JP2015010094A - Curing agent composition, and epoxy resin cured product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing agent composition which can reduce an odor of a curing agent, and an epoxy resin cured product using the curing agent composition.SOLUTION: This invention relates to a curing agent composition comprising (A) at least one curing agent selected from the group consisting of polyamine and polymercaptan, and (B) specific hydroxy group-containing aromatic compound, and an epoxy resin cured product obtained by mixing and curing the curing agent composition and (C) epoxy resin.

Description

  The present invention relates to a curing agent composition, a cured product of an epoxy resin using the same, and a method for producing a cured epoxy resin.

  An epoxy resin is a resin obtained by polyaddition reaction of a bifunctional epoxy compound and a diamine. A cured product obtained by curing the epoxy resin with a curing agent has heat resistance, chemical resistance, electrical properties, and mechanical properties. Etc. are excellent. Therefore, the epoxy resin (prepolymer) before curing is used as a paint, an adhesive, and various molding materials, etc., and after molding, processing, and construction, the epoxy resin is cured, and a wide range of fields according to desired physical properties, It can be applied in use.

  It is known that a curing agent used for curing an epoxy resin contains polyamine, polymercaptan, or the like as a main component.

  Polyamines and polymercaptans used as the main component of the curing agent are often accompanied by strong irritation and odor, and there are sensitizing properties although there are differences among individuals, and it is recognized that they cause symptoms such as rash and rash. In addition, the strong odor of the curing agent not only brings about a significant reduction in work efficiency during molding, processing and construction to obtain a cured epoxy resin, but also the odor migrates to the surrounding walls, equipment, clothes, etc. The odor causes various problems.

  In order to suppress such an odor derived from the curing agent, attempts have been made to modify the curing agent as the main component.

  For example, in Patent Documents 1 to 3, an amine curing agent that is a curing agent is reacted with phenol and an aldehyde such as formaldehyde (Mannich reaction) and modified, or an epoxy compound is added to the amine curing agent and modified. Thus, a method for polymerizing an amine curing agent to suppress odor due to transpiration of the amine curing agent is disclosed.

  In this way, the amine-based curing agent is modified to prevent transpiration, but the present situation is that odor suppression cannot be sufficiently improved by some remaining free polyamines.

  In addition, as in Patent Documents 1 to 3, the phenol added to suppress the odor due to the transpiration of the amine curing agent remains partially unreacted in the curing agent composition, and the phenol-derived odor Is also a problem.

JP 2007-056152 A JP 2007-302753 A JP 2008-214567 A

  An object of this invention is to provide the hardening | curing agent composition which can reduce the odor of a hardening | curing agent, and the hardened | cured material of the epoxy resin using the said hardening | curing agent composition.

  In view of the present situation, the present inventors have conducted extensive studies to solve the above problems, and as a result, the curing agent further contains a specific hydroxyl group-containing aromatic compound, thereby producing a odor peculiar to the curing agent. It has been found that it can be greatly reduced.

  The present invention has been completed on the basis of such findings, and has been completed. The curing agent composition according to the following items 1 to 6, the cured product of the epoxy resin, and the method for producing the cured epoxy resin: It is to provide.

Item 1. At least one curing agent (A) selected from the group consisting of polyamines and polymercaptans, and general formula (1):

(In Formula (1), n is an integer of 1-3,
R ¹ is
It has at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, a hydroxyl group, and an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms. An optionally substituted phenylalkyl group;
An alkyl group having 1 to 6 carbon atoms;
Carboxyl group;
A hydroxyl group;
A phenyl group optionally having an alkyl group having 1 to 6 carbon atoms; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms;
when n is 2 or more, R ¹ may be the same or different), or the general formula (2):

(In formula (2), n is an integer of 1 to 3,
R ² is
Hydrogen atom;
It has at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, a hydroxyl group, and an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms. An optionally substituted phenylalkyl group;
An alkyl group having 1 to 6 carbon atoms;
Carboxyl group;
A hydroxyl group;
A phenyl group optionally having an alkyl group having 1 to 6 carbon atoms; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms;
When n is 2 or more, R ² may be the same or different)
Hydroxyl group-containing aromatic compound (B)
A curing agent composition comprising:

  Item 2. Item 2. The curing agent composition according to item 1, comprising 5-2000 parts by weight of the hydroxyl group-containing aromatic compound (B) with respect to 100 parts by weight of the curing agent (A).

  Item 3. Item 3. The curing agent composition according to Item 1 or 2, wherein the polyamine is at least one polyamine selected from the group consisting of a chain aliphatic polyamine, a cycloaliphatic polyamine, an aromatic polyamine, and a polyamide.

  Item 4. Item 4. The curing agent composition according to any one of Items 1 to 3, which is used for curing an epoxy resin.

Item 5. The hardening | curing agent composition in any one of claim | item 1-4, and an epoxy resin (C)
A cured product of an epoxy resin obtained by mixing and curing.

  Item 6. Item 5. A method for producing a cured epoxy resin product comprising a step of mixing the curing agent composition according to any one of Items 1 to 4 and an epoxy resin (C) and curing the mixture.

  According to the hardening | curing agent composition of this invention, the odor derived from a hardening | curing agent can be drastically reduced by further containing a specific hydroxyl-containing aromatic compound with respect to a hardening | curing agent. In particular, in construction of restaurants such as restaurants, it is possible to reduce the transfer of odor derived from the curing agent to the interior, etc., so that time such as ventilation after construction can be significantly reduced.

  In addition, when a conventional general curing agent passes for a long period of time, the curing agent chemically changes in the container with time, and the odor tends to increase. On the other hand, according to the hardening | curing agent composition of this invention, suppression of an odor can be maintained continuously. Therefore, the curing agent composition of the present invention is excellent in storage stability.

  Furthermore, the epoxy resin cured product obtained by using the above-described curing agent composition is not impaired in mechanical strength by the blending of the hydroxyl group-containing aromatic compound contained in the composition, It has the same mechanical strength as the cured product.

1. Curing Agent Composition The curing agent composition of the present invention includes a curing agent (A) and a hydroxyl group-containing aromatic compound (B). Hereinafter, each component will be described in detail.

1-1. Curing agent (component (A))
The curing agent (A) is at least one selected from the group consisting of polyamines and polymercaptans.

  Examples of the polyamine include divalent or higher, preferably 2 to 6 polyvalent amines, and at least one polyamine selected from the group consisting of chain aliphatic polyamines, cyclic aliphatic polyamines, aromatic polyamines, and polyamides. Is mentioned.

  Examples of chain aliphatic polyamines include methylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, dipropylenediamine, dipropylenetriamine, diethylaminopropylamine, 1,2- Examples include diaminopropane, tripropylenetetramine, and trimethylhexamethylenediamine.

  Cycloaliphatic polyamines include N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, isophoronediamine, mensendiamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis ( 3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 1,4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexyl Amine, norbornadiamine, bis (aminomethyl) cyclohexane, diaminodicyclohexylmethane and the like can be mentioned.

  As aromatic polyamines, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, bis (aminoalkyl) benzene, bis (aminoalkyl) naphthalene, m-phenylenediamine, p-phenylenediamine, tolylene- 2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, mesitylene-2,6-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltri Ren-2,6-diamine, biphenylenediamine, 4,4-diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis (4-aminophenyl) propane, 2,5-naphthylenediamine, 2,6-naphthylene Amine, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzo Enone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4 , 4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene and the like.

  Examples of the polyamide include those having a reactive monoamine and diamine in the molecule produced by a condensation reaction of a dicarboxylic acid and a polyamine.

  Specific examples of the dicarboxylic acid include polymerized fatty acid, monomeric fatty acid, epoxidized unsaturated fatty acid, alkenyl succinic acid, dibasic cyclohexane ring substituted compound and the like. Specific examples of the polyamine include polyethylene polyamine: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyoxyalkylenepolyamine, metaxylenediamine, and the like.

  Polymercaptan is a compound having at least two thiol groups in the molecule and is not particularly limited. For example, polyoxypropylene poly-2-hydroxythiol, ethylene glycol di (poly) hydroxyl Ether type polymercaptan, phthalate type dimercaptan, trimethylolpropane polymercaptopropionate, pentaerythritol polymercapto such as thiol, limonene dihydroxythiol, bisphenol A type dihydroxythiol, bisphenol F type dihydrooxythiol Examples include ester type polymercaptans such as propionate.

  These curing agents (A) can be obtained as commercial products, for example, ADEKA HARDNER EH-451N, EH-479A, EH-6024, EH-6028 manufactured by ADEKA CORPORATION; Ancamine 2702 manufactured by Air Products. 2706, 2730; Daito Sangaku Co., Ltd. Daitokural X1777A, FH; T & K TOKA Co., Ltd. Fuji Cure, tomide, etc. are mentioned.

  The curing agent (A) may be a polyamine or a part of the skeleton of polymercaptan modified, for example, a modified polyamine modified with diaminodiphenylmethane or the like.

  These curing agents (A) may be used alone or as a mixture of two or more.

  Among these curing agents (A), aliphatic polyamines, cycloaliphatic polyamines, and mixtures thereof are preferable from the viewpoint of excellent reactivity with the hydroxyl group-containing aromatic compound (B).

1-2. Hydroxyl group-containing aromatic compound (component (B))
As a hydroxyl-containing aromatic compound (B), it is a compound represented by General formula (1) or General formula (2).
General formula (1):

In the formula (1), n is an integer of 1 to 3, and may be a mixture of hydroxyl group-containing aromatic compounds having different numbers of n.

R ¹ is an amino group which may be substituted for an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a carboxyl group, a phenyl group, a hydroxyl group, or an alkyl group having 1 to 6 carbon atoms. A phenylalkyl group optionally having at least one substituent selected from the group consisting of: an alkyl group having 1 to 6 carbon atoms; a carboxyl group; a hydroxyl group; an alkyl group having 1 to 6 carbon atoms. A phenyl group which may be substituted; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms, and when n is 2 or more, R ¹ may be the same or different.

Among the above R ^1, the alkyl group substituted by the phenyl group when R ¹ is a phenylalkyl group which may have the above substituent, has 1 to 6 carbon atoms, preferably 1 carbon atom. ~ 4. Further, as a more specific compound, the formula (1 ′):

(In the formula (1 ′), n ′ is an integer of 1 to 3 and may be a mixture of compounds having different numbers of n ′. Ra and Rb are the same or different and are a hydrogen atom or a carbon number of 1; Rc is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), a hydroxyl group, 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms). Preferably, it is an amino group which may be substituted with an alkyl group having 1 to 4 carbon atoms).

  General formula (2):

In the formula (2), n is an integer of 1 to 3, and may be a mixture of hydroxyl group-containing aromatic compounds having different numbers of n.

R ² is an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a carboxyl group, a phenyl group, a hydroxyl group, and an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). A phenylalkyl group optionally having at least one substituent selected from the group consisting of amino groups optionally substituted; a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; a carboxyl group; a hydroxyl group; A phenyl group which may have an alkyl group having 1 to 6 carbon atoms; or an amino group which may substitute an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), and n is In the case of 2 or more, R ² may be the same or different.

As more specific examples of the hydroxyl group-containing aromatic compound represented by the general formulas (1) and (2),
General formula (1 "):

(In the formula (1 ″), n ′ is an integer of 1 to 3, and a mixture of compounds having different numbers of n ′ may be used.)
A styrenated phenol represented by:
Benzylphenol; dibenzylphenol; tribenzylphenol; bisphenol F; phenylphenol; salicylic acid; hydroquinone; bisphenol A, phenylphenol, tert-butylphenol; aminobenzylphenol; aminophenol;

In the general formula (1), the position of R ¹ may be substituted at any position of ortho position, meta position, and para position.

  These hydroxyl group-containing aromatic compounds (B) may be liquid or solid at room temperature, but the liquid hydroxyl group-containing aromatic compound (B) can be used only by mixing with a curing agent. It is preferable in that a curing agent composition can be easily prepared. Moreover, even if it is a solid hydroxyl-containing aromatic compound (B), if it can mix uniformly with a hardening | curing agent (A), it can be used as it is, and a solid hydroxyl-containing aromatic compound is previously contained in a solvent. The aromatic compound (B) can be dissolved and mixed with the curing agent (A) to prepare a curing agent composition. The solvent is not particularly limited as long as it is a solvent capable of dissolving the solid hydroxyl group-containing aromatic compound (B) and does not impair the effects of the present invention. Etc.

  From the above viewpoint, styrenated phenol and benzylphenol are liquid hydroxyl group-containing aromatic compounds (B), and are preferable because they can be uniformly mixed with the curing agent (A) without using the solvent. Moreover, even if it is a solid hydroxyl group-containing aromatic compound (B) such as phenylphenol, tert-butylphenol, bisphenol A, naphthol, etc., it is uniform when mixed with the curing agent (A) using the above solvent. Can be mixed. In any form, the odor derived from the curing agent can be sufficiently suppressed.

  These hydroxyl group-containing aromatic compounds (B) may be used alone or as a mixture of two or more.

  The content of the hydroxyl group-containing aromatic compound (B) is preferably 2000 parts by weight or less, more preferably 1500 parts by weight or less, still more preferably 1300 parts by weight or less, with respect to 100 parts by weight of the curing agent (A). Parts by weight or less, more preferably 400 parts by weight or less, still more preferably 300 parts by weight or less, still more preferably 250 parts by weight or less, still more preferably about 100 parts by weight, most preferably 60 parts by weight or less. Moreover, 5 weight part or more is preferable, as for content of a hydroxyl-containing aromatic compound (B), 10 weight part or more is more preferable, and 30 weight part or more is further more preferable. By setting the content of the hydroxyl group-containing aromatic compound (B) within the above range, the odor derived from the curing agent can be suppressed.

  In addition, when an epoxy resin is hardened | cured with the hardening | curing agent composition obtained later, from a viewpoint that characteristics, such as mechanical strength of hardened | cured material, can be exhibited, content of a hydroxyl-containing aromatic compound (B) is shown. It is preferable to set it to 1300 parts by weight or less.

1-3. Other components The curing agent composition of the present invention further includes a solvent, a filler, a leveling agent, an antifoaming agent, a viscosity modifier, a diluent, a curing accelerator, a plasticizer, a dye, a pigment, an antioxidant, and an ultraviolet absorber. , Optional components such as a light stabilizer, a flame retardant, and an anti-sagging agent can be contained. The contents of these optional components are not particularly limited as long as they do not affect the predetermined effects of the present invention, and are applied within a desired range. These optional components are appropriately set and blended as a curing agent composition and in the curing agent described later as long as the effects of the present invention are not impaired.

  Solvents include ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane; iso- or n-butanol, iso- or n-propanol, amyl alcohol, benzyl alcohol, furfuryl alcohol, tetrahydrofur Alcohols such as furyl alcohol; ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl butyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone; esters such as ethyl acetate and n-butyl acetate; benzene, toluene , Xylene and other aromatic hydrocarbons; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; high-boiling paraffinic solvents; aniline; triethylamine; pyridine; ; Acetonitrile.

As filler, aluminum; lead oxide; hydrated alumina; diatomaceous earth; zinc;
Calcium carbonate; Barium carbonate; Barium sulfate; Glass fiber; Glass bead; Glass microballoon; Carbon fiber; Cellulose; Silica sand; Cement; Kaolin; Clay; Aluminum hydroxide; Iron; bituminous substance; wollastonite; hydrous aluminum silicate clay minerals such as pyrophyllite; hydrous magnesium silicate clay minerals such as talc. The shape of these fillers is not particularly limited, and may be any shape such as fibrous, (fine) powder, granular, flake, plate, or rod.

  Leveling agents and antifoaming agents include acrylic ester, acrylic ester-vinyl copolymer, acrylic polyhydric carboxylic acid leveling agent, isoparaffin, liquid paraffin, silicone oil, polysiloxane oligomer A fluorine-based compound and the like.

  Examples of the viscosity modifier include synthetic silica; wax such as amide wax; clay mineral such as bentonite; colloidal calcium carbonate.

  Diluent phthalate; dibutyl phthalate; benzyl alcohol; ketones such as methyl isobutyl ketone and methyl ethyl ketone; alcohols such as butanol; aromatic hydrocarbons such as xylene; ethylene dichloride; acrylonitrile; methyl tert-butyl ether, propylene And ethers such as glycol monomethyl ether.

  Further, chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene and chlorinated polypropylene as thermoplastic resins; (meth) methyl acrylate copolymers, (meth) ethyl acrylate copolymers, (meth) propyl acrylate Copolymer, acrylic resin such as (meth) butyl acrylate copolymer, (meth) cyclohexyl cyclohexyl copolymer; vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer , Vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether copolymer, vinyl chloride-ethyl vinyl ether copolymer, and other vinyl chloride resins (vinyl chloride copolymers); styrene resins; aromatic petroleum resins Aliphatic petroleum resin; Urea aldehyde condensation resin; Ketone resin and benzyl alcohol Lumpur and the like can be used as well.

  Examples of the curing accelerator include trimethylamine, ethyldimethylamine, propyldimethylamine, N, N′-dimethylpiperazine, pyridine, picoline, 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), benzyl Tertiary amines such as dimethylamine, 2- (dimethylaminomethyl) phenol (DMP-10), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30); phenol novolak, o-cresol novolak, p Phenol compounds such as cresol novolak, tert-butylphenol novolak, dicyclopentadiene cresol, bisphenol A, bisphenol F, phenol, alkylphenol having an alkyl chain having 16 or less carbon atoms; p-toluenesulfonic acid, thio 1-aminopyrrolidine salt of an acid; phosphorous acid phenyl ester such as triphenyl phosphite, diphenyl hydrogen phosphite, diphenyl monodecyl phosphite; polyhydric alcohol such as trimethylolpropane, glycerin; 2,4,6-tris (Dimethylaminomethyl) phenol (DMP-30); butyric acid; cellulose acetate and the like.

  Examples of the plasticizer include polybasic acid esters such as dioctyl phthalate, dibutyl phthalate and dioctyl adipate; polyhydric alcohol esters such as diethylene glycol dibenzoate, diethylene glycol dioctate and glycerol tributyrate; 9,10-epoxy Examples include epoxidized esters such as octyl stearate, epoxidized vegetable oil, and dioctyl 4,5-epoxyhexahydrophthalate; and phosphoric esters of triphenyl phosphate, trioctyl phosphate, diphenyl monoisopropyl phosphate, and the like.

  Examples of the dyes and pigments include titanium oxide, carbon black, iron oxide, yellow lead, disazo yellow, quinophthalone yellow, monoazo red, benzimidazolone red, and phthalocyanine blue.

  Examples of the antioxidant include hindered phenol-based antioxidants such as dibutylhydroxytoluene; sulfur-based antioxidants such as dilauryl thiodipropionate and 2-mercaptobenzimidazole; tridecyl phosphite, triuryl trithiophos. Examples thereof include phosphites such as fights.

  Examples of the ultraviolet absorber include benzotriazole compounds such as 2 (2, -hydroxy-5′-methylphenyl) benzotriazole; benzophenone compounds such as 2,4-dihydroxybenzophenone; salicylic acid ester compounds such as phenyl salicylate. Etc.

  Examples of the light stabilizer include hindered amine compounds such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.

  Examples of the flame retardant include antimony trioxide, chlorinated paraffin, chlorinated diphenyl, and phosphate ester.

  Examples of the anti-sagging agent include colloidal shear force, hydrogenated castor oil-based wax, polyethylene wax, amide wax, organic bentonite, aluminum stearate, and zinc stearate.

  The hardening | curing agent composition of this invention is used in order to harden curable resin, and is used suitably as a hardening | curing agent of an epoxy resin especially as curable resin.

1-4. Form of Curing Agent Composition and Its Use The curing agent composition of the present invention is storage stable when used as a curing agent composition of a type in which an epoxy resin composition containing an epoxy resin is separately provided and two liquids are mixed at the time of use. It is preferable in that it can react quickly after mixing and an expected cured product can be obtained.

  The curing agent composition of the present invention is combined with the epoxy resin composition as the main agent, for example, a paint for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, flooring, etc. Adhesive: Adhesive tape for packaging, adhesive label, frozen food label, removable label, POS label, adhesive wallpaper, adhesive for adhesive flooring; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier Processed paper such as impregnated paper; fiber treatment agents such as converging agents such as natural fibers, synthetic fibers, glass fibers, carbon fibers and metal fibers, anti-fraying agents and processing agents; sealing materials (for example, shield segments and box culverts) Sealing materials for connecting parts), lining materials (for example, lining materials for water tanks such as water pits), civil engineering repair materials (for example, concrete) Grout for crack repair, defective repair materials, packing sealing material, etc.), cement admixture, etc. building materials such as waterproof material, can be used in a wide variety of applications.

  Since the curing agent composition of the present invention can greatly suppress the odor peculiar to the curing agent, it is particularly preferable to use it for paints or adhesives used for construction in interiors of restaurants and the like. preferable.

  As a viscosity of the hardening | curing agent composition of this invention, it sets suitably according to said use, It can prepare suitably using a solvent, a diluent, etc.

  The curing agent composition of the present invention can reduce the odor peculiar to the curing agent without using an aldehyde such as formaldehyde used in the conventional method for modifying the curing agent by the Mannich reaction.

2. Cured product of epoxy resin and production method thereof The cured product of the epoxy resin of the present invention is produced by mixing and curing the curing agent composition and the epoxy resin (C).

2-1. Curing Agent Composition As the curing agent composition, those listed in the above-mentioned “1. Curing agent composition” can be used.

2-2. Epoxy resin (component C)
It does not specifically limit as an epoxy resin (C), A general purpose epoxy resin can be used, If it contains two or more epoxy groups in a molecule | numerator, it can be used without a restriction | limiting. Examples thereof include a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and an alicyclic epoxy resin. These epoxy resins may be used alone or in combination of two or more.

  The epoxy resin may be in a liquid state, and when it is a solid epoxy resin, it may be mixed with another liquid resin by heating. Examples of the liquid resin include, but are not limited to, bisphenol A type liquid epoxy resin and bisphenol F type liquid epoxy resin.

  The blending amount of the epoxy resin (C) of the present invention is not particularly limited as long as a predetermined effect is obtained, but usually in the epoxy resin with respect to 1 equivalent of active hydrogen in the curing agent (A). In the range of 0.5 to 1.5 equivalents, preferably 0.7 to 1.2 equivalents. By setting the compounding amount of the epoxy resin within the above range, the obtained cured product is excellent in mechanical strength and excellent in transparency of the cured product.

  As a curing method performed after mixing the epoxy resin (C) and the curing agent composition, only the step of mixing the epoxy resin (C) and the curing agent composition, the epoxy resin (C) and the curing agent (A). When the reaction rate of this reaction (crosslinking reaction) is high, there is no particular need. However, for example, curing can be promoted by curing by heating, curing by UV irradiation, or the like. In these curing methods, curing by heat is preferable from the viewpoint of easy workability.

  Although it does not specifically limit in the range in which desired hardened | cured material is obtained when it hardens | cures by heating, For example, about 50-150 degreeC is preferable, about 70-150 degreeC is more preferable, 100- About 150 ° C. is more preferable.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.

Examples 1 to 17 and Comparative Example 1
Styrenated phenol (viscosity (measured under the following viscosity measurement conditions): 505 mPa · s) and aliphatic polyamine (Adeka Hardener EH-234 manufactured by Adeka Co., Ltd.) were mixed at the contents shown in Table 1, and each curing agent was mixed. A composition was obtained. About each obtained hardening | curing agent composition, the viscosity and odor were measured and evaluated by the following measuring methods. Table 1 shows the content of styrenated phenol and aliphatic polyamine, and evaluation of physical properties.

<Viscosity>
Using a BM type viscometer (BM type viscometer manufactured by Toki Sangyo Co., Ltd.), at 23 ° C., the rotor and the number of revolutions were appropriately changed and measured.

<Odor evaluation>
Measurements using detector tubes and human sensory tests were performed.

  In the human sensory test, the following standards are obtained by collecting each curing agent (aliphatic polyamine) from a container containing a mixture of styrenated phenol and aliphatic polyamine in a cup and sniffing it directly. Was used to evaluate the odor. The following criteria are relatively evaluated based on the evaluation “1” of Comparative Example 1.

5: The odor of amine is not confirmed at all. 4: The odor of amine is scarcely confirmed. 3: The odor of amine is slightly confirmed, but there is no effect on construction work. 2: The odor of amine is confirmed. However, there is no effect on construction work, etc. 1: The amine odor is remarkable

<Results and discussion>
From the results of Examples 1 to 17, the viscosity increased with an increase in the content of styrenated phenol. In the odor evaluation, the effect of reducing odor was observed when the content of styrenated phenol was 5 parts by weight or more, and the effect of reducing odor was particularly prominent when the content of styrenated phenol was 30 parts by weight or more.

Examples 18 to 19 and Comparative Examples 2 to 10
As a curing agent, 70 parts by weight of an aliphatic polyamine (ADEKA HARDNER EH-479A manufactured by ADEKA CORPORATION) and 30 parts by weight of n-aminopiperazine were used, and the curing agent (total amount: 100 parts by weight) Each additive (30 parts by weight) shown in Table 1 was mixed to obtain each curing agent composition. The viscosity of each of the obtained curing agent compositions was measured, and the odor was measured and evaluated by the following methods and standards. The viscosity was measured by the same method as in Example 1. Table 2 shows the components of the additives in each curing agent composition and the evaluation of physical properties.

  Moreover, the high boiling point aromatic hydrocarbon compound shown as an additive shown in Table 2 used Hysol SAS-296 made by JX Nippon Mining & Energy Corporation; Nixanol Y-50 made by Fudou Co., Ltd. was used as the xylene resin. .

<Odor evaluation>
Measurements using detector tubes and human sensory tests were performed. For the odor measurement by the detector tube, the odor was measured by the same method as that used in Example 1.

  In the sensory test by humans, each of the curing agents was collected so that the amount of the curing agent was the same amount, and sealed in a 500 ml square can container. Then, after leaving for 24 hours, it was opened and sealed again. Furthermore, 30 minutes and 1.5 hours later, each was opened, and the odor at the time of each opening was directly smelled, and evaluated according to the following criteria. The following criteria are relatively evaluated based on the evaluation “1” of Comparative Example 2.

5: The odor of amine is not confirmed at all. 4: The odor of amine is scarcely confirmed. 3: The odor of amine is slightly confirmed, but there is no effect on construction work. 2: The odor of amine is confirmed. However, there is no effect on construction work, etc. 1: The amine odor is remarkable

<Results and discussion>
From Examples 18 and 19, when tribenzylphenol and styrenated phenol were used as additives, the effect of reducing the odor of amine could be confirmed.

  On the other hand, the additives used in Comparative Examples 2 to 10 did not provide a sufficient amine odor suppression effect. In Comparative Examples 3, 5, 6, and 8 to 10, some amine odors were somewhat reduced, but the odor of the additive itself was confirmed, and sufficient effects were not exhibited. .

Examples 20-32
As the curing agent, 70 parts by weight of an aliphatic polyamine (ADEKA HARDNER EH-479A manufactured by ADEKA CORPORATION) and 30 parts by weight of n-aminopiperazine were used, and the curing agent (total amount: 100 parts by weight) The additives (30 parts by weight) shown in the above were mixed while being heated at 90 ° C. for 30 minutes to obtain each curing agent composition. About each obtained hardening | curing agent composition, the viscosity and odor were measured and evaluated by the method similar to Example 18, and a reference | standard. Table 3 shows the components of the additives in each curing agent composition and the evaluation of physical properties.

  In addition, in the additive shown in Table 3, the additive diluted with 50% of the concentration with benzyl alcohol was used for the additive of Examples 20-24.

<Results and discussion>
As in Examples 25 to 32, even when the additive was solid, it was found that an amine odor suppressing effect can be obtained by sufficiently uniformly mixing with the amine curing agent.

  Further, as in Examples 20 to 24, even when diluted with benzyl alcohol to a concentration of 50%, the amount of the compound in the additive capable of relatively exerting the odor suppressing effect decreased, but even in that case, It was found that the odor suppression of amine can be sufficiently obtained.

  In Example 32, a naphthol odor was confirmed, but the amine odor evaluation was as high as “4”, and it was confirmed that odor suppression was sufficiently obtained.

Examples 33-40
The curing agent shown in Table 4 and the styrenated phenol were mixed so as to have the contents shown in Table 4 to obtain each curing agent composition. About each obtained hardening | curing agent composition, the viscosity and odor were measured and evaluated by the method similar to Example 18, and a reference | standard. Table 4 shows the content of the curing agent composition, the components of the additives in each curing agent composition, and the evaluation of physical properties.

  In the curing agent shown in Table 4, the amidoamine of Example 37 is Zenamide 747 manufactured by Cognis Japan Co., Ltd .; the mercaptan of Example 38 is QX-11 manufactured by Mitsubishi Chemical Corporation; the DDM-modified polyamine of Example 39 (Diaminodiphenylmethane modified polyamine) Daito Sangyo Co., Ltd. Daitokural M-1086; the tertiary amine of Example 40 used Adeka Hardener EHC-30 manufactured by Adeka Corporation.

<Results and discussion>
As shown in Examples 33 to 40, it was confirmed that the effect of suppressing odor derived from the curing agent was obtained by using the additive of the present invention regardless of the type of the curing agent.

Examples 41-61
In the curing agent composition, the curing agent composition obtained in Examples 7, 8, and 18 to 36 and an epoxy resin (Corresin EC (for winter) manufactured by Hattori Shoten Co., Ltd. (epoxy equivalent: 300 equivalents)) It mixed so that the epoxy equivalent in Core Resin EC (for winter) might become 1 equivalent with respect to 1 equivalent of active hydrogen equivalents of the hardening | curing agent.

  Moreover, each obtained mixture was apply | coated to the slate board on the conditions of 23 degreeC and humidity 50%, the coating film was formed, and the coating film was hardened on conditions of 23 degreeC and humidity 50%.

  About the obtained hardened | cured material, gloss / surface state, water-whitening, pencil hardness, and D hardness (type D hardness) were measured with the following method. In addition, said physical property value is a physical property after leaving to stand for 24 hours after hardening. The measurement results are shown in Tables 5 and 6.

<Gloss / Surface condition>
The appearance of the surface of the obtained cured product was evaluated according to the following criteria.

5: Glossy, surface is very smooth 4: Glossy, surface is smooth 3: Extremely small Yuzu skin is seen 2: Fine Yuzu skin is seen, sufficient gloss is obtained 1: No gloss at all <Water whitening>
The appearance of the surface of the obtained cured product was evaluated according to the following criteria.

5: No whitening can be confirmed 4: Although whitening has occurred slightly, there is no influence on the physical properties of other coatings 3: Whitening has occurred, and other physical properties of the coatings are affected 2 : Whitening is remarkable 1: Large craters are generated on the surface of the cured product <Pencil hardness>
The pencil hardness was measured according to JIS K-5600.

<D hardness (type D hardness)>
The D hardness was measured in accordance with JIS K7215D using a hardness meter (GS-702N manufactured by Teclock Co., Ltd.).

Comparative Examples 11-15
The curing agent composition obtained in Comparative Examples 3 to 7 and an epoxy resin (Corresin EC (for winter) manufactured by Hattori Shoten Co., Ltd.) are used with respect to 1 equivalent of active hydrogen equivalent of amine in the curing agent composition. The mixture was mixed so that the epoxy equivalent in Core Resin EC (for winter) was 1 equivalent. The obtained mixture was applied under the same conditions as in Example 41 to form a coating film, and the coating film was cured.

  About the obtained hardened | cured material, gloss / surface state, pencil hardness, and D hardness were measured by the method similar to Example 41. FIG. Table 7 shows the measurement results.

<Results and discussion>
From the results of Table 5 to Table 7, as in Examples 41 to 61, in the formation of the cured resin, the blending of the additive does not affect the physical properties and properties of the coating film, and has good hardness. It was confirmed that the cured coating film can be obtained.

  In addition, when Example 9-15 was used as a hardening | curing agent composition and the coating film was formed by the method similar to Example 41 and the coating film was hardened, with the increase in content of styrenated phenol, Although the cured product tended to soften, it was confirmed that the cured state was good.

Claims (6)

At least one curing agent (A) selected from the group consisting of polyamines and polymercaptans, and general formula (1):

(In Formula (1), n is an integer of 1-3,
R ¹ is
It has at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, a hydroxyl group, and an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms. An optionally substituted phenylalkyl group;
An alkyl group having 1 to 6 carbon atoms;
Carboxyl group;
A hydroxyl group;
A phenyl group optionally having an alkyl group having 1 to 6 carbon atoms; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms;
when n is 2 or more, R ¹ may be the same or different), or the general formula (2):

(In formula (2), n is an integer of 1 to 3,
R ² is
Hydrogen atom;
It has at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, a hydroxyl group, and an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms. An optionally substituted phenylalkyl group;
An alkyl group having 1 to 6 carbon atoms;
Carboxyl group;
A hydroxyl group;
A phenyl group optionally having an alkyl group having 1 to 6 carbon atoms; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms;
When n is 2 or more, R ² may be the same or different)
Hydroxyl group-containing aromatic compound (B)
A curing agent composition comprising: The hardening | curing agent composition of Claim 1 which contains 5-2000 weight part of hydroxyl-containing aromatic compounds (B) with respect to 100 weight part of hardening | curing agents (A). The curing agent composition according to claim 1 or 2, wherein the polyamine is at least one polyamine selected from the group consisting of chain aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines, and polyamides. The hardening | curing agent composition in any one of Claims 1-3 used for hardening of an epoxy resin. Hardener composition in any one of Claims 1-4, and an epoxy resin (C)
A cured product of an epoxy resin obtained by mixing and curing. The manufacturing method of the epoxy resin hardened | cured material including the process of mixing and hardening | curing the hardening | curing agent composition in any one of Claims 1-4, and an epoxy resin (C).