JP2017226711A - Epoxy-amine adduct, resin composition, sizing agent, sizing agent-coated carbon fiber, and fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy-amine adduct which has high reactivity, can improve adhesiveness between a resin and an addition material in a polymer-based composite, is excellent in heat resistance and water solubility and has a rather high glass transition temperature and excellent hardness.SOLUTION: An epoxy-amine adduct is obtained by reaction of an epoxy compound (A) which is a compound having two or more amino groups in the molecule and has two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule, and uses a compound (A1) having one or more 5-membered rings in the molecule as the epoxy compound (A).SELECTED DRAWING: None

Description

  The present invention relates to an epoxy-amine adduct, a resin composition containing the epoxy-amine adduct, and a fiber-reinforced composite material formed from a prepreg obtained by impregnating or coating the resin composition on a reinforcing fiber. The present invention further relates to a sizing agent containing the above epoxy-amine adduct, a sizing agent-coated carbon fiber obtained by applying the sizing agent to carbon fiber, and a fiber-reinforced composite material including the sizing agent-coated carbon fiber.

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

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

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

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

  The amine adduct is easily blended with other materials when it is assumed to be used as an additive to other materials (for example, curable resins such as thermoplastic resins and epoxy compounds). We need to be able to do it. However, for example, an adduct of an epoxy compound having a glycidyl group, such as bisphenol A diglycidyl ether, which is conventionally known as an amine adduct, and a polyamine compound is softened or melted even when heated because a crosslinked structure is formed. Thus, uniform blending with other materials was difficult.

  Furthermore, the amine adduct is excellent in solubility in water (water-soluble) so that it can be used in the form of an aqueous solution or aqueous dispersion from the viewpoint of environmental protection or safety of the working environment. Preferably there is. For example, since it is excellent in water solubility, it can be applied to products (for example, water-based paints (water-soluble paints) and the like) using water or a solvent mainly containing water as a medium. Furthermore, the amine adduct has, for example, excellent heat resistance that can withstand even when the above polymer composite is processed at high temperature, and to prevent contamination due to adhesion to a processing machine or the like. It is also required to have a somewhat high glass transition temperature (for example, a glass transition temperature of room temperature or higher).

  Further, for example, when the amine adduct is used in a form in which the amine adduct is applied to an object to be coated such as a base material or a reinforcing fiber, it may be desirable to impart hardness to the object to be coated. For this reason, as said amine adduct, a hard thing (thing excellent in hardness) is also calculated | required. The above-mentioned known amine adducts were all soft and insufficient in hardness.

Therefore, the object of the present invention is highly reactive, can improve the adhesion between a resin and an additive (reinforced fiber, etc.) in a polymer-based composite (fiber reinforced composite material, etc.), and further has heat resistance and water solubility. It is an object of the present invention to provide an epoxy-amine adduct having excellent glass transition temperature and excellent hardness.
Another object of the present invention is to provide a resin composition that can form a polymer composite having high reactivity and excellent adhesion between a resin and an additive.
Furthermore, another object of the present invention is to provide a fiber-reinforced composite material having excellent adhesion between a resin and reinforcing fibers and having high mechanical properties (for example, toughness).
Furthermore, the other object of this invention is to provide the sizing agent which can improve the high-order workability of carbon fiber and can improve the adhesiveness of carbon fiber and a matrix resin.
Furthermore, another object of the present invention is to provide a sizing agent-coated carbon fiber excellent in high-order processability and excellent adhesion between carbon fibers and a matrix resin, and a fiber-reinforced composite material containing the sizing agent-coated carbon fiber. There is.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an epoxy-amine adduct (amine adduct) or a specific structural unit obtained by reacting a specific epoxy compound with a specific amine compound. Epoxy-amine adducts (amine adducts) have high reactivity, can improve the adhesion between the resin and the additive in the polymer composite, and are excellent in heat resistance and water solubility, and have a somewhat high glass transition. It has been found that it has temperature and excellent hardness and has completed the present invention.

［式中、Ｘは、単結合、又は１以上の原子を有する二価の基を示す。］
［３］アミン化合物（Ｂ）として、下記式（１）で表されるアミン化合物（Ｂ１）を用いる［１］又は［２］に記載のエポキシ−アミン付加物。

［式中、Ｒ¹及びＲ²は、同一又は異なって、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが直接又はヘテロ原子を含む連結基を介して連結した二価の基を示す。ｍは、０又は１以上の整数を示す。］
［４］アミン化合物（Ｂ）として、下記式（２）で表されるアミン化合物（Ｂ２）及び下記式（３）で表されるアミン化合物（Ｂ３）を用いる［１］又は［２］に記載のエポキシ−アミン付加物。

［式中、Ｒ³及びＲ⁴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。ｐは、１以上の整数を示す。］

［式中、Ｒ⁵及びＲ⁷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。ｑは、０又は１を示す。Ｒ⁶は、一価の有機基、酸素原子含有基、硫黄原子含有基、窒素原子含有基、又はハロゲン原子を示す。ｒは、０〜１０の整数を示す。］
［５］下記式（Ia）で表される構成単位、下記式（Ib）で表される構成単位、及び下記式（Ic）で表される構成単位からなる群より選択される少なくとも一種の構成単位と、下記式（II）で表される構成単位とを含み、両末端にアミノ基を有するエポキシ−アミン付加物。

［式中、Ｘは、単結合、又は１以上の原子を有する二価の基を示す。］

［式中、Ｒ¹及びＲ²は、同一又は異なって、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが直接又はヘテロ原子を含む連結基を介して連結した二価の基を示す。ｍは、０又は１以上の整数を示す。］
［６］［１］〜［５］のいずれか１つに記載のエポキシ−アミン付加物と、熱可塑性樹脂とを含む樹脂組成物。
［７］繊維強化複合材料用樹脂組成物である［６］に記載の樹脂組成物。
［８］［７］に記載の樹脂組成物を強化繊維に含浸又は塗工して得られるプリプレグ。
［９］［８］に記載のプリプレグより形成される繊維強化複合材料。
［１０］［１］〜［５］のいずれか１つに記載のエポキシ−アミン付加物を含むサイジング剤。
［１１］［１０］に記載のサイジング剤を炭素繊維に塗布して得られるサイジング剤塗布炭素繊維。
［１２］［１１］に記載のサイジング剤塗布炭素繊維と、熱可塑性樹脂又は硬化性化合物を硬化させて得られる硬化物とを含む繊維強化複合材料。
［１３］［１］〜［５］のいずれか１つに記載のエポキシ−アミン付加物を含む水性塗料。 That is, the present invention relates to the following.
[1] A compound having two or more amino groups in the molecule,
Obtained by a reaction between an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule;
An epoxy-amine adduct characterized by using a compound (A1) having one or more 5-membered rings in the molecule as the epoxy compound (A).
[2] The compound (A1) is at least selected from the group consisting of a compound represented by the following formula (a), a compound represented by the following formula (b), and a compound represented by the following formula (c). The epoxy-amine adduct according to [1], which is a kind of compound.

[Wherein, X represents a single bond or a divalent group having one or more atoms. ]
[3] The epoxy-amine adduct according to [1] or [2], wherein an amine compound (B1) represented by the following formula (1) is used as the amine compound (B).

[Wherein, R ¹ and R ² are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group in which the above and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. m represents 0 or an integer of 1 or more. ]
[4] As the amine compound (B), an amine compound (B2) represented by the following formula (2) and an amine compound (B3) represented by the following formula (3) are used [1] or [2] An epoxy-amine adduct of

[Wherein, R ³ and R ⁴ are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group or a linear or branched aliphatic hydrocarbon group. A divalent group formed by linking the above and one or more cyclic aliphatic hydrocarbon groups. p represents an integer of 1 or more. ]

[Wherein, R ⁵ and R ⁷ are the same or different and each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. q represents 0 or 1; R ⁶ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. r represents an integer of 0 to 10. ]
[5] At least one component selected from the group consisting of a structural unit represented by the following formula (Ia), a structural unit represented by the following formula (Ib), and a structural unit represented by the following formula (Ic) An epoxy-amine adduct containing a unit and a structural unit represented by the following formula (II) and having amino groups at both ends.

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

[Wherein, R ¹ and R ² are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group in which the above and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. m represents 0 or an integer of 1 or more. ]
[6] A resin composition comprising the epoxy-amine adduct according to any one of [1] to [5] and a thermoplastic resin.
[7] The resin composition according to [6], which is a resin composition for fiber-reinforced composite materials.
[8] A prepreg obtained by impregnating or coating the reinforcing fiber with the resin composition according to [7].
[9] A fiber-reinforced composite material formed from the prepreg according to [8].
[10] A sizing agent comprising the epoxy-amine adduct according to any one of [1] to [5].
[11] A sizing agent-coated carbon fiber obtained by applying the sizing agent according to [10] to carbon fiber.
[12] A fiber-reinforced composite material comprising the sizing agent-coated carbon fiber according to [11] and a cured product obtained by curing a thermoplastic resin or a curable compound.
[13] A water-based paint containing the epoxy-amine adduct according to any one of [1] to [5].

  Since the epoxy-amine adduct of the present invention has the above-described configuration, for example, it has high reactivity with respect to functional groups such as hydroxy groups, carboxy groups, and epoxy groups present on the surface of additives such as reinforcing fibers and fillers. The adhesion between the resin and the additive in a polymer composite such as a composite material or a nanocomposite can be effectively improved. Moreover, since the epoxy-amine adduct of the present invention is excellent in water solubility, it can be easily prepared in the form of an aqueous solution or an aqueous dispersion. The ability to be used in the form of such an aqueous solution or aqueous dispersion is advantageous in terms of environmental protection and ensuring work safety. Furthermore, since the epoxy-amine adduct of the present invention has a high thermal decomposition temperature and excellent heat resistance, it can be applied to processing at a high temperature, and can contribute to an improvement in the productivity of the polymer composite. Furthermore, since the epoxy-amine adduct of the present invention has a glass transition temperature that is somewhat high, contamination of a processing machine (such as a roll) is prevented and the handleability is also excellent. Furthermore, since the epoxy-amine adduct of the present invention has excellent hardness, it is possible to impart hardness to an object to be coated such as a substrate and reinforcing fibers. Therefore, by using the epoxy-amine adduct of the present invention, a resin composition capable of forming a polymer-based composite (fiber reinforced composite material or the like) having excellent adhesion between the resin and the additive (reinforced fiber or the like) can be obtained. . In addition, a fiber-reinforced composite material having excellent adhesion between the resin and the reinforcing fiber and having high mechanical properties (particularly toughness) can be obtained with high productivity.

  Moreover, since the sizing agent of this invention has the said structure, the higher-order workability of carbon fiber can be improved, and the adhesiveness of carbon fiber and matrix resin can be improved. Moreover, it is applicable to heat processing (for example, manufacture of sizing agent application | coating carbon fiber) at high temperature, and can also contribute to the productivity improvement of a fiber reinforced composite material. Furthermore, contamination of the processing machine (roll or the like) can be prevented, and excellent texture and handleability can be imparted to reinforcing fibers (for example, sizing agent-coated carbon fibers) coated with a sizing agent. . For this reason, the sizing agent-coated carbon fiber obtained by applying the sizing agent of the present invention to carbon fiber is excellent in high-order processability, and excellent in adhesion and adhesion between the carbon fiber and the matrix resin. Furthermore, the fiber-reinforced composite material including the sizing agent-coated carbon fiber has excellent heat resistance and mechanical strength, and has high productivity.

<Epoxy-amine adduct>
The epoxy-amine adduct of the present invention is a compound (polyamine) having two or more amino groups in the molecule, and an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule (simply By reaction with an amine compound (B) having two or more amino groups in the molecule (sometimes simply referred to as “amine compound (B)”). The resulting compound. More specifically, the epoxy-amine adduct of the present invention is obtained by reacting an alicyclic epoxy group possessed by the epoxy compound (A) with an amino group possessed by the amine compound (B). An epoxy-amine adduct having the above amino group. In the present specification, the term “amino group” simply means —NH ₂ (unsubstituted amino group), and “—NH— group” refers to the unsubstituted amino group (—NH ₂ ). Shall not be included.

  The epoxy-amine adduct of the present invention is a compound having at least one 5-membered ring in the molecule (referred to as “compound (A1)”) as the epoxy compound (A) among the above-mentioned epoxy-amine adducts. Is a compound obtained by using That is, the epoxy-amine adduct of the present invention is a compound obtained by reacting at least the compound (A1) and the amine compound (B). The epoxy-amine adduct of the present invention has such a structure, so that it has high reactivity and can improve the adhesion between the resin and the additive (reinforced fiber, etc.) in the polymer composite (fiber reinforced composite material, etc.). Furthermore, it has excellent heat resistance and water solubility, has a somewhat high glass transition temperature, and in particular has excellent (hard) properties.

  The epoxy-amine adduct of the present invention is described later as an amine compound (B) from the viewpoints of adhesion to additives (reinforcing fibers, fillers, etc.), wettability with resin, heat resistance, handleability, and water solubility. Epoxy-amine adduct using the amine compound (B1) represented by the formula (1) (sometimes referred to as “first aspect of the epoxy-amine adduct of the present invention”); An epoxy compound (B2) represented by the formula (2) and an amine compound (B3) represented by the following formula (3) are used in an epoxy-amine adduct (“the epoxy-amine adduct of the present invention”). It may be referred to as “second aspect”). Hereinafter, the first embodiment and the second embodiment of the epoxy-amine adduct of the present invention may be collectively referred to simply as “the epoxy-amine adduct of the present invention”. Among these, the first aspect of the epoxy-amine adduct of the present invention is preferable in terms of heat resistance, adhesion to additives (such as reinforcing fibers and fillers), and wettability with the resin. The second embodiment of the epoxy-amine adduct of the present invention is preferred.

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

  Although the alicyclic epoxy group which an epoxy compound (A) has is not specifically limited, For example, C4-C16 aliphatic rings (aliphatic hydrocarbon), such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring And an epoxy group composed of two adjacent carbon atoms constituting a ring) and an oxygen atom. Among these, as the alicyclic epoxy group, an epoxy group (cyclopentene oxide group) composed of two carbon atoms constituting a cyclopentane ring and an oxygen atom, two carbon atoms constituting a cyclohexane ring, and an oxygen atom The epoxy group (cyclohexene oxide group) comprised by these is preferable. In addition, an epoxy compound (A) may have only 1 type of alicyclic epoxy groups, and may have 2 or more types. As described later, for example, a compound (A1) has two or more alicyclic epoxy groups in the molecule and at least one of the alicyclic epoxy groups includes a 5-membered ring structure.

  The number (total number) of the alicyclic epoxy groups in the molecule of the epoxy compound (A) may be two or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, and further Preferably two or three. By setting the number of alicyclic epoxy groups to 6 or less, blending with other components of the epoxy-amine adduct generated by the reaction with the amine compound (B) can be facilitated, and the epoxy -The water solubility of the amine adduct tends to be further improved.

  The compound (A1), which is an essential raw material of the epoxy-amine adduct of the present invention, has two or more alicyclic epoxy groups in the molecule, and one or more five-membered rings (5-membered in the molecule). A ring structure). As described above, the number (total number) of the alicyclic epoxy groups that the compound (A1) has in the molecule is preferably 2 to 6, more preferably 2 to 5, and further preferably 2 or 3. is there.

  In addition, the 5-membered ring that the compound (A1) has in the molecule may be a 5-membered ring in which all of the atoms constituting the ring are carbon atoms, or the atoms that constitute the ring may be carbon atoms and heteroatoms (for example, , A nitrogen atom, an oxygen atom, a sulfur atom, etc.). The number of 5-membered rings that the compound (A1) has in the molecule is not particularly limited as long as it is 1 or more, but 1 to 5 (for example, 1 to 3) is preferable. The number of 5-membered rings included in the condensed ring means the number of 5-membered rings constituting the condensed ring. For example, the number of 5-membered rings included in the pentalene structure or dicyclopentadiene structure is 2 each. is there.

  Although it does not specifically limit as a compound (A1), The compound [For example, an alicyclic hydrocarbon group (for example, a cyclopentyl group, a cyclopentenyl group etc.), an alicyclic ring which has one or more groups containing a 5-membered ring in a molecule | numerator. Epoxy group (for example, cyclopentene oxide group, dicyclopentadiene dioxide group), heterocyclic group (for example, tetrahydrofuranyl group, furanyl group, etc.), bridged cyclic group or condensed cyclic group (for example, dicyclo group) A compound having a pentadienyl group or the like]; a cyclic compound containing a five-membered ring [for example, dicyclopentadiene diepoxide] or the like.

As the compound (A1), compounds represented by the following formulas (a) to (c) are particularly preferable in terms of particularly excellent balance of reactivity, heat resistance, water solubility, glass transition temperature, and hardness.

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

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

  Examples of the epoxy compound (A) in which X in the above formulas (b) and (c) is a single bond include 3,4,3 ′, 4′-diepoxybicyclopentane and 1- (3,4-epoxy). Cyclopentyl) -3,4-epoxycyclohexane and the like.

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

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

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

  Among the compounds represented by the above formulas (a) to (c), the compound represented by the formula (a) is particularly preferable in terms of excellent hardness.

As the epoxy compound (A) which is a raw material of the epoxy-amine adduct of the present invention, only the compound (A1) can be used, or a compound other than the compound (A1) (when referred to as “compound (A2)”) Can be used in combination. Although it does not specifically limit as a compound (A2), The compound represented with a following formula (d) is especially preferable at the point of availability.

  Y in the above formula (d) represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include the same linking groups as those exemplified as X. For example, a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized (epoxidation). Alkenylene group), a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, a group in which two or more of these groups are linked, and the like. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexoxide group) in the formula (d).

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

  As the linking group Y, 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 more of these groups are linked to one or more of divalent hydrocarbon groups, and the like.

Representative examples of the alicyclic epoxy compound represented by the above formula (d) include compounds represented by the following formulas (d-1) to (d-10), 2,2-bis (3,4) -Epoxycyclohexane-1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1- Yl) ethane, bis (3,4-epoxycyclohexylmethyl) ether, and the like. In the following formulas (d-5) and (d-7), k and l each represent an integer of 1 to 30. R ^′ in the following formula (d-5) represents an alkylene group having 1 to 8 carbon atoms, for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene. And straight-chain or branched alkylene groups such as a hexylene group, a heptylene group, and an octylene group. Among these, C1-C3 linear or branched alkylene groups, such as a methylene group, ethylene group, a propylene group, an isopropylene group, are preferable. N1 to n6 in the following formulas (d-9) and (d-10) each represent an integer of 1 to 30.

  Among the compounds represented by the above formula (d), in particular, from the viewpoint of heat resistance and handleability, the compound represented by the above formula (d-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy). ) Cyclohexanecarboxylate; trade name “Celoxide 2021P” (manufactured by Daicel Corporation) and the like] are preferable.

[Amine compound (B)]
The amine compound (B) that is a raw material (precursor) of the epoxy-amine adduct of the present invention is a polyamine compound having two or more amino groups (—NH ₂ ; unsubstituted amino group) in the molecule. The number of amino groups in the molecule of the amine compound (B) may be two or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, still more preferably 2 or 3 It is a piece. By setting the number of amino groups to 6 or less, blending with other components of the epoxy-amine adduct produced by the reaction with the epoxy compound (A) can be facilitated, and the addition of the epoxy-amine is also possible. There exists a tendency for the water solubility of a thing to improve more.

Examples of the amine compound (B) include a compound represented by the following formula (1) (referred to as “amine compound (B1)”). The amine compound (B1) is an essential raw material in the first embodiment of the epoxy-amine adduct of the present invention. The first aspect of the epoxy-amine adduct of the present invention has a constitutional unit derived from the amine compound (B1) in the molecule, and in particular, the heat resistance, water solubility, carbon fiber, etc. of the epoxy-amine adduct. There exists a tendency which can improve efficiently the adhesiveness with respect to additives, such as a reinforced fiber and a filler, and the adhesiveness of resin and additive materials (reinforced fiber etc.) in polymer type composites (fiber reinforced composite material etc.).

  In the first embodiment of the epoxy-amine adduct of the present invention, as the amine compound (B), in addition to the above-described amine compound (B1), an amine compound (B3) represented by the following formula (3) is further added. It is preferable to use together. In the first aspect of the epoxy-amine adduct of the present invention, when both the structural unit derived from the amine compound (B1) and the structural unit derived from the amine compound (B3) are contained in the molecule, the epoxy- Adhesion of amine adducts to reinforced fibers such as carbon fibers and additives such as fillers, and adhesion between resin and additives (reinforced fibers, etc.) in polymer composites (fiber reinforced composite materials, etc.) tend to improve efficiently There is.

In the above formula (1), R ¹ and R ² are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon. A divalent group in which one or more of the groups and one or more of the cyclic aliphatic hydrocarbon groups are linked directly or via a linking group (a divalent group) containing a hetero atom. Examples of the divalent linear or branched 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, an octylene group, Linear or branched chain having 1 to 30 carbon atoms (C _1-30 ) such as nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, etc. Alkylene group (preferably C _1-18 alkylene group)], alkenylene group [alkenylene group corresponding to the above alkylene group, for example, a linear or branched alkenylene group having 2 to 30 carbon atoms such as vinylene group, arylene group, etc. (Preferably a C _2-18 alkenylene group) and the like]. Examples of the divalent cyclic aliphatic hydrocarbon group include a cycloalkylene group [for example, a cycloalkylene group having 3 to 20 carbon atoms such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group ( Preferably a C _3-15 cycloalkylene group)], cycloalkenylene group [cycloalkenylene group corresponding to the above cycloalkylene group, for example, a cycloalkenylene group having 3 to 20 carbon atoms such as a cyclohexenylene group (preferably C _{3 -15} cycloalkenylene group), etc.], cycloalkylidene group [cycloalkylidene group corresponding to the above cycloalkylene group, for example, cyclopentylidene group, cyclohexylidene group, etc., having 3 to 20 carbon atoms (preferably C _3-15 cycloalkylidene group), etc.], cycloalkadienyl Eni alkylene group [the Cycloalkadienyl Eni alkylene groups corresponding to Kuroarukiren group, for example, cyclopentadienylide cycloalkadienyl Eni alkylene group (preferably a C _4-15 cycloalkadienyl Eni alkylene group) having 4 to 20 carbon atoms such as alkylene group or the like], divalent A polycyclic hydrocarbon group [e.g., a spiro hydrocarbon (e.g., spiro [4.4] nonane, spiro [4.5] decane, etc.)-a divalent spiro hydrocarbon group such as a diyl group; (For example, bicyclopropyl and the like) -divalent ring assembly hydrocarbon group such as diyl group; bridged ring hydrocarbon (for example, bicyclo [2.1.0] pentane, bicyclo [3.2.1] octane, norbornane , Norbornene, adamantane and the like) -divalent bridged ring hydrocarbon groups such as diyl group] and the like.

Examples of the linking group (divalent group) containing a hetero atom include -CO- (carbonyl group), -O- (ether bond), -CO-O- (ester bond), -O-CO-O. — (Carbonate group), —CO—NH— (amide group), —CO—NR ^a — (substituted amide group; R ^a represents an alkyl group), —NH—, —NR ^b — (R ^b is an alkyl group) A divalent group containing a hetero atom (oxygen atom, nitrogen atom, sulfur atom, etc.) such as —SO— or —SO ₂ —, a divalent group in which a plurality of these are linked, and the like.

  One or more of the above-mentioned linear, branched or cyclic divalent aliphatic hydrocarbon groups, linear or branched aliphatic hydrocarbon groups and one or more cyclic aliphatic hydrocarbon groups are linked. The divalent group formed in this way may have various substituents (that is, at least one hydrogen atom of the above-mentioned divalent group is substituted with various substituents. May be). Examples of the substituent include a halogen atom, an oxo group, a hydroxy group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, and an acyloxy group), a carboxy group, and a substituted oxycarbonyl group (alkoxycarbonyl group). Aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group and the like. The hydroxy group and carboxy group may be protected with a protective group commonly used in the field of organic synthesis (for example, acyl group, alkoxycarbonyl group, organic silyl group, alkoxyalkyl group, oxacycloalkyl group, etc.).

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

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

Among these, as R ¹ , a linear or branched divalent aliphatic hydrocarbon group is preferable, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. -4 linear or branched alkylene groups (especially ethylene group, trimethylene group, propylene group).

Among these, R ² is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. -4 linear or branched alkylene groups (especially ethylene group, trimethylene group, propylene group). In the case of m is 2 or more integer, R ² in each of the parentheses (multiple R ²⁾ may be the same or different. Furthermore, addition forms (polymerized form) in the structure when, m is attached in brackets having two or more R ² may be the random type or may be a block type.

  In the above formula (1), m represents 0 or an integer of 1 or more. As m, for example, 0 to 100 is preferable, more preferably 0 to 70, still more preferably 1 to 30, and particularly preferably 1 to 8. When m is 100 or less, the heat resistance of the epoxy-amine adduct of the present invention and the heat resistance and mechanical properties (toughness, etc.) of the polymer composite (particularly fiber reinforced composite material) are further improved depending on the application. Tend to.

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

  Among them, the compounds represented by the above formula (1) include ethylenediamine (EDA) and diethylenetriamine (DETA) from the viewpoints of adhesion, wettability, and heat resistance to additives (particularly reinforcing fibers) of the epoxy-amine adduct. , Triethylenetetramine (TETA) and tetraethylenepentamine (TEPA) are preferable, and triethylenetetramine is more preferable. Moreover, a commercial item can also be used as a compound represented by the said Formula (1).

Examples of the amine compound (B) include a compound represented by the following formula (2) (referred to as “amine compound (B2)”) and a compound represented by the following formula (3) (“amine compound (B3)”). ")". The amine compound (B2) and the amine compound (B3) are essential raw materials in the second embodiment of the epoxy-amine adduct of the present invention. In the second embodiment of the epoxy-amine adduct of the present invention, particularly when both the structural unit derived from the amine compound (B2) and the structural unit derived from the amine compound (B3) are included, the heat resistance tends to be further improved. .

R ³ in the above formula (2) is a linear, branched or cyclic divalent aliphatic hydrocarbon group, or one or more of a linear or branched aliphatic hydrocarbon group and a cyclic aliphatic. A divalent group formed by linking one or more hydrocarbon groups. Examples of R ³ include the divalent groups exemplified as R ¹ described above. In addition, one or more of a linear, branched or cyclic divalent aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group as R ³ and a cyclic aliphatic hydrocarbon group. The divalent group formed by linking to the above may have a substituent, and examples of the substituent include the same substituents as those described above for R ¹ .

Among them, R ³ is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. -4 linear or branched alkylene groups (especially ethylene group, trimethylene group, propylene group).

R ⁴ in the above formula (2) is a linear, branched or cyclic divalent aliphatic hydrocarbon group, or one or more of a linear or branched aliphatic hydrocarbon group and a cyclic aliphatic group. A divalent group formed by linking one or more hydrocarbon groups. Examples of R ⁴ include the divalent groups exemplified as R ¹ described above. In addition, one or more of a linear, branched or cyclic divalent aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group as R ⁴ and a cyclic aliphatic hydrocarbon group. The divalent group formed by linking to the above may have a substituent, and examples of the substituent include the same substituents as those described above for R ¹ .

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

  In the above formula (2), p (the number of repeating structural units in parentheses to which p is attached) represents an integer of 1 or more. As p, 1-100 are preferable, for example, More preferably, it is 1-70, More preferably, it is 1-30. When p exceeds 100, the heat resistance of the epoxy-amine adduct of the present invention and the heat resistance and mechanical properties (toughness, etc.) of the polymer composite (particularly fiber-reinforced composite material) may be insufficient depending on applications. There is.

R ³ and R ⁴ in the above formula (2) may be the same or different.

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

R ⁵ and R ⁷ in the above formula (3) are the same or different and represent an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. Specific examples of R ⁵ and R ⁷ include groups exemplified as R ¹ in the formula (1); substitution such as o-phenylene group, m-phenylene group, p-phenylene group, naphthalenylene group, alkyl-substituted phenylene group, or the like; An unsubstituted arylene group etc. are mentioned.

  Q in the above formula (3) represents 0 or 1.

R ⁶ in the above formula (3) represents a substituent on the cyclohexane ring shown in the formula, and is the same or different and is a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom-containing group. Represents a monovalent nitrogen atom-containing group or a halogen atom. Specific examples of R ⁶ include, for example, alkyl groups, halogen atoms (fluorine atoms, chlorine atoms, etc.), hydroxy groups, carboxy groups, alkoxy groups, alkenyloxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, Mercapto group, alkylthio group, alkenylthio group, arylthio group, aralkylthio group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group, nitro group, mono- or dialkylamino group, acylamino group, epoxy group, glycidyl Group, acyl group, cyano group, isocyanate group, isothiocyanate group, carbamoyl group, sulfo group and the like. Furthermore, r in the formula (3) represents the number of substituents on the cyclohexane ring shown in formula (R ^6), it represents an integer of 0. When r in the above formula (3) is an integer of 2 or more, each R ⁶ 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 (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-cyclohexylene- Cyclohexylene such as ethylene group, cyclohexylidene-ethylene group, methylene-1,5,5-trimethyl-1,3-cyclohexylene group (a divalent group formed by removing two amino groups from isophoronediamine) -Alkylene group; 1,2-cyclohexylene-phenylene group, 1,3-cyclohexylene-phenylene group, 1,4-cyclohexylene- Cyclohexylene-arylene groups such as an enylene group; alkylene-cyclohexyl such as a methylene-1,2-cyclohexylene-methylene group, a methylene-1,3-cyclohexylene-methylene group, a methylene-1,4-cyclohexylene-methylene group, etc. Silylene-alkylene group; alkylene-cyclohexylene-phenylene group such as methylene-1,2-cyclohexylene-phenylene group, methylene-1,3-cyclohexylene-phenylene group, methylene-1,4-cyclohexylene-phenylene group; Examples include arylene-cyclohexylene-arylene groups such as phenylene-1,2-cyclohexylene-phenylene group, phenylene-1,3-cyclohexylene-phenylene group, and phenylene-1,4-cyclohexylene-phenylene group.

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

  As the amine compound (B), amine compounds other than the above-described amine compound (B1), amine compound (B2), and amine compound (B3) can also be used. Examples of such amine compounds (B) include compounds having 3 or more amino groups in the molecule, aromatic amine compounds (compounds having an amino group substituted on an aromatic ring), and the like.

  Moreover, as a raw material of the 1st aspect of the epoxy-amine adduct of this invention, amine compounds (for example, amine compound (B2), amine compound (B3) etc.) other than amine compound (B1) can also be used together. . As described above, as the raw material of the first aspect of the epoxy-amine adduct of the present invention, it is preferable to use the amine compound (B3) together with the amine compound (B1). As a raw material of the second aspect of the epoxy-amine adduct of the present invention, an amine compound other than the amine compound (B2) and the amine compound (B3) (for example, an amine compound (B1)) can be used in combination.

[Production Method of Epoxy-Amine Adduct; Reaction of Epoxy Compound (A) and Amine Compound (B)]
The epoxy-amine adduct of the present invention can be produced by reacting an epoxy compound (A) with an amine compound (B). More specifically, the epoxy-amine adduct of the present invention is generated by reacting the alicyclic epoxy group of the epoxy compound (A) with the amino group of the amine compound (B).

  Specifically, in the first aspect of the epoxy-amine adduct of the present invention, the epoxy compound (A) (compound (A1) is essential; preferably, compounds represented by formulas (a) to (c) ) And the amine compound (B1) (preferably the amine compound (B1) and the amine compound (B3)) as the amine compound (B). The second aspect of the epoxy-amine adduct of the present invention is an epoxy compound (A) (comprising compound (A1) as an essential component; preferably, a compound represented by formulas (a) to (c)), It can be obtained by using the amine compound (B2) and the amine compound (B3) as essential raw materials as the amine compound (B).

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

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

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

  The ratio of the compound (A1) in the total amount (100% by weight) of the epoxy compound (A) that is a raw material of the epoxy-amine adduct of the present invention is not particularly limited, but is 70% by weight or more (for example, 70 to 100% by weight). %), More preferably 80% by weight or more (for example, 80 to 95% by weight), and still more preferably 90% by weight or more. By adjusting the ratio of the compound (A1) to 70% by weight or more, the adhesion of the epoxy-amine adduct to the additive (especially reinforcing fiber such as carbon fiber), the resin in the polymer composite (particularly fiber reinforced composite material) and There is a tendency that the adhesion of the additive (particularly the reinforcing fiber) is efficiently improved, and in particular, the hardness is further improved.

  The ratio of the compounds represented by the formulas (a) to (c) in the total amount (100% by weight) of the compound (A1) that is a raw material of the epoxy-amine adduct of the present invention is not particularly limited, but is 80% by weight. The above is preferable, More preferably, it is 90 weight% or more, More preferably, it is 98-100 weight%. By setting the ratio of the total amount to 80% by weight or more, adhesion to an additive of epoxy-amine adduct (especially reinforcing fiber such as carbon fiber), resin and additive in polymer composite (especially fiber reinforced composite material) There is a tendency that the adhesion of (especially reinforcing fibers) is improved efficiently, and in particular, the hardness is further improved.

  As the epoxy compound (A) that is the raw material of the epoxy-amine adduct of the present invention, the compound (A1) (particularly the compounds represented by the formulas (a) to (c)) and the compound (A2) (particularly the formula ( When a compound represented by a) is used in combination, the ratio of these compounds (weight ratio; compound (A1) / compound (A2)) is not particularly limited, but is 1/99 to 99.9 in weight ratio. /0.1 is preferable, more preferably 10/90 to 90/10, and still more preferably 20/80 to 80/20. By controlling the ratio of the compound (A1) to the compound (A2) within the above range, adhesion to additives (especially reinforcing fibers such as carbon fibers), resins and additives in polymer composites (especially fiber reinforced composite materials) There exists a tendency for the epoxy-amine adduct excellent in the balance of various physical properties, such as adhesiveness (especially reinforcement fiber), and hardness, to be obtained.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The number of amino groups (—NH ₂ ; unsubstituted amino group) contained in the epoxy-amine adduct of the present invention is 2 or more, preferably 2 to 10, more preferably 2 to 4, and still more preferably. Two or three. Moreover, the epoxy-amine adduct of the present invention has substantially no epoxy group (in particular, an alicyclic epoxy group derived from the epoxy compound (A)).

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

As described above, the epoxy-amine adduct of the present invention reacts with the alicyclic epoxy group of the epoxy compound (A) and the amino group (—NH ₂ ; unsubstituted amino group) of the amine compound (B). Generate. The epoxy-amine adduct of the present invention includes an —NH— group (substituted amino group) produced by the reaction of the alicyclic epoxy group and an amino group or an —NH— group (m is 1 or more) of the amine compound (B1). In this case, it is assumed that the reactivity between the epoxy compound (A) and the alicyclic epoxy group of the epoxy compound (A) is poor, but usually the —NH— group remains unreacted in the molecule. The number of —NH— groups in the molecule of the epoxy-amine adduct of the present invention is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, and still more preferably 2 to 100. . When the epoxy-amine adduct does not have a -NH- group, the reactivity may be lowered, or depending on the application, the effect of improving the adhesion between the resin and the reinforcing fiber in the fiber-reinforced composite material may not be sufficiently obtained. . The number of —NH— groups in the epoxy-amine adduct is, for example, the epoxy constituting the epoxy-amine adduct using the molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). It is possible to calculate by obtaining the number of the compound (A) and the amine compound (B).

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

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

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

The 5% weight loss temperature (Td ₅ ) of the epoxy-amine adduct of the present invention 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), it tends to be applicable to processing at higher temperatures (for example, production of sizing agent-coated carbon fibers). The 5% weight loss temperature of the epoxy-amine adduct can be measured by TG / DTA. More specifically, it is measured by the method disclosed in the examples.

［式（Ib）及び式（Ic）中、Ｘは、上記式（ｂ）及び式（ｃ）におけるものと同じ。］

［式（II）中、Ｒ¹、Ｒ²、及びｍは、上記式（１）におけるものと同じ。］

［式（III）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、ｑ、及びｒは、上記式（３）におけるものと同じ。］ The first aspect of the epoxy-amine adduct of the present invention is particularly the compound represented by the above formula (a), the compound represented by the above formula (b), and the above formula (c) as the epoxy compound (A). When at least one compound selected from the group consisting of compounds represented by formula (Ia) is used, a structural unit (structural unit; structural unit derived from a compound represented by formula (a) ), A structural unit represented by the following formula (Ib) (a structural unit derived from the compound represented by the formula (b)), and a structural unit represented by the following formula (Ic) (represented by the formula (c)) Including at least one structural unit selected from the group consisting of a structural unit derived from a compound and a structural unit represented by the following formula (II) (a structural unit derived from an amine compound (B1)), It is an epoxy-amine adduct having an amino group at the terminal. The first embodiment of the epoxy-amine adduct of the present invention preferably further contains a structural unit represented by the following formula (III).

[In Formula (Ib) and Formula (Ic), X is the same as in Formula (b) and Formula (c) above. ]

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

[In the formula (III), R ⁵ , R ⁶ , R ⁷ , q and r are the same as those in the above formula (3). ]

The first aspect of the above-described epoxy-amine adduct of the present invention includes a structural unit derived from the epoxy compound (A) (for example, structural units represented by formulas (Ia) to (Ic)) and an amine compound (B ) Derived molecular units (for example, a structural unit represented by the formula (II), a structural unit represented by the formula (III)) are alternately arranged at both ends of the molecular chain. It is an epoxy-amine adduct having an amino group (—NH ₂ ) (that is, having a structural unit derived from the amine compound (B) at both ends). The addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be a random type or a block type.

［式（IV）中、Ｒ³、Ｒ⁴、及びｐは、上記式（２）におけるものと同じ。］ In the second embodiment of the epoxy-amine adduct of the present invention, in particular, the compound represented by the above formula (a), the compound represented by the above formula (b), and the above formula (c) as the epoxy compound (A). When at least one compound selected from the group consisting of the compounds represented by formula (Ia) is used, the structural unit represented by the formula (Ia), the structural unit represented by the formula (Ib), and the formula (Ic) ) At least one structural unit selected from the group consisting of structural units represented by formula (IV), a structural unit represented by the following formula (IV) (structural unit derived from the amine compound (B2)), and the above formula (III) Is an epoxy-amine adduct having an amino group at both ends.

[In the formula (IV), R ³ , R ⁴ and p are the same as those in the above formula (2). ]

In the second aspect of the epoxy-amine adduct of the present invention described above, a structural unit derived from the epoxy compound (A) (for example, structural units represented by the formulas (Ia) to (Ic)) and an amine compound (B ) -Derived structural units (for example, a structural unit represented by the formula (III), a structural unit represented by the formula (IV)) are alternately arranged at both ends of the molecular chain. It is an epoxy-amine adduct having an amino group (—NH ₂ ) (that is, having a structural unit derived from the amine compound (B) at both ends). The addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be a random type or a block type.

  The use of the epoxy-amine adduct of the present invention is not particularly limited. For example, the epoxy-amine adduct of the present invention is an adhesion improver (adhesion improver) for improving the adhesion between a resin and an additive in a polymer composite, and an adhesion for an adherend. Adhesion improver (adhesion improver), compatibility improver (compatibilizer) to improve the solubility of two or more different components (especially polymers), improve dispersibility of additives in polymer composites Various additives such as dispersibility improvers, fluidity improvers, fluidity inhibitors, plasticizers, crosslinking agents such as epoxy resins, etc .; adhesives; paints; sealants; sizing agents, etc. it can. Since the epoxy-amine adduct of the present invention is excellent in water solubility and has the above-mentioned various properties, it can be preferably used, for example, as an aqueous paint containing the epoxy-amine adduct. The water-based paint is a paint (usually including a binder component, a pigment, and the like) using water or a solvent mainly containing water as a medium.

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

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

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

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

  The content (blending amount) of the epoxy-amine adduct of the present invention in the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 200 parts by weight, more preferably 100 parts by weight of the resin. Is 1 to 100 parts by weight, more preferably 2 to 50 parts by weight. By setting the content of the epoxy-amine adduct of the present invention to 0.1 parts by weight or more, the adhesion between the resin and the additive (particularly the reinforcing fiber) in the polymer composite (particularly the fiber-reinforced composite material) is further improved. Tend. On the other hand, by setting the content of the epoxy-amine adduct of the present invention to 200 parts by weight or less, the heat resistance and mechanical properties (toughness, etc.) of the polymer composite (particularly fiber reinforced composite material) tend to be further improved. is there.

  In addition to the resin and the epoxy-amine adduct of the present invention, the resin composition of the present invention includes, for example, a polymerization initiator (thermal polymerization initiator, photopolymerization initiator, etc.), a curing agent, a curing accelerator, and an antifoaming agent. Agent, leveling agent, coupling agent (silane coupling agent, etc.), surfactant, inorganic filler (silica, alumina, etc.), flame retardant, colorant, antioxidant, ultraviolet absorber, ion adsorbent, pigment, Conventional additives such as phosphors and mold release agents may be included.

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

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

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

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

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

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

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

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

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

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

[Sizing agent]
As described above, the epoxy-amine adduct of the present invention has high reactivity with respect to functional groups such as hydroxy groups, carboxy groups, and epoxy groups present on the surface of the reinforcing fiber, and the resin and the reinforcing fiber in the fiber-reinforced composite material. Since adhesiveness can be improved effectively, it can be preferably used as a sizing agent (particularly, a sizing agent for carbon fiber). A sizing agent is a process applied (coated) to reinforcing fibers to improve handling in the reinforcing fiber manufacturing process and higher-order processing processes (textile process, prepreg process, and other molding processes). Agent, sometimes referred to as sizing agent. In the present specification, the sizing agent containing the epoxy-amine adduct of the present invention may be referred to as “the sizing agent of the present invention”.

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

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

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

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

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

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

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

  Since the sizing agent-coated carbon fiber of the present invention is coated with the epoxy-amine adduct (epoxy-amine adduct of the present invention) in the sizing agent of the present invention, it has excellent adhesion to the resin. Moreover, since the epoxy-amine adduct in the sizing agent of the present invention is excellent in heat resistance, it can be applied to high-temperature processing (for example, production of carbon fiber coated with sizing agent), and the productivity of fiber-reinforced composite materials is improved. Can also contribute. Furthermore, since the epoxy-amine adduct in the sizing agent of the present invention has a glass transition temperature that is somewhat high, contamination of processing machines (rolls, etc.) is prevented, and reinforcing fibers (for example, sizing) coated with a sizing agent It is also possible to impart excellent texture and handleability to the agent-coated carbon fiber. Furthermore, since the sizing agent of the present invention has excellent functions as a general sizing agent such as a function of converging carbon fibers and a function of imparting flexibility to the carbon fibers, the sizing agent-coated carbon of the present invention The fiber has good handleability and excellent high-order processability.

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

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

  The epoxy-amine adduct of the present invention is used, for example, as a wet paper strength enhancer in papermaking and paper processing fields; for facilitating drainage in papermaking processes, improving drainage; fine fibers, sizing agents, various fillers, pigments, dyes, etc. As a yield improver; it can be used for purposes such as clarification of white water and paper wastewater treatment. More specifically, the epoxy-amine adduct of the present invention is improved in water resistance of water-based inks utilizing the reactivity of the epoxy-amine adduct of the present invention and an acid dye, for example, by treatment with the epoxy-amine adduct of the present invention. Ink jet recording paper; oil-resistant paper treated with a reaction product of a phosphate ester and an epoxy-amine adduct of the present invention; dyed paper using a quaternized or ethoxylated epoxy-amine adduct of the present invention; anionic Alkali or neutral sizing agent using sizing agent and epoxy-amine adduct of the present invention (retention agent); paper using reaction product of epoxy-amine adduct of the present invention, fatty acid and epichlorohydrin Softening, size and wet strength improvement; heat-resistant paper using polyphosphoric flame retardant and epoxy-amine adduct of the present invention; alkoxylated epoxy of the present invention It can be used in the manner and application of the deinking agent of wastepaper using the Min adduct.

  The epoxy-amine adduct of the present invention can be used in the adhesive industry field, for example, as a water-soluble adhesion promoter (laminate anchor agent). More specifically, the epoxy-amine adduct of the present invention is, for example, an FRP product treated with the epoxy-amine adduct of the present invention; an aqueous dispersion comprising a reaction product of the epoxy-amine adduct of the present invention and a polyepoxy compound. Adhesive composition; adhesive composition for packaging and masking tape comprising a diene polymer and the epoxy-amine adduct of the present invention; containing a metal complex comprising an epoxy-amine adduct of the present invention and a nickel or cobalt salt Rubber / metal adhesion promoter; water-soluble vinyl acetate copolymer emulsion adhesive modified with the epoxy-amine adduct of the present invention; for wood, tile, etc. comprising the epoxy-amine adduct of the present invention and acetoacetylated polyvinyl alcohol Two-component fast-curing aqueous adhesive; epoxy-amine adduct of the present invention and hydroxy-substituted organic They can be used in the manner and application of the moisture actuated heat melting adhesive made from the object and compatibility adhesive.

  The epoxy-amine adduct of the present invention is used in the field of ink and photographic industry, for example, improvement of storage stability of color developing solution, color contamination, etc .; addition of antistatic property in silver halide photographic light-sensitive materials; Can be used for applications such as improving water fastness characteristics. More specifically, the epoxy-amine adduct of the present invention is, for example, a color developing solution containing diethylhydroxyamine and the epoxy-amine adduct of the present invention; an ion comprising the epoxy-amine adduct of the present invention and a metal salt. A silver halide photographic light-sensitive material using a conductive polymer complex; can be used in embodiments and applications such as an inkjet composition comprising a hydroxyethylated epoxy-amine adduct of the present invention and a water-soluble dye.

  The epoxy-amine adduct of the present invention can be used in the textile industry, for example, for applications such as improving the dyeability of various fibers including cellulose fibers, shrinkage prevention, flameproofing treatment, and antistatic treatment. More particularly, the epoxy-amine adducts of the present invention are, for example, antistatic polyamide compositions treated with acylates of the epoxy-amine adducts of the present invention; alkylene oxides and ethylenes in the epoxy-amine adducts of the present invention. An antistatic agent for synthetic fibers using an amphoteric polymer obtained by adding a photo-unsaturated monomer; a fiber sheet in which an epoxy-amine adduct of the present invention and an anionic latex are internally added to a fiber slurry; an epoxy-amine of the present invention Functional fiber obtained by mixing adduct and polyvinyl alcohol, dry spinning and cross-linking with glutaraldehyde, etc .; can be used in embodiments and applications such as flame retardant fiber treated with epoxy-amine adduct of the present invention and halophosphite .

  As described above, the epoxy-amine adduct of the present invention can be used as a flocculant, a clarifying agent, and a flotation agent. For example, an exchange agent for purifying wastewater; a flocculant for activated sludge; a flocculant for pulp wastewater; Water treatment agent for removing organic and inorganic substances dispersed and emulsified in water; Treatment of water containing waste paint in wet paint booth circulating water; Aggregation and recovery of silica dissolved in geothermal water; Coal and mineral aggregation Collection of harmful heavy metals contained in wastewater; use for recovering oil from wastewater in oil recovery. More specifically, the epoxy-amine adduct of the present invention is, for example, an exchange agent for wastewater purification using a modified product of cellulose or a derivative thereof by the epoxy-amine adduct of the present invention; the epoxy-amine addition of the present invention. A flocculant for pulp wastewater comprising a product and an inorganic salt; a porous water treatment material comprising polyethylene, silica and the epoxy-amine adduct of the present invention; by an adduct of starch xanthate and the epoxy-amine adduct of the present invention Coal and mineral agglomeration; can be used in aspects and applications such as oil recovery from wastewater in oil recovery by the reaction product of the epoxy-amine adduct of the present invention and epichlorohydrin.

  As described above, the epoxy-amine adduct of the present invention can be used as a chelate resin, ion exchange resin, separation membrane, adsorbent, anion exchange resin; heavy metal adsorbent; chelate resin; uranium adsorbent; low molecular metal chelate. Adsorbents; High performance reverse osmosis composite membranes; Control release by high electrolyte microcapsule separation membrane; Ion selective electrode; Acid gas adsorbent; Separation membrane for production of high-concentration sugar liquor. More specifically, the epoxy-amine adduct of the present invention includes, for example, an anion exchange resin formed from the epoxy-amine adduct of the present invention and epihalohydrin, etc .; activated carbon of the epoxy-amine adduct of the present invention and carbon disulfide. Heavy metal adsorbent with reaction product attached; Chelate resin grafted with epoxy-amine adduct of the present invention and epichlorohydrin on chloromethylated crosslinked polystyrene; Polymer containing carboxy group and epoxy-amine addition of the present invention Adsorbent of uranium adsorbed with a polyion complex formed from the product; Adsorbent of low molecular metal chelate using an ion exchanger having an active group derived from the epoxy-amine adduct of the present invention; Epoxy-amine adduct of the present invention or its An ion-selective electrode using a membrane containing a derivative; It can be used in the manner and application of the separation membrane of the high concentration sugar solution prepared by the reaction product of an amine adduct and dialdehyde such as - epoxy of the present invention; acid gas adsorbent deposited or reacting the amine adduct.

  The epoxy-amine adduct of the present invention is used in cosmetics and toiletries, for example, bar soap for washing skin; cosmetics for hair (shampoo, rinsing, treatment, etc.); nail enamel composition; removal of mud stains and prevention of recontamination Can be used for More specifically, the epoxy-amine adduct of the present invention is a soap for washing skin containing the epoxy-amine adduct of the present invention or a modified product thereof; hair containing the epoxy-amine adduct of the present invention or a derivative thereof. Cosmetics; Neel enamel composition comprising a polyion complex synthesized by reaction of an anionic polymer salt with the epoxy-amine adduct of the present invention; Using an ethoxylated epoxy-amine adduct of the present invention It can be used in modes and applications such as removing mud dirt and preventing recontamination.

  As described above, the epoxy-amine adduct of the present invention can be used as a lubricant, a rust inhibitor, and a dispersant. For example, a metal working oil composition; a metal rolling lubricant; a ceramic dispersant; a magnetic recording medium It can be used for applications such as dispersing in a magnetic layer; dispersing agent for a coal-water slurry; prevention of adhesion of ash to a metal or the like in a pulverized coal-oil mixture; More specifically, the epoxy-amine adduct of the present invention is, for example, a metalworking oil composition containing, as an active ingredient, a condensate of a carboxylic acid and the epoxy-amine adduct of the present invention; A metal rolling lubricant containing an adduct epoxy adduct dispersant; a magnetic recording medium comprising as a dispersant a reaction product of the epoxy-amine adduct of the present invention and a carboxy group-containing polyester in the magnetic layer; Dispersant for coal-water slurry comprising polyoxyalkylene ether of epoxy-amine adduct of the invention and formalin condensate of aromatic sulfonate; addition of alkylene oxide of epoxy-amine adduct of the present invention to pulverized coal-oil mixture It can be used in modes and applications such as prevention of adhesion of ash to metals by adding body.

  As described above, the epoxy-amine adduct of the present invention can be used as a plating agent, for example, improving glossiness; electrodeposition of bright copper to electronic circuit printed boards; acidic zinc plating; high-speed copper electroplating; It can be used for purposes such as forming a plating film. More specifically, the epoxy-amine adduct of the present invention improves glossiness by, for example, addition to a plating bath (for example, a black rhodium plating bath); a transparent conductive film is activated with the epoxy-amine adduct of the present invention. It can be used in aspects and applications such as forming an electroless plating film.

  The epoxy-amine adduct of the present invention can be used in the biological, medical, and enzyme fields, for example, comprehensive immobilization of enzymes (for example, production of palatinose by α-glucosyl transferase, immobilization of sucrose mutase, alcohol oxidase, glucose oxidase, Immobilization of cholesterol oxidase, etc. Immobilization of Bacillus subtilis using the elimination product of 3-acetoxy group from 7-β-acylamide cephalosporanic acid, from transcinnamic acid by immobilized Sporoboromyces roseus cells L-phenylalanine production); purification of DNA polymerase III from cell-free extract of E. coli; detection of analyte by antibody immunofluorescence; purification of human interferon-β; purification of monoclonal and monoclonal antibodies; anticoagulant Synthesis; use of enzyme-immobilized membrane It can be used. More specifically, the epoxy-amine adduct of the present invention includes, for example, comprehensive immobilization of an enzyme with the epoxy-amine adduct of the present invention or a derivative thereof and glutaraldehyde, alginic acid, tannic acid, etc .; Of an analyte by an antibody immunofluorescence method using a reaction product of a product and a functional fluorescent dye molecule; purification of a monoclonal or monoclonal antibody using silica gel carrying an epoxy-amine adduct of the present invention; Synthesis of an anticoagulant using an epoxy-amine adduct of the present invention; it can be used in an embodiment or application such as an enzyme-immobilized membrane by crosslinking of the epoxy-amine adduct of the present invention with a dialdehyde.

  As described above, the epoxy-amine adduct of the present invention can be used as a cement additive and an oil mining agent, for example, a cement water reducing agent; a fluid loss agent in oil mining cementing; and a concrete admixture. Can be used in More particularly, the epoxy-amine adduct of the present invention is, for example, a cement water reducing agent using a hydroxyalkylated epoxy-amine adduct of the present invention; a carboxyethylated epoxy-amine adduct of the present invention. It can be used in aspects and applications such as concrete admixtures using

  The epoxy-amine adducts of the present invention are, for example, solid electrolyte compositions; metal ion binding; monomolecular film accumulation (accumulation method); sustained-release microcapsule production; Can be used for various purposes. More specifically, the epoxy-amine adduct of the present invention includes, for example, a solid electrolyte composition using a cross-linked product of the epoxy-amine adduct of the present invention and a polyfunctional epoxy compound; the epoxy-amine adduct of the present invention or Bonding of metal ions by the derivative; accumulation of monomolecular films by previously treating the surface of the solid substrate with the epoxy-amine adduct of the present invention (accumulation method); epoxy-amine adduct of the present invention and diisocyanate compound Production of sustained-release microcapsules by interfacial polymerization; can be used in antibacterial and antibacterial conditions in water using polystyrene grafted with the epoxy-amine adduct of the present invention.

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

Example 1
[Production of epoxy-amine adduct]
As the epoxy compound (A), a dicyclopentadiene type epoxy [manufactured by Nippon Kayaku Co., Ltd., trade name “XD-1000”, a compound represented by the formula (a)] is used as an amine compound (B). Triethylenetetramine [manufactured by HUNTSMAN, trade name “TETA”] and isophoronediamine [manufactured by Evonik Degussa Japan Co., Ltd., trade name “Vestamine IPD”] were used.
In a 50 mL glass reaction vessel, 2.28 g of triethylenetetramine, 1.71 g of isophoronediamine, and 12.65 g of the epoxy compound (A) were mixed. The resulting mixture was stirred and reacted at 160 ° C. for 3 hours to produce an epoxy-amine adduct (amine adduct).
After allowing to cool, the content of the content is flowable (130 to 150 ° C.), and then poured onto a release paper from the reaction vessel, further cooled and solidified, and then pulverized to give an epoxy-amine An adduct was obtained.

Comparative Example 1
As the epoxy compound (A), 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate [manufactured by Daicel Corporation, trade name “Celoxide 2021P”] was used. Ethylenetetramine [manufactured by HUNTSMAN, trade name “TETA”] and isophoronediamine [manufactured by Evonik Degussa Japan Co., Ltd., trade name “Vestamine IPD”] were used.
In a 50 mL glass reaction vessel, 2.28 g of triethylenetetramine, 1.71 g of isophoronediamine, and 6.33 g of epoxy compound (A) were mixed. The resulting mixture was stirred and reacted at 160 ° C. for 3 hours to produce an epoxy-amine adduct (amine adduct).
After allowing to cool, the content of the content is flowable (130 to 150 ° C.), and then poured onto a release paper from the reaction vessel, further cooled and solidified, and then pulverized to give an epoxy-amine An adduct was obtained.

[Evaluation]
The epoxy-amine adducts obtained in Examples and Comparative Examples were made into a 20% ethanol solution, and then the solution was applied to a polyethylene film (thickness: 100 μm). By drying this, a coating film having a thickness of 20 μm was obtained. The polyethylene film on which this coating film was formed was cut into a size of 10 cm × 10 cm, and the state of the film when one end was lifted was observed.
The film having the epoxy-amine adduct coating film obtained in Example 1 is less bent than the film having the epoxy-amine adduct coating film obtained in Comparative Example 1, and obtained in Example 1. It was confirmed that the resulting epoxy-amine adduct coating film was harder.

Claims (8)

A compound having two or more amino groups in the molecule,
Obtained by a reaction between an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule;
An epoxy-amine adduct characterized by using a compound (A1) having one or more 5-membered rings in the molecule as the epoxy compound (A). The compound (A1) is at least one compound selected from the group consisting of a compound represented by the following formula (a), a compound represented by the following formula (b), and a compound represented by the following formula (c) The epoxy-amine adduct of claim 1 wherein

[Wherein, X represents a single bond or a divalent group having one or more atoms. ] The epoxy-amine adduct according to claim 1 or 2, wherein an amine compound (B1) represented by the following formula (1) is used as the amine compound (B).

[In Formula (1), R ¹ and R ² are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon. A divalent group in which one or more of the groups and one or more of the cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom. m represents 0 or an integer of 1 or more. ] The epoxy-amine addition according to claim 1 or 2, wherein an amine compound (B2) represented by the following formula (2) and an amine compound (B3) represented by the following formula (3) are used as the amine compound (B). object.

[Wherein, R ³ and R ⁴ are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group or a linear or branched aliphatic hydrocarbon group. A divalent group formed by linking the above and one or more cyclic aliphatic hydrocarbon groups. p represents an integer of 1 or more. ]

[Wherein, R ⁵ and R ⁷ are the same or different and each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. q represents 0 or 1; R ⁶ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. r represents an integer of 0 to 10. ] At least one structural unit selected from the group consisting of a structural unit represented by the following formula (Ia), a structural unit represented by the following formula (Ib), and a structural unit represented by the following formula (Ic); An epoxy-amine adduct containing a structural unit represented by the following formula (II) and having amino groups at both ends.

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

[Wherein, R ¹ and R ² are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group in which the above and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. m represents 0 or an integer of 1 or more. ]   The resin composition containing the epoxy-amine adduct as described in any one of Claims 1-5, and a thermoplastic resin.   The resin composition according to claim 6, which is a resin composition for fiber-reinforced composite materials.   A water-based paint comprising the epoxy-amine adduct according to any one of claims 1 to 5.