Demonstrates high mechanical properties (especially toughness).

2-3. Method for Producing Component [I-2] (Lactone-Modified Epoxy-Amine Adduct) As described above, the component [I-2] is obtained by subjecting the epoxy-amine adduct to a ring-opening addition reaction of the lactone compound (C). can get. The -NH- group in the epoxy-amine adduct can also be the starting point of the ring-opening addition reaction of the lactone compound (C), but since it has low reactivity with amino groups, hydroxy groups and the like, the component [I- Usually, the -NH- group remains in 2].

The above reaction can be carried out by a known or conventional method (a known or conventional method in which a lactone is subjected to a ring-opening addition reaction to a compound having an amino group and / or a hydroxy group in the molecule), and usually, epoxy-amine addition is carried out. It can be advanced by heating the substance and the lactone compound (C). In the above reaction, other components such as a co-catalyst can be used if necessary.

The reaction can be carried out in the presence of a solvent or in the absence of a solvent (ie, in the absence of a solvent). The solvent is not particularly limited, and for example, those exemplified in the reaction between the epoxy compound (A) and the amine compound (B) can be used. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination. Further, the amount of the solvent used in the above reaction is not particularly limited and can be appropriately set. When the above reaction is carried out without a solvent, even if the epoxy-amine adduct is a solid, the epoxy-amine adduct is usually dissolved in the lactone compound (C) by heating to efficiently carry out the reaction. It can be carried out.

The ratio of the epoxy-amine adduct to the lactone compound (C) to be subjected to the above reaction (reaction of the epoxy-amine adduct and the lactone compound (C)) is not particularly limited, but the amino group 1 of the epoxy-amine adduct 1 It is preferable to use 1 to 300 mol of the lactone compound (C) per mol, more preferably 2 to 200 mol, still more preferably 5 to 100 mol. In terms of weight ratio, the amount (total amount) of the lactone compound (C) used is preferably 3 to 200 parts by weight, more preferably 10 to 150 parts by weight, still more preferably 10 parts by weight, based on 100 parts by weight of the epoxy-amine adduct. Is 20 to 100 parts by weight. By controlling the ratio of the epoxy-amine adduct and the lactone compound (C) to the above reaction within the above range, the glass transition temperature of the component [I-2] is maintained at a high value to some extent, and the woven fabric of organic fibers can be used. While maintaining the adhesion of the fiber reinforced composite material, its toughness and flexibility tend to be improved and its durability tends to be further improved.

The operation for carrying out the above reaction is not particularly limited, and for example, the epoxy-amine adduct and the lactone compound (C) can be collectively charged into a reaction vessel and reacted, or the epoxy-amine adduct and the lactone compound can be reacted. It is also possible to charge one of (C) in a reaction vessel and add the other (for example, the above-mentioned sequential addition) to react. Further, both can be reacted while being added to the reaction vessel.

The temperature (reaction temperature) in the above reaction is not particularly limited and can be appropriately selected from the range of, for example, 80 to 250 ° C. (for example, 100 to 200 ° C.). Further, the time (reaction time) for carrying out the above reaction is not particularly limited, and can be appropriately selected from the range of, for example, 0.2 to 20 hours (for example, 1 to 8 hours).

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

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

The above reaction produces the component [I-2]. After the above reaction, the component [I-2] is obtained by, for example, a known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these. It can be separated and purified.

The component [I-2] is formed by ring-opening addition of the lactone compound (C) starting from the amino group (-NH ₂ ; unsubstituted amino group) and / or the hydroxy group of the epoxy-amine adduct. It has a structure in which a molecular chain formed by ring-opening addition of a lactone compound (C) is usually bonded to an amino group and / or a hydroxy group portion of an epoxy-amine adduct. The component [I-2] may be one in which the lactone compound (C) is ring-opened and added to all of the amino groups and hydroxy groups of the epoxy-amine adduct, or only a part of the lactone compound (C). May be cycloaddition. The terminal of the molecular chain formed by the ring-opening addition of the lactone compound (C) contained in the component [I-2] is not particularly limited, but is usually a hydroxy group. In addition, this hydroxy group may be converted into another functional group by a technique commonly used in organic synthesis. The component [I-2] may or may not have an amino group, and the same applies to the hydroxy group.

The component [I-2] usually has at least an -NH- group (substituted amino group) derived from an epoxy-amine adduct in the molecule. The number of -NH- groups contained in the molecule of the component [I-2] is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, and even more preferably 2 to 100. The component [I-2] has high reactivity and can further improve the adhesion between the organic fiber woven fabric and the fiber reinforced composite material. The number of -NH- groups in the component [I-2] can be calculated by the same method as the method for calculating the number of -NH- groups in the above-mentioned component [I-1]. The fact that the -NH- group remains unreacted (without reacting with the epoxy compound (A)) in the component [I-2] means that the component [I-2] has thermoplasticity and is soluble in a solvent. It has excellent properties (for example, water solubility and water dispersibility), and also has the effect of being easy to mix with other components.

The number average molecular weight of the component [I-2] is not particularly limited, but is preferably 600 to 80,000, more preferably 800 to 60,000, still more preferably 1,000 to 40,000. By setting the number average molecular weight to 600 or more, the toughness and flexibility of the coating film are improved, and the glass transition temperature is raised to some extent, so that contamination of the processing machine (roll or the like) tends to be suppressed. In addition, there is a tendency to impart excellent texture and handleability to organic fibers coated with a sizing agent. On the other hand, when the number average molecular weight is 80,000 or less, the compounding with other components becomes easy, and the solubility in a solvent may be further improved. The number average molecular weight of the component [I-2] can be calculated by using the molecular weight in terms of standard polystyrene measured by the gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the component [I-2] is not particularly limited, but is preferably −50 to 150 ° C., more preferably −40 to 120 ° C., still more preferably −30 to 100 ° C., and particularly preferably 20 ° C. It is -80 ° C. By setting Tg to −50 ° C. or higher (particularly 20 ° C. or higher), the heat resistance and mechanical characteristics (toughness, etc.) of the organic fiber coated with the sizing agent tend to be further improved. In addition, contamination of processing machines (rolls and the like) is suppressed, and there is a tendency that excellent texture and handleability can be imparted to organic fibers coated with a sizing agent. On the other hand, by setting Tg to 150 ° C. or lower, it may be easy to mix with other components. The glass transition temperature of the component [I-2] is measured by the same method as the Tg of the above-mentioned component [I-1].

The 5% weight loss temperature (Td ₅ ) of the component [I-2] is not particularly limited, but is preferably 280 ° C. or higher, more preferably 290 ° C. or higher. By setting the 5% weight loss temperature to 280 ° C. or higher (particularly 290 ° C. or higher), it tends to be applicable to processing at a higher temperature (for example, production of organic fiber coated with a sizing agent). The 5% weight loss temperature of the component [I-2] is measured by the same method as Td ₅ of the above-mentioned component [I-1].

The component [I-2] can be used as it is, or can be used as a solution (for example, an aqueous solution) or a dispersion. For example, the component [I-2] may be used as an aqueous dispersion by using a surfactant as necessary and then dispersing it in water. In addition, the component [I-2] is a salt with an anion (for example, carbonate, carboxylate, etc.) by protonating a part or all of a basic group such as an amino group or -NH- group in the molecule with an acid. ) Can also be used. By using a salt, the effect of improving the solubility in water can be obtained. By increasing the water solubility of the component [I-2], it tends to be in the state of an aqueous solution or an aqueous dispersion. The method for forming the salt of the component [I-2] is not particularly limited, and for example, it can be carried out according to the method for forming the salt of the component [I-1] described above.

3. 3. Ingredient [I-3]
The component [I-3] is a polyfunctional urethane having a structure in which a polyfunctional urethane (meth) acrylate (D) having two or more (meth) acryloyl groups in the molecule is added to the component [I-1]. Meta) Acrylate-modified epoxy-amine adduct. More specifically, a molecule is added to an epoxy-amine adduct (component [I-1]) having two or more amino groups in the molecule obtained by the reaction of the epoxy compound (A) and the amine compound (B). Addition reaction (Michael addition reaction) is a polyfunctional urethane (meth) acrylate (D) having two or more (meth) acryloyl groups inside (sometimes referred to simply as "polyfunctional urethane (meth) acrylate (D)"). ) Is a polyfunctional urethane (meth) acrylate-modified epoxy-amine adduct (sometimes referred to simply as "urethane-modified epoxy-amine adduct"). Specifically, the component [I-3] is Michael-added by the amino group contained in the molecule of the epoxy-amine adduct and the (meth) acryloyl group contained in the molecule of the polyfunctional urethane (meth) acrylate (D). This is an adduct of one or more molecules of the above epoxy-amine adduct and one or more molecules of polyfunctional urethane (meth) acrylate (D). In addition, in this specification, "(meth) acrylate" means acrylate and / or methacrylate, and the same applies to "(meth) acrylic" and the like.

3-1. Epoxy-amine adduct The epoxy-amine adduct as a raw material for the component [I-3] is the component [I-1]. As described above, the component [I-1] has two or more amino groups in the molecule.

3-2. Polyfunctional urethane (meth) acrylate (D)
As described above, the polyfunctional urethane (meth) acrylate (D) as a raw material for the component [I-3] is a polyfunctional urethane (meth) acrylate having two or more (meth) acryloyl groups in the molecule. .. As the polyfunctional urethane (meth) acrylate (D), a known or commonly used polyfunctional urethane (meth) acrylate can be used, and is not particularly limited, but for example, an aliphatic urethane (meth) acrylate or an aromatic urethane (aroma). Meta) acrylate and the like can be mentioned. The polyfunctional urethane (meth) acrylate (D) may have only one of an acryloyl group and a methacryloyl group, or may have both an acryloyl group and a methacryloyl group.

The number of (meth) acryloyl groups contained in the molecule of the polyfunctional urethane (meth) acrylate (D) may be 2 or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 4. The number is, more preferably two or three. Since the number of (meth) acryloyl groups is two or more, the molecular weight of the component [I-3] tends to be high, so that the component [I-3] can exhibit excellent toughness. In addition, by reducing the number of (meth) acryloyl groups to 6 or less, the water solubility or water dispersibility of the component [I-3] is further improved, and it becomes easier to dissolve by heating, so that it can be blended with other components. It tends to be easier to do.

The weight average molecular weight (Mw) of the polyfunctional urethane (meth) acrylate (D) is not particularly limited, but is preferably 500 to 10000, more preferably 500 to 7000, and even more preferably 500 to 5000. By setting the weight average molecular weight to 500 or more, the flexibility and toughness of the component [I-3] tend to be improved. On the other hand, by setting the weight average molecular weight to 10,000 or less, the compatibility of the component [I-3] with other components tends to be further improved, and the heat resistance tends to be improved. The weight average molecular weight can be calculated from the standard polystyrene-equivalent molecular weight measured by the gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the polyfunctional urethane (meth) acrylate (D) is not particularly limited, but is preferably −70 to 30 ° C., more preferably −60 to 20 ° C., still more preferably −55 to 0 ° C. be. By setting Tg to −70 ° C. or higher, the heat resistance of the component [I-3] tends to be improved. On the other hand, when the Tg is 30 ° C. or lower, the toughness of the component [I-3] tends to be improved. The glass transition temperature of the polyfunctional urethane (meth) acrylate (D) is measured by the same method as Tg of the above-mentioned component [I-1].

The polyfunctional urethane (meth) acrylate (D) is produced by a known or conventional method, and is not particularly limited, but usually, a polyol (X), a polyisocyanate (Y), and a hydroxy group-containing (meth) acrylate (Z). ), Or by reacting the polyisocyanate (Y) with the hydroxy group-containing (meth) acrylate (Z).

The polyol (X) is a compound having two or more hydroxy groups in the molecule. As the polyol (X), one kind or two or more kinds are used. As the polyol (X), a known or commonly used polyol is used, and is not particularly limited. For example, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, and 1,4-butanediol are used. , 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, polyoxy C _2-4 alkylene glycol (polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, etc.), bisphenol A and its alkylene oxide. Additives, bisphenol F and its alkylene oxide adduct, hydride bisphenol A and its alkylene oxide adduct, hydride bisphenol F and its alkylene oxide adduct, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, isosorbide, xylene Glycols, polyester diols, polyether diols, polycarbonate diols and other diols; glycerin, 1,1,1-tris (hydroxymethyl) propane, D-sorbitol, xylitol, D-mannitol, D-mannit, diglycerin, polyglycerin , Trimethylol ethane, trimethylol propane, pentaerythritol, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicon polyol, fluoropolycol, polyolefin polyol, etc. Examples thereof include polyols having a group.

Polyisocyanate (Y) is a compound having two or more isocyanate groups in the molecule. As the polyisocyanate (Y), one kind or two or more kinds are used. As the polyisocyanate (Y), a known or commonly used polyisocyanate is used, and is not particularly limited, but for example, 1,6-hexane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl. Diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate; Examples include the trimer of.

The hydroxy group-containing (meth) acrylate (Z) has one or more (particularly one) hydroxy groups in the molecule and one or more (particularly one) (meth) acryloyl groups in the molecule. It is a compound. As the hydroxy group-containing (meth) acrylate (Z), one kind or two or more kinds are used. As the hydroxy group-containing (meth) acrylate (Z), known or conventional hydroxy group-containing (meth) acrylates are used, and are not particularly limited, but for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. ) Acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, cyclohexanedimethanol (meth) acrylate, bisphenol A diglycidyl diacrylate and other epoxy acrylates. Examples include those with water.

The reaction of the above-mentioned polyol (X), polyisocyanate (Y), and hydroxy group-containing (meth) acrylate (Z) can be carried out by a known or conventional method. -The method described in JP-A-95837, JP-A-2002-145936, JP-A-2011-52227, etc. can be used.

Among the polyfunctional urethane (meth) acrylates (D), polyoxy C _2-4 alkylene glycol (polyethylene glycol, polypropylene) is used as a constituent unit derived from the polyol (X) from the viewpoint of the toughness of the component [I-3]. It is preferable to contain at least a structural unit derived from (glycol, polyoxytetramethylene glycol, etc.). As such a polyfunctional urethane (meth) acrylate (D), for example, trade names "EBECRYL 230", "EBECRYL 270" (all manufactured by Daicel Ornex Co., Ltd.) and the like can be used.

Commercially available products can also be used as the polyfunctional urethane (meth) acrylate (D), for example, trade names "EBECRYL 210", "EBECRYL 215", "EBECRYL 6202", "EBECRYL 230", "EBECRYL 244", "EBECRYL 245", "EBECRYL 270", "EBECRYL 280/15IB", "EBECRYL 2002", "EBECRYL 8307", "EBECRYL 8411", "EBECRYL 8804", "EBECRYL 8804", "EBECRYL 8704" , "EBECRYL 284", "EBECRYL 285", "EBECRYL 4835", "EBECRYL 4858", "EBECRYL 4883", "EBECRYL 6700", "EBECRYL 8402", "EBECRYL 8402" ), Product names "UX-2201", "UX-8101" (all manufactured by Nippon Kayaku Co., Ltd.), product names "UF-8001", "UF-8003", "UX-6101", "UX-" Bifunctional urethane (meth) acrylate (urethane di (meth) acrylate) such as "8101" (all manufactured by Kyoeisha Chemical Co., Ltd.); trade names "EBECRYL 204", "EBECRYL 205", "EBECRYL 254", "EBECRYL 264" , "EBECRYL 265", "EBECRYL 1259", "EBECRYL 9260", "KRM8296", "EBECRYL 294/25 HD", "EBECRYL 4820", "EBECRYL 8311", "EBECRYL 8701" ) Etc. trifunctional urethane (meth) acrylate; trade names "EBECRYL 220", "KRM8200", "KRM8200AE", "EBECRYL 5129", "EBECRYL 8210", "EBECRYL 8301", "KRM8452", "EBECRY" , "EBECRYL 1290k", "KRM7804" (all manufactured by Daicel Ornex Co., Ltd.) and the like, and examples thereof include tetrafunctional or higher functional urethane (meth) acrylates.

3-3. Method for Producing Component [I-3] (Urethane-Modified Epoxy-Amine Adduct) As described above, the component [I-3] consists of an epoxy-amine adduct (component [I-1]) and a polyfunctional urethane (meth). ) It is obtained by subjecting an acrylate (D) to an addition reaction (Michael addition reaction). The -NH- group in the epoxy-amine adduct does not react with the (meth) acryloyl group in the polyfunctional urethane (meth) acrylate (D).

The reaction can be carried out in the presence of a solvent or in the absence of a solvent (ie, in the absence of a solvent). The solvent is not particularly limited, and for example, those exemplified in the reaction between the epoxy compound (A) and the amine compound (B) can be used. Of these, alcohol is preferable. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination. Further, the amount of the solvent used in the above reaction is not particularly limited and can be appropriately set.

The ratio of the epoxy-amine adduct to the polyfunctional urethane (meth) acrylate (D) to be subjected to the above reaction is not particularly limited, but the (meth) acryloyl group (meth) acryloyl group possessed by the polyfunctional urethane (meth) acrylate (D) in the above reaction. The ratio [acryloyl group and methacryloyl group / amino group] (equivalent ratio) between the acryloyl group and the methacryloyl group and the amino group (-NH ₂ ) of the epoxy-amine adduct is more preferably 0.05 to 1.00 (equivalent ratio). Is preferably controlled to be 0.10 to 0.95, more preferably 0.15 to 0.90). By setting the above ratio [acryloyl group and methacryloyl group / amino group] to 0.05 (particularly 0.5) or more, unreacted epoxy-amine adducts tend to be less likely to remain in the product. On the other hand, by setting the above ratio [acryloyl group and methacryloyl group / amino group] to 1.00 or less, unreacted polyfunctional urethane (meth) acrylate (D) tends to be less likely to remain in the product.

The above reaction can be carried out by a known or conventional method, and is not particularly limited. For example, an epoxy-amine adduct and a polyfunctional urethane (meth) acrylate (D) are collectively charged into a reaction vessel and reacted. Alternatively, one of the epoxy-amine adduct and the polyfunctional urethane (meth) acrylate (D) may be charged in a reaction vessel, and the other may be added (for example, the above-mentioned sequential addition) for reaction. can. Further, both can be reacted while being added to the reaction vessel. Above all, from the viewpoint of obtaining a component [I-3] having a more uniform composition, an epoxy-amine adduct (preferably an epoxy-amine adduct solution) is charged in a reaction vessel, and a polyfunctional urethane (meth) acrylate is charged therein. It is preferable to react by sequentially adding (D).

The temperature (reaction temperature) in the above reaction is not particularly limited and can be appropriately selected from the range of, for example, 0 to 200 ° C. (for example, 15 to 100 ° C.). Further, the time (reaction time) for carrying out the above reaction is not particularly limited, and can be appropriately selected from the range of, for example, 0.2 to 20 hours (for example, 1 to 8 hours).

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

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

By the above reaction, the component [I-3] is obtained. After the above reaction, the component [I-3] is obtained by, for example, a known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a separation means combining these. It can be separated and purified.

The component [I-3] has a structure formed by an addition reaction between the epoxy-amine adduct and the polyfunctional urethane (meth) acrylate, and is usually a structural unit derived from the epoxy-amine adduct. And have a molecular chain in which structural units derived from polyfunctional urethane (meth) acrylate are alternately arranged. The component [I-3] may or may not have an amino group (-NH ₂ ; unsubstituted amino group), and may or may not have, for example, 2 to 10 (more preferably 2 to 2 to). It is preferable to have 4 amino groups, more preferably 2 or 3) amino groups.

The component [I-3] has a -NH- group (substituted amino group) derived from the epoxy-amine adduct in the molecule. The number of -NH- groups contained in the molecule of the component [I-3] is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, and even more preferably 2 to 100. By having the -NH- group in the molecule, the component [I-3] can further improve the adhesion between the organic fiber woven fabric and the fiber-reinforced composite material. The number of -NH- groups in the component [I-3] can be calculated by the same method as the method for calculating the number of -NH- groups in the above-mentioned epoxy-amine adduct. The fact that the -NH- group remains unreacted in the component [I-3] means that the urethane-modified epoxy-amine adduct has thermoplasticity and is soluble in a solvent (for example, water-soluble and water-dispersible). It has the effect of being easy to mix with other ingredients.

The number average molecular weight of the component [I-3] is not particularly limited, but is preferably 600 to 80,000, more preferably 800 to 60,000, still more preferably 1,000 to 40,000. By setting the number average molecular weight to 600 or more, the toughness and flexibility of the component [I-3] are improved, and the glass transition temperature is raised to some extent, so that contamination of the processing machine (roll, etc.) tends to be suppressed. There is. In addition, there is a tendency to impart excellent texture and handleability to organic fibers coated with a sizing agent. On the other hand, when the number average molecular weight is 80,000 or less, the compounding with other components becomes easy, and the solubility in a solvent may be further improved. The number average molecular weight of the component [I-3] can be calculated using the molecular weight in terms of standard polystyrene measured by the gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the component [I-3] is not particularly limited, but is preferably −50 to 150 ° C., more preferably −40 to 120 ° C., still more preferably −30 to 100 ° C., and particularly preferably 20 ° C. It is -80 ° C. By setting Tg to −50 ° C. or higher (particularly 20 ° C. or higher), the heat resistance and mechanical properties (toughness, etc.) of the coating film and the reinforced organic fiber tend to be further improved. In addition, contamination of processing machines (rolls and the like) is suppressed, and there is a tendency that excellent texture and handleability can be imparted to organic fibers coated with a sizing agent. On the other hand, by setting Tg to 150 ° C. or lower, it may be easy to mix with other components. The glass transition temperature of the component [I-3] is measured by the same method as the Tg of the above-mentioned component [I-1]. When the component [I-3] has a plurality of glass transition temperatures, it is preferable that at least one (more preferably all) glass transition temperatures are controlled within the above range.

The 5% weight loss temperature (Td ₅ ) of the component [I-3] is not particularly limited, but is preferably 280 ° C. or higher, more preferably 300 ° C. or higher. By setting the 5% weight loss temperature to 280 ° C. or higher (particularly 300 ° C. or higher), it tends to be applicable to processing at a higher temperature (for example, production of organic fiber coated with a sizing agent). The 5% weight loss temperature of the component [I-3] is measured by the same method as Td ₅ of the above-mentioned component [I-1].

The component [I-3] can be used as it is, or can be used as a solution (for example, an aqueous solution) or a dispersion. For example, the component [I-3] may be used as an aqueous dispersion by using a surfactant as necessary and then dispersing it in water. In addition, the component [I-3] is a salt with an anion (for example, a carbonate, a carboxylate, etc.) by protonating a part or all of a basic group such as an amino group or a -NH- group in the molecule with an acid. ) Can also be used. By using a salt, the effect of improving the solubility in water can be obtained. By increasing the water solubility of the component [I-3], it tends to be in the state of an aqueous solution or an aqueous dispersion. The method for forming the salt of the component [I-3] is not particularly limited, and for example, it can be carried out according to the method for forming the salt of the component [I-1] described above.

In the sizing agent for organic fibers of the present invention, one kind of each of the component [I-1], the component [I-2], and the component [I-3] as the epoxy-amine adduct derivative [I] is used alone. It can be used in combination, or two or more types can be used in combination.

[Ingredient [II]]
The component [II] in the sizing agent for organic fibers of the present invention is an aliphatic epoxy compound (E) or a derivative thereof.

4. Aliphatic epoxy compound (E)
The aliphatic epoxy compound (E) is a compound having an epoxy group composed of two adjacent carbon atoms constituting an aliphatic hydrocarbon chain and an oxygen atom. Examples of the aliphatic epoxy compound (E) include glycidyl ethers of alcohols having no w-valent cyclic structure (w is a natural number); monovalent or polyvalent carboxylic acids [eg, acetic acid, propionic acid, fatty acid, etc. Steadic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] glycidyl ester; epoxidized oils and fats having double bonds such as epoxidized flaxseed oil, epoxidized soybean oil, epoxidized ash oil; epoxidized polybutadiene, etc. Examples thereof include epoxides of polyolefins (including polyalkaziene). Examples of the alcohol having no w-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol and 1-butanol; ethylene glycol, 1,2-propanediol, 1 , 3-Propanediol, 1,4-Butanediol, Neopentylglycol, 1,6-hexanediol, Diethylene glycol, Triethylene glycol, Tetraethylene glycol, Dipropylene glycol, Polyethylene glycol, Polypropylene glycol and other dihydric alcohols; Examples thereof include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. Further, the w-valent alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol or the like. Among them, the epoxidized polyolefin is preferable, and epoxidized polybutadiene is more preferable.

The epoxidized polybutadiene can be easily obtained by epoxidizing a commercially available polybutadiene with a hydrogen peroxide solution or a peracid. The number average molecular weight of the polybutadiene used is not particularly limited, but is preferably in the range of about 500 to about 15,000. When the number average molecular weight of polybutadiene is in the above range, the number average molecular weight of the obtained epoxidized polybutadiene tends to be in the range of 500 to 20000. The polybutadiene may be linear or branched.

Examples of commercially available polybutadiene include product names "B-1000", "B-3000", "G-1000", "G-3000" (all manufactured by Nippon Soda Co., Ltd.) and product name "B-1000". , "B-2000", "B-3000", "B-4000" (all manufactured by Nippon Oil Co., Ltd.), product names "R-15HT", "R-45HT", "R-45M" (The above is manufactured by Idemitsu Kosan Co., Ltd.), the product names "Epolide PB3600", "Epolide PB4700" (the above are manufactured by Daicel Co., Ltd.) and the like.

The oxygen oxygen concentration of the epoxidized polybutadiene is not particularly limited, but is preferably 1 to 18% by weight, more preferably 3 to 15% by weight, and further preferably 6 to 12% by weight. When the oxygen concentration of oxylan is 1% by weight or more (particularly, 3% by weight or more), the compatibility with other components tends to be improved. On the other hand, when it is 18% by weight or less, the applicability of the sizing agent for organic fibers tends to be improved.

Among the aliphatic epoxy compound derivatives as the component [II], the aliphatic epoxy compound derivative having a structure in which the aliphatic epoxy compound (E) and the ethylenically unsaturated monomer (F) are added (“Component [II]). II-1] ”). That is, the aliphatic epoxy compound derivative as the component [II] is preferably an aliphatic epoxy compound derivative obtained by reacting the aliphatic epoxy compound (E) with the ethylenically unsaturated monomer (F).

5. Ethylene unsaturated monomer (F)
Examples of the ethylenically unsaturated monomer (F) include an acrylic monomer, a styrene monomer, an olefin monomer, a vinyl ester monomer and the like. Examples of the ethylenically unsaturated monomer include (a) an ethylenically unsaturated monomer having no hydrophilic group (sometimes simply referred to as “monomer (a)”) and (b) the single amount. Ethylene unsaturated monomers having a hydrophilic group copolymerizable with the body (a) (sometimes simply referred to as “monomer (b)”) can be used.

The ratio (weight ratio) of the monomer (a) to the monomer (b) is not particularly limited, but as (a) / (b), 70/30 to 99/1 is preferable, and 80 / is more preferable. It is 20 to 95/5, more preferably 85/15 to 90/10. With such a ratio, the water dispersibility of the component [II-1] can be improved.

5-1. Monomer (a)
Examples of the monomer (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and (meth) acrylic. (Meta) acrylic acid alkyl esters such as cyclohexyl acid, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate; styrene, vinyltoluene, α-methyl Examples thereof include styrene-based monomers such as styrene; olefin-based monomers such as ethylene, propylene, and 1-butene; and vinyl ester-based monomers such as vinyl acetate and vinyl propionate. As the monomer (a), only one kind may be used, or two or more kinds may be used.

The content of the monomer (a) in the ethylenically unsaturated monomer is not particularly limited, but is 70 to 99% by weight based on the total amount (100% by weight) of the ethylenically unsaturated monomer (F). % Is preferable, more preferably 80 to 99% by weight, still more preferably 85 to 95% by weight. When the content of the monomer (a) is within the above range, the adhesion between the organic fiber woven fabric and the fiber-reinforced composite material tends to be further improved.

5-2. Monomer (b)
Examples of the monomer (b) include a monomer having a carboxy group such as acrylic acid, methacrylic acid, maleic acid, and crotonic acid; a (meth) acrylate having a polyoxyethylene chain; acrylamide, N-methylolacrylamide, and the like. Monomer having an amide group such as N-butoxymethylacrylamide; hydroxy C _2-8 alkyl ester of (meth) acrylic acid such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; diethylaminoethyl acrylate, diethylaminoethyl Examples thereof include (meth) acrylic acid esters containing amino groups such as methacrylate; N-vinylpyrrolidone; vinylpyridine and the like.

Further, as the monomer (b), an oxylan ring (epoxide group) -containing polymerizable unsaturated compound may be used, for example, oxylanyl (meth) acrylate, glycidyl (meth) acrylate, and 2-methylglycidyl (meth). ) Acrylate, 2-ethylglycidyl (meth) acrylate, 2-oxylanylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate , Etc., a polymerizable unsaturated compound ((meth) acrylic acid ester derivative, etc.) containing an oxylan ring (monocycle); 3,4-epoxide cyclohexyl (meth) acrylate, 3,4-epoxide cyclohexylmethyl (meth) acrylate, 2, -(3,4-Epoxide Cyclohexyl) ethyl (meth) acrylate, 2- (3,4-epoxidecyclohexylmethyloxy) ethyl (meth) acrylate, 3- (3,4-epoxidecyclohexylmethyloxy) propyl (meth) acrylate 3,4-Epoxide Cyclohexane ring, etc. Epoxide group-containing alicyclic carbon ring-containing polymerizable unsaturated compound ((meth) acrylic acid ester derivative, etc.); 5,6-epoxide-2-bicyclo [2.2 .1] 5,6-Epoxide-2-bicyclo such as heptyl (meth) acrylate [2.2.1] Polymerizable unsaturated compound containing heptane ring ((meth) acrylic acid ester derivative, etc.); epoxidized dicyclo Pentenyl (meth) acrylate [3,4-epoxide tricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate; 3,4-epoxide tricyclo [5.2.1.0] ^2,6 ] Decane-8-yl (meth) acrylate], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxidotricyclo [5.2.1.0 ^2,6 ] decane] -9-Iloxy) ethyl (meth) acrylate; 2- (3,4-epoxide tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl (meth) acrylate], epoxidized dicyclo A polymerizable unsaturated compound containing a 3,4-epoxidotricyclo [5.2.1.0 ^2,6 ] decane ring such as pentenyloxybutyl (meth) acrylate and epoxidized dicyclopentenyloxyhexyl (meth) acrylate. (Meta) acrylic acid ester derivative, etc.) and the like. As another oxylan ring (epoxide group) -containing polymerizable unsaturated compound, a vinyl ether compound containing an epoxy group, an allyl ether compound containing an epoxy group, or the like can also be used.

Further, as the monomer (b), an oxetan ring (oxetanyl group) -containing polymerizable unsaturated compound may be used, for example, oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, and the like. 3-Ethyl-3-oxetanyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3) -Oxetanyl) ethyl (meth) acrylate, 2- (3-ethyl-3-oxetanyl) ethyl (meth) acrylate, 2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 2-[ (3-Ethyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 3-[(3-methyl-3-oxetanyl) methyloxy] propyl (meth) acrylate, 3-[(3-ethyl-3-oxetanyl) ) Methyloxy] propyl (meth) acrylate, a vinyl ether compound containing an oxetanyl group, an allyl ether compound containing an oxetanyl group, or the like can also be used.

Further, as the monomer (b), an oxolan ring (oxolanyl group) -containing polymerizable unsaturated compound may be used, for example, a tetrahydrofurfuryl (meth) acrylate, a vinyl ether compound containing an oxolanyl group, or an oxolanyl group. Examples thereof include allyl ether compounds containing. Specifically, a pyrrole ring-containing C _1-24 alkyl ester of (meth) acrylic acid such as (meth) acrylic acid-1-methyl-2-pyrrolidone and (meth) acrylic acid-1-ethyl-2-pyrrolidone; Oxazole ring-containing C _1-24 alkyl ester of (meth) acrylic acid such as (meth) acrylic acid-1-methyl-2-oxazolidone, (meth) acrylic acid-1-ethyl-2-oxazolidone; γ-methacrylic oxytri. Radical polymerizable silane compounds such as methoxysilane, γ-methacryloxytriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane can also be used. As the monomer (b), only one kind may be used, or two or more kinds may be used.

The content of the monomer (b) in the ethylenically unsaturated monomer is not particularly limited, but is 0 to 30% by weight with respect to the total amount (100% by weight) of the ethylenically unsaturated monomer (F). % Is preferable, more preferably 3 to 20% by weight, still more preferably 5 to 10% by weight. When the content of the monomer (b) is in the above range, the water dispersibility of the sizing agent for organic fibers tends to be improved.

The component [II-1] contains an aliphatic epoxy compound (E) and at least one kind of ethylenically unsaturated monomer (F) in an aqueous medium in the presence of a surfactant and a water-soluble radical polymerization initiator. It is preferably obtained by the emulsification copolymerization of.

Examples of the above-mentioned surfactant include ordinary anionic surfactants, nonionic surfactants, cationic surfactants and the like. Examples of the anionic surfactant include sulfonate-type surfactants such as dodecylbenzene sulfonate and alkylene disulfonate; sulfuric acid such as polyoxyethylene polycyclic phenyl ether sulfate ester salt and polyoxyethylene aryl ether sulfate ester salt. Examples thereof include ester salt-type surfactants. As the anionic surfactant, a sulfuric acid ester salt type surfactant is preferable, and specifically, trade names "NEWCOL707SF", "NEWCOL707SFC", "NEWCOL707SN" (all manufactured by Nippon Embroidery Co., Ltd.) and the like can be used.

In addition to the above, examples of the anionic surfactant include reactive surfactants having a radically polymerizable polymerizable functional group. Examples of the reactive surfactant include a surfactant having a radically polymerizable unsaturated double bond introduced into the molecule of the sulfate ester salt of polyoxyethylene alkyl phenyl ether, and a sulfosuccinic acid alkyl ester salt in the molecule. Surfactants having a radically polymerizable unsaturated double bond introduced therein can be mentioned, and as commercial products, the former are trade names "Aqualon KH-10" and "Aqualon HS-10" (above, Daiichi Kogyo). Pharmaceutical Co., Ltd.), "Adecaria Soap SE-10N" (Adeca Co., Ltd.), as the latter, trade names "Ereminol JS2", "Ereminol RN-30" (all manufactured by Sanyo Kasei Kogyo Co., Ltd.) , Trade names "Latemuru S-180", "Latemuru S-180A" (all manufactured by Kao Co., Ltd.) and the like can be mentioned.

Examples of the nonionic surfactant include nonionic surfactants such as polyoxyalkylene alkyl ether type and polycyclic phenyl ether type. Of these, polyoxyalkylene alkyl ether type nonionic surfactants are preferable, and as commercial products, specifically, the trade names are "Neugen EA-197D", "Neugen XL", "Neugen ET-B", and "Neugen TDS". "(The above is manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like can be used.

In addition to the above, as non-ionic surfactants, surfactants in which a radically polymerizable unsaturated double bond is introduced into the molecule of polyoxyethylene alkyl phenyl ether, trade names "Aqualon RN-20", " RN-50 ”(above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), trade name“ Adecaria Soap NE-20 ”,“ NE-40 ”(above, manufactured by Adeca Co., Ltd.) and the like can be mentioned.

Examples of the cationic surfactant include quaternary ammonium salt types such as tetramethylammonium chloride and tetramethylammonium hydroxide; alkylamine salt types such as monomethylamine hydrochloride and dimethylamine hydrochloride; butylpyridinium chloride, dodecylpyridinium chloride and the like. Examples thereof include substances having a pyridine ring of.

As the surfactant, only one kind may be used, or two or more kinds may be used. As the above-mentioned surfactant, it is preferable to use a combination of an anionic surfactant and a nonionic surfactant. In this case, the ratio (weight ratio) of the amount of the anionic surfactant to the nonionic surfactant used is not particularly limited, but the anionic surfactant / nonionic surfactant is 90/10 to 10/10. It is preferably / 90, more preferably 70/30 to 30/70, and even more preferably 60/40 to 30/70.

Examples of the water-soluble radical polymerization initiator include persulfates, peroxides, azo compounds and the like. Specifically, for example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2'-azobisisobutyronitrile, 2, Examples thereof include 2'-azobis (2-diaminopropane) hydroxychloride. As the water-soluble radical polymerization initiator, only one kind may be used, or two or more kinds may be used. The amount of the water-soluble radical polymerization initiator used is preferably 0.05 to 2 parts by weight with respect to the total amount (100 parts by weight) of the aliphatic epoxy compound (E) and the ethylenically unsaturated monomer (F). , More preferably 0.1 to 0.5 parts by weight. When it is desired to accelerate the polymerization rate and polymerize at a low temperature, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid salt, or longalit can be used in combination with the radical polymerization initiator. Further, for adjusting the molecular weight, a chain transfer agent such as dodecyl mercaptan or α-methylstyrene dimer may be used.

Examples of the aqueous medium include aliphatic water-soluble alcohols such as methanol, ethanol and n-propanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether. Can be mentioned. As the solvent, only one kind may be used, or two or more kinds may be used.

The method of the emulsification copolymerization is not particularly limited, but is, for example, in the presence of an aqueous medium, an aqueous component (G) described later (particularly a surfactant), and the water-soluble radical polymerization initiator. Monomer dropping method in which a mixture of a) and the monomer (b) is dropped; the mixture of the monomer (a) and the monomer (b) is emulsified in the presence of an aqueous medium and an aqueous component (G). Pre-emulsion method in which polymerization is carried out while dropping a mixture of water-based medium, aqueous component (G), water-soluble radical polymerization initiator, monomer (a), and monomer (b). A one-bath polymerization method in which polymerization is carried out can be mentioned. Further, in the monomer dropping method and the pre-emulsion method, 1 to 50% by weight, preferably 1 to 30% by weight, can be added before the start of polymerization with respect to the total amount of dropping. From the viewpoint of safety, the monomer dropping method and the pre-emulsion method are preferable, and among them, the pre-emulsion method is preferable.

[Sizing agent for organic fibers]
The sizing agent for organic fibers of the present invention may contain at least the component [I] or the component [II]. Among them, those containing the component [I] or the component [II], that is, those containing only one of the component [I] and the component [II] are preferable.

Further, the sizing agent for organic fibers of the present invention may contain a solvent, other additives and the like in addition to the component [I] and the component [II], and the component [I] and / or the component [ II] may be the only component.

The solvent that may be contained in the sizing agent for organic fibers of the present invention is not particularly limited, but is limited to water; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; benzene, toluene and the like. Aromatic hydrocarbons such as xylene, ethylbenzene; halogenated hydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane; ketones such as acetone, methylethylketone, methylisobutylketone; Ethers such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, benzonitrile; methanol, ethanol, isopropyl alcohol , Butanol and the like; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like; dimethyl sulfoxide and the like. Of these, water and alcohol (particularly water) are preferable because they have a small load on the environment and work environment. That is, the sizing agent for organic fibers of the present invention is a solution (particularly, an aqueous solution) or dispersion of the component [I] and / or the component [II] containing water and / or alcohol (either one or both of water and alcohol). It may be a liquid (particularly, an aqueous dispersion). When the component [I] is a salt of the component [I-1], a salt of the component [I-2], or a salt of the component [I-3], the sizing agent for organic fibers of the present invention has a particularly low concentration. It has a great merit in that it is easy to prepare as an aqueous solution of. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination.

The sizing agent for organic fibers of the present invention may also contain various additives such as lubricants such as fatty acids, amides and esters; and coupling agents such as silane coupling agents and titanium coupling agents.

When the above component [II] is an aliphatic epoxy compound (E), the sizing agent for organic fibers of the present invention further comprises (iii) a surfactant, (iv) in addition to the aliphatic epoxy compound (E). Selected from the group consisting of a polymer dispersant and (v) a water-soluble or water-dispersible vinyl polymer having no polymerizable unsaturated group in the side chain (sometimes referred to as "vinyl polymer (v)"). It is preferable to include one or more water-based components (sometimes referred to as “water-based component (G)”) and an aqueous medium (H).

As the above-mentioned (iii) surfactant, for example, those exemplified as the surfactant used for the emulsion copolymerization of the above-mentioned component [II-1] can be used. As the surfactant, only one kind may be used, or two or more kinds may be used. Above all, it is preferable to use a combination of an anionic surfactant and a nonionic surfactant.

(Iii) The ratio of the amount of the anionic surfactant and the nonionic surfactant used as the surfactant [anionic surfactant / nonionic surfactant] (weight ratio) is not particularly limited, but It is preferably 90/10 to 10/90, more preferably 70/30 to 30/70, and even more preferably 60/40 to 30/70.

(Iv) Examples of the polymer dispersant include polyvinyl alcohol, polyvinylpyrrolidone, metal salts and ammonium salts of ethylene vinyl ether maleic acid copolymers, metal salts and ammonium salts of styrene maleic acid copolymers, carboxymethyl cellulose and the like. Be done.

Examples of the vinyl polymer include polymers of radically polymerizable monomers such as acrylic monomers, styrene monomers, olefin monomers, and vinyl ester monomers. Examples of the radically polymerizable monomer include the above-mentioned monomers (a) and the above-mentioned monomers (b). Above all, it is preferable to use the above-mentioned monomer (b) as the above-mentioned radically polymerizable monomer, which tends to facilitate the acquisition of a water-soluble or water-dispersible vinyl polymer.

(V) The ratio of the monomer (a) to the monomer (b) [monomer (a) / monomer (b)] (weight ratio) used for synthesizing the vinyl polymer is not particularly limited. However, it is preferably 70/30 to 99/1, more preferably 80/20 to 95/5, and even more preferably 85/15 to 95/5. When the above ratio is in the above range, it tends to be easy to obtain a water-soluble or water-dispersible vinyl polymer of the aliphatic epoxy compound (E).

(V) The method for synthesizing the vinyl polymer is not particularly limited, but a method of polymerizing a mixture of radically polymerizable monomers in the presence of a solvent and an initiator is preferable. After completion of the polymerization, it is preferable to add water to remove the solvent used for the polymerization. The above-mentioned polymerization may be a drop polymerization or a batch polymerization.

The solvent used for the above polymerization is not particularly limited, but a water-soluble solvent having a boiling point of 200 ° C. or lower at normal pressure is preferable. Examples of the water-soluble solvent include those exemplified as an aqueous medium used for the emulsion copolymerization of the component [II-1]. As the solvent, only one kind may be used, or two or more kinds may be used.

As the initiator, a water-soluble or oil-soluble persulfate, peroxide, azo compound or the like can be used. Among them, those exemplified as the water-soluble radical polymerization initiator used for the emulsion copolymerization of the component [II-1] are preferable. As the initiator, only one kind may be used, or two or more kinds may be used. The amount of the initiator used is preferably 0.05 to 2 parts by weight, more preferably 0.1 to 0 parts by weight, based on (v) the total amount of the radically polymerizable monomer (100 parts by weight) forming the vinyl polymer. 5 parts by weight. When it is desired to accelerate the polymerization rate and polymerize at a low temperature, the above-mentioned reducing agent can be used in combination with the initiator. In addition, the above-mentioned chain transfer agent may be used for adjusting the molecular weight.

The content of the aqueous component (G) in the sizing agent for organic fibers of the present invention is not particularly limited, but is preferably 1 to 50% by weight with respect to the total amount (100% by weight) of the sizing agent for organic fibers. It is more preferably 1 to 30% by weight, still more preferably 1 to 10% by weight. When the content of the aqueous component (G) is in the above range, the water solubility or water dispersibility of the aliphatic epoxy compound (E) tends to be further improved.

When the aqueous component (G) is (iii) a surfactant, the content of (iii) the surfactant is not particularly limited, but is 1 to 50 with respect to 100 parts by weight of the aliphatic epoxy compound (E). It is preferably by weight, more preferably 1 to 30 parts by weight, and even more preferably 5 to 15 parts by weight. When the aqueous component (G) is a (v) vinyl polymer, the content of the (v) vinyl polymer is not particularly limited, but is 10 to 100 with respect to 100 parts by weight of the aliphatic epoxy compound (E). It is preferably by weight, more preferably 30 to 100 parts by weight, and even more preferably 50 to 100 parts by weight. When the content of the aqueous component (G) is in the above range, the water solubility or water dispersibility of the aliphatic epoxy compound (E) tends to be further improved.

The water-based medium (H) (water-based medium contained in the sizing agent for organic fibers containing the aliphatic epoxy compound (E) and the aqueous component (G)) is the water-based medium used for the emulsification copolymerization of the component [II-1]. Examples thereof include those exemplified as a medium. As the aqueous medium, only one kind may be used, or two or more kinds may be used.

The content of the component [I] and the component [II] in the sizing agent for organic fibers of the present invention (when both are contained, the total amount of the component [I] and the component [II]) is not particularly limited, but is organic other than the solvent. It is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 50% by weight or more, still more preferably 90% by weight or more, based on the total amount (100% by weight) of the sizing agent for fibers.

The organic fiber to which the sizing agent for organic fiber of the present invention is applied does not include the reinforcing fiber. Examples of the resin constituting the organic fiber include polyolefin (for example, polyethylene, polypropylene, polybutadiene, etc.), vinyl-based polymer (for example, acrylic resin, polystyrene, etc.), polyamide (for example, nylon 6, nylon 66, nylon 11). , Nylon 12, Nylon 610, Nylon 612, Nylon 61, Nylon 6T, Nylon 9T, etc.), Polyester (eg Polyethylene terephthalate, Polybutylene terephthalate), Polyvinyl chloride, Polyvinylidene chloride, Polycarbonate, Polyacetal, Polyphenylene oxide, Polyphenylene sulfide , Polyether sulfone, polyether ether ketone and other thermoplastic resins; epoxy resin, unsaturated polyester, vinyl ester resin, allyl resin (for example, diallyl phthalate resin, etc.), phenol resin, polyimide, cyanate resin, maleimide resin, urea resin. , Curable resin (curable compound) such as melamine resin and silicone resin (for example, thermosetting resin (thermosetting compound), photocurable resin (photocurable compound), etc.) and the like. However, the above-mentioned "resin" does not include the component [I] and the component [II]. The above resins may be used alone or in combination of two or more.

The content of the resin in the organic fiber is not particularly limited, but is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 70% by weight or more, based on the total amount of the organic fiber (100% by weight). 80% by weight or more.

Further, in the present specification, the above-mentioned reinforcing fiber refers to a known or commonly used reinforcing fiber, and is a carbon fiber, a glass fiber, an aramid fiber, a boron fiber, a graphite fiber, a silicon carbide fiber, a high-strength polyethylene fiber, or a tungsten carbide. Fibers, polyparaphenylene benzoxazole fibers (PBO fibers) are included. Examples of the carbon fiber include polyacrylonitrile (PAN) -based carbon fiber, pitch-based carbon fiber, gas phase-grown carbon fiber and the like.

[Organic fiber coated with sizing agent]
By applying (coating) the sizing agent for organic fibers of the present invention to the organic fibers, the organic fibers are coated with the sizing agent for organic fibers of the present invention. (Sometimes referred to as "fiber") is obtained.

The method of applying the sizing agent for organic fibers of the present invention to the organic fibers is not particularly limited, but for example, a method of immersing the organic fibers in the sizing agent for organic fibers of the present invention and the sizing agent for organic fibers of the present invention adhere to the organic fibers. Known or conventional methods such as a method of bringing the organic fiber into contact with the roller and a method of atomizing the sizing agent for organic fiber of the present invention and spraying the organic fiber onto the organic fiber can be mentioned. The sizing agent for organic fibers of the present invention may be applied to the entire surface of the organic fibers or to a part of the surface of the organic fibers. Further, the coating thickness and the coating amount can be adjusted as appropriate, and are not particularly limited.

After applying the sizing agent for organic fibers of the present invention, heat treatment may be performed if necessary. The conditions of the heat treatment are not particularly limited, but the heating temperature is preferably 40 to 300 ° C, more preferably 60 to 250 ° C. The heating time can be appropriately adjusted according to the heating temperature, and is not particularly limited, but is preferably 1 second to 60 minutes, more preferably 5 seconds to 10 minutes. In the above heat treatment, the heating temperature can be constant, or can be changed continuously or stepwise. Further, the heat treatment may be continuously performed in one step, or may be intermittently performed in two or more steps. The heat treatment is generally carried out to promote the impregnation of the sizing agent and to dry the solvent. The heat treatment can be performed by a known or conventional method (for example, heating using a hot air oven). Further, when the sizing agent for organic fibers of the present invention has curability, it may be cured by the above heat treatment or separately.

Since the sizing agent-coated organic fiber of the present invention is coated with the component [I] and / or the component [II] in the sizing agent for organic fiber of the present invention, it has excellent adhesion to the fiber-reinforced composite material. Further, when an epoxy-amine adduct having particularly excellent heat resistance is used as the component [I] in the sizing agent for organic fibers of the present invention, it can be applied to processing at a high temperature (for example, production of organic fibers coated with a sizing agent). Therefore, it can also contribute to improving the productivity of organic fiber woven fabrics. Furthermore, when an epoxy-amine adduct having a glass transition temperature high to some extent is used as the component [I] in the sizing agent for organic fibers of the present invention, contamination of the processing machine (roll, etc.) is prevented, and the sizing agent is also used. It is also possible to impart excellent texture and handleability to the coated organic fiber. Further, the sizing agent for organic fibers of the present invention also has excellent functions as a general sizing agent such as a function of converging organic fibers and a function of imparting flexibility to organic fibers. Therefore, the sizing agent of the present invention is provided. The agent-coated organic fiber has good handleability and excellent high-order processability.

Since the sizing agent-coated organic fiber of the present invention has the above-mentioned characteristics, the woven fabric obtained by using the sizing agent-coated organic fiber (sometimes referred to as "the woven fabric of the present invention") is excellent for the fiber-reinforced composite material. Has good adhesion. In addition, it has excellent heat resistance and mechanical strength, and has high productivity. The woven fabric of the present invention can be produced by a known or conventional method.

The sizing agent-coated organic fiber woven fabric of the present invention has excellent adhesion to a fiber-reinforced composite material using reinforcing fibers (particularly carbon fibers). The fiber-reinforced composite material is formed of, for example, a prepreg obtained by impregnating or coating a reinforcing fiber with a resin composition containing a resin (for example, the resin constituting the above-mentioned organic fiber). The method for producing the fiber-reinforced composite material is not particularly limited, but is known or commonly used, for example, a hand lay-up method, a prepreg method, an RTM method, a pull-fusion method, a filament winding method, a spray-up method, a pultrusion method, and the like. It can be manufactured by a melt impregnation method, a powder method, or the like.

By laminating the woven fabric of the present invention with the fiber-reinforced composite material, it is possible to obtain a laminate in which the woven fabric of the present invention and the fiber-reinforced composite material of the reinforcing fibers are laminated. The above-mentioned laminate can be used as a material for various structures, and is not particularly limited, for example, an aircraft fuselage, a main wing, a tail wing, a moving wing, a fairing, a cowl, a door, etc .; a spacecraft motor case, etc. Main wings, etc .; Artificial satellite structure; Automobile parts such as automobile chassis; Railroad vehicle structure; Bicycle structure; Ship structure; Wind power generation blade; Pressure vessel; Fishing rod; Tennis racket; Golf shaft; Robot arm; Cable ( For example, it can be preferably used as a material for a structure such as a cable core material).

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

Example 1
3,4-Epoxy Cyclohexylmethyl (3,4-Epoxy) Cyclohexanecarboxylate (trade name "Ceroxide 2021P", manufactured by Daicel Co., Ltd.) 30.0 parts by weight, and amine-terminated polypropylene glycol (trade name "JEFFAMINE D-230") , HUNTSMAN) 35.9 parts by weight were mixed, and then the reaction was carried out at 160 ° C. for 2 hours with stirring to synthesize an epoxy-amine adduct. To 70 parts by weight of the epoxy-amine adduct, 100 parts by weight of the trade name "NEWCOL780SF" (surfactant, manufactured by Nippon Emulsifying Co., Ltd., active ingredient: 30% by weight) was charged and dissolved. Next, 300 parts by weight of ion-exchanged water was added dropwise over about 10 minutes under stirring and mixing, and after the addition was completed, the mixture was forcibly emulsified at 10000 rpm for 1 hour using a homomixer to obtain an epoxy-amine adduct water-dispersed resin composition. rice field. Further, the organic solvent contained in the water-dispersible resin composition was removed under reduced pressure to obtain the desired epoxy-amine adduct water-dispersed resin composition having a solid content weight of 14%, a viscosity of 10 mPa · s and a pH of 9.0. rice field.

Example 2
Epoxidized polybutadiene (trade name "Epolide PB3600", manufactured by Dycel Co., Ltd.) 90 parts by weight, trade name "NEWCOL707SF" (surfactant, manufactured by Nippon Embroidery Co., Ltd., active ingredient: 30% by weight) 6 weight 6 parts by weight of "Neugen EA-197D" (surfactant, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., active ingredient: 60% by weight) was charged and mixed. Next, 180 parts by weight of ion-exchanged water was added dropwise over about 2 hours under stirring and mixing, and after the addition was completed, the mixture was forcibly emulsified at 10000 rpm for 1 minute using a homomixer to obtain the desired epoxidized polybutadiene water-dispersed resin composition. rice field.

Example 3
Bisphenol A-diglycidyl ether (trade name "jER828", manufactured by Mitsubishi Chemical Corporation) is mixed with 100 parts by weight of isophorone diamine (trade name "Vestamine IPD", manufactured by Epoxy Japan Co., Ltd.) by 23 parts by weight. An epoxy-amine adduct water-dispersed resin composition was obtained.

[evaluation]
The following evaluation was performed using the water-dispersible resin composition obtained in the examples.

(1) Wetness PPS (polyphenylene sulfide) fiber (trade name "Procon", manufactured by Toyobo Co., Ltd.) is impregnated with the water-dispersible resin composition obtained in Example 1 and then dried and removed. Epoxy obtained in Example 2 on PPS fiber coated with an epoxy-amine adduct (referred to as "PPS fiber A") and PPS fiber (trade name "Procon", manufactured by Toyobo Co., Ltd.). A fiber coated with polybutadiene (referred to as "PPS fiber B") was obtained. The water-dispersible resin composition obtained in Examples 1 and 2 had good wettability with respect to PPS fibers.

(2) Adhesion Aramid fiber (trade name "Kevlar", manufactured by Toray DuPont Co., Ltd.) is impregnated with the water-dispersible resin composition obtained in Example 1 and then dried and removed to remove the aramid fiber. The epoxidation obtained in Example 2 on a fiber coated with an epoxy-amine adduct (referred to as "aramid fiber A") and an aramid fiber (trade name "Kevlar", manufactured by Toray DuPont Co., Ltd.). A fiber coated with polybutadiene (referred to as "aramid fiber B") was obtained. The wettability of the water-dispersed resin composition obtained in Examples 1 and 2 to the aramid fiber was good. Next, woven fabrics using the PPS fibers A and B were prepared, respectively, and these were pressure-bonded to the fiber-reinforced composite material using the aramid fibers A and B and bonded to each other. I confirmed that there was no problem with. On the other hand, when a woven fabric was prepared using PPS fiber (trade name "Procon", manufactured by Toyobo Co., Ltd.), and this was pressure-bonded to a fiber-reinforced composite material using the above-mentioned aramid fibers A and B, they adhered to each other. The sex was relatively inadequate.

(3) Shear stress The water-dispersed resin composition obtained in Example 3 is formed into a ball having a diameter of about 100 μm in each of the PPS fiber A, the PPS fiber B, the aramid fiber A, and the aramid fiber B. The fibers were adhered and cured at 80 ° C. for 2 hours and further at 120 ° C. for 2 hours to bond the resin balls to the fibers. These were measured by a test method called the microdrop red test to measure the shear stress between the resin balls and the fibers. As a comparative example, a resin ball was similarly bonded to a fiber to which nothing was applied, and the shear stress between the resin ball and the fiber was measured by a microdrop red test. The measurement results are shown in Table 1. As shown in Table 1, the water-dispersed resin composition obtained in Example 3 was able to improve the shear stress of the fibers with respect to both the organic fibers and the reinforcing fibers.

Claims (9)

An epoxy-amine adduct having a structure in which an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule are added, or an adduct thereof. It contains at least one selected from the group consisting of a derivative component [I] and a polyolefin epoxide or a derivative thereof [II].
The epoxy compound (A) has the following formula (a).

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

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

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

[In the formula (b-3), R ⁶ and R ⁸ represent the same or different alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. s indicates 0 or 1. R ⁷ represents a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom-containing group, a monovalent nitrogen atom-containing group, or a halogen atom. t represents an integer from 0 to 10. ]
It is at least one selected from the group consisting of the amine compound (B3) represented by .
A sizing agent used for coating polyphenylene sulfide fibers that form a woven fabric to be laminated with a fiber-reinforced composite material using reinforcing fibers . The sizing agent according to claim 1, wherein the component [I] is at least one selected from the group consisting of the following component [I-1], component [I-2], and component [I-3].
Component [I-1]: An epoxy-amine adduct component [I-2] having a structure in which the epoxy compound (A) and the amine compound (B) are added and having two or more amino groups in the molecule. ]: A lactone-modified epoxy-amine adduct having a structure in which the lactone compound (C) is ring-opened and added to the component [I-1]. Component [I-3]: Two or more in the molecule of the component [I-1]. Polyfunctional urethane (meth) acrylate-modified epoxy-amine adduct having a structure to which a polyfunctional urethane (meth) acrylate (D) having a (meth) acryloyl group is added. The sizing agent according to claim 1 or 2, wherein the component [II] is an aliphatic epoxy compound derivative having a structure in which an epoxidized polyolefin and an ethylenically unsaturated monomer (F) are added. The component [II] is an epoxidized polyolefin, and further, (iii) a surfactant, (iv) a polymer dispersant, and (v) a water-soluble or water-dispersed substance having no polymerizable unsaturated group in the side chain. The sizing agent according to any one of claims 1 to 3, which comprises one or more water-based components (G) selected from the group consisting of sex vinyl polymers and an aqueous medium (H). The sizing agent according to any one of claims 1 to 4, wherein the epoxidized product of the polyolefin is epoxidized polybutadiene. The content of the component [I] and the component [II] in the sizing agent (when both are contained, the total amount of the component [I] and the component [II]) is 50 with respect to the total amount of the sizing agent other than the solvent. The sizing agent according to any one of claims 1 to 5, which is in an amount of% by weight or more. A sizing agent-coated organic fiber in which the polyphenylene sulfide fiber is coated with the sizing agent according to any one of claims 1 to 6 . A woven fabric containing the sizing agent-coated organic fiber according to claim 7 . A laminate in which the woven fabric according to claim 8 and a fiber-reinforced composite material are laminated.