JP2006070125A - Curing agent composition for epoxy resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing agent for an epoxy resin, which can give a coating material capable of having a high solids concentration, curable even at ordinary temperature, and capable of forming a coating film excellent in weather resistance. <P>SOLUTION: The curing agent composition for the epoxy resin mainly consists of (a) a modified polyamide represented by formula (I) and (b) a cyclic polyamine/epoxy compound adduct. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curing agent composition for an epoxy resin, and more particularly to a curing agent composition for an epoxy resin mainly composed of an epoxy adduct of a specific modified polyamine and a cyclic polyamine. The present invention also relates to a curable epoxy resin composition using a combination of the epoxy resin curing agent composition and a polyepoxy compound. The curable epoxy resin composition can form a coating film excellent in weather resistance and the like, and is suitable for coating materials.

  Epoxy resins have excellent adhesion to various substrates, and cured products obtained by curing epoxy resins with curing agents have relatively good heat resistance, chemical resistance, electrical properties, mechanical properties, etc. Therefore, it is used in a wide range of fields, especially in the field of paints and adhesives.

  Epoxy resin paints obtained from epoxy resins are particularly suitable as undercoat paints and intermediate paints for steel structures because of their excellent adhesion to substrates and corrosion resistance. On the other hand, since the epoxy resin paint has a defect that it is inferior in weather resistance, top coating such as acrylic resin paint and polyurethane resin paint excellent in weather resistance is applied.

  Here, when a ship, bridge, or other structure is painted outdoors, it takes a long time to apply the top coat after applying the undercoat or intermediate coat using epoxy resin paint. May cause problems such as deterioration of the anticorrosion performance of the epoxy resin paint due to deterioration of the surface of the undercoat or intermediate coat, and a decrease in adhesion to the topcoat. Accordingly, even when top coating is performed, a certain degree of weather resistance is required for the epoxy resin paint.

  In recent years, in order to simplify the painting process, there is a demand for a paint that can be used as both a base coat and an intermediate coat and a top coat. Therefore, there is a stronger demand for high weather resistance of epoxy resin paints. It has become.

  The polyamidoamine curing agent obtained by modifying an aliphatic polyamine such as polyethylene polyamine with a carboxylic acid such as dimer acid can be cured at room temperature by combining with a polyepoxy compound such as bisphenol A type epoxy resin, It is known that a paint having excellent weather resistance can be provided. In recent years, there has been a tendency to reduce the amount of solvent in the paint due to the problem of environmental impact. In such a case, in the paint using the polyamidoamine-based curing agent, the cured coating film becomes cloudy due to the compatibility problem. Etc. arise. On the other hand, polyamidoamine-based curing agents obtained by modifying polyamines having an aromatic ring such as metaxylenediamine with dimer acid have excellent compatibility with epoxy resins, but have a problem that the weather resistance is significantly reduced. there were.

  Moreover, since it is difficult to increase the concentration of solids when using existing polyamides as curing agents, it becomes a product that violates VOC regulations. There was also a problem that the number of processes increased and labor costs increased.

  For example, Patent Document 1 discloses that an epoxy resin curing agent having an excellent physical property of an epoxy resin cured product is a polyamide composed of dibasic acid (ester), acrylic acid derivative, monocarboxylic acid (ester), and polyalkylene polyamine. It is described that it can be provided. However, the polyamide alone is slow to cure, and when trying to make it highly solid due to environmental problems, the compatibility with the liquid bisphenol diglycidyl ether used as the main agent is poor, and the coating film is tacky and normal. There was a drawback that a coating film was not formed.

JP-A-55-78014

  Accordingly, an object of the present invention is to provide a curing agent composition for an epoxy resin that can contain a high concentration of solids, can be cured even at room temperature, and can provide a paint that forms a coating film having excellent weather resistance. To provide things.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by combining a modified polyamine obtained by reacting a polyamine compound and a (meth) acrylic acid ester with a cyclic polyamine adduct. The headline, the present invention has been reached.

  That is, the present invention comprises (a) an epoxy resin curing agent composition comprising as a main component an epoxy adduct of a modified polyamine represented by the following general formula (I) and (b) a cyclic polyamine, and (A The present invention provides a curable epoxy resin composition comprising a polyepoxy compound and (B) the epoxy resin curing agent composition.

  The curing agent composition for epoxy resin of the present invention is a curable epoxy resin composition having a solid content concentration of 70% by mass or more, excellent curability at normal temperature and weather resistance, and suitable for paints. Can be provided.

  Hereinafter, the hardening | curing agent composition for epoxy resins of this invention is demonstrated in detail.

  The curing agent composition for epoxy resins of the present invention comprises (a) a modified polyamine represented by the following general formula (I) and (b) an epoxy adduct of a cyclic polyamine as a main component. In the curing agent composition for use, the content of the component (A) is preferably 15 to 80% by mass, and the content of the component (B) is preferably 10 to 70% by mass.

  The modified polyamine represented by the general formula (I) used in the present invention is not particularly limited by the production method thereof. For example, (a) a polyamine compound and (b) acrylic acid Or it can manufacture easily by making the ester compound of methacrylic acid react.

  Examples of the (a) polyamine compound used herein include compounds having two or more primary or secondary amino groups in the molecule, and specific examples thereof include ethylenediamine, hexamethylenediamine, metaxylene. Alkylene diamines such as diamine (m-xylylenediamine) and 1,3-bis (aminomethyl) cyclohexane; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine; 1,2-diaminocyclohexane, 1,3 -Diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, norbornenediamine, dicyclopentanediamine, diaminodicyclomethane, dicyclopentadienedimethylamine, N-cyclohexylpropylene Examples include alicyclic polyamines such as amines; heterocyclic polyamines such as 1,4-bis (3-aminopropyl) piperazine; aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, and the like. Or may be used in combination. Among these, metaxylenediamine and 1,3-bis (aminomethyl) cyclohexane are particularly preferable because they can form a cured coating film having excellent compatibility with the polyepoxy compound and excellent weather resistance.

  Examples of the ester compound of (b) acrylic acid or methacrylic acid used here include acrylic acid or methyl methacrylate, -ethyl, -propyl, -isopropyl, -butyl, -isobutyl, -secondary butyl, -secondary Tributyl, -amyl, -isoamyl, -tertiary amyl, -hexyl, -heptyl, -octyl, -isooctyl, -tertiary octyl, -2-ethylhexyl and the like, these may be used alone, Or you may use together. Among these, methyl acrylate is particularly preferable because amides can be easily formed.

  The modified polyamine, which is the component (A) used in the present invention, is 0.1 to 1.8 mol of the ester compound of (b) acrylic acid or methacrylic acid with respect to 1 mol of the polyamine compound (a). In particular, it is preferably obtained by reacting 0.4 to 1.2 mol. When the modified polyamine obtained at this reaction ratio is used, a curable epoxy resin composition having excellent curability and excellent coating film properties such as weather resistance can be obtained.

  The epoxy adduct of the cyclic polyamine which is the component (b) used in the present invention is easily obtained by reacting (c) the cyclic polyamine with (d) the epoxy compound.

  Examples of the (c) cyclic polyamine used here include 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophorone diamine, norbornene diamine, and dicyclohexane. Examples include alicyclic polyamines such as pentanediamine, diaminodicyclomethane, dicyclopentadienedimethylamine, and N-cyclohexylpropylenediamine; and aromatic group-containing polyamines such as metaxylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Among these, it is preferable to use at least one selected from 1,3-diaminocyclohexane, metaxylenediamine, norbornenediamine, and isophoronediamine.

  Examples of the (d) epoxy compound used here include phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, sec-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, Monoglycidyl ether compounds such as stearyl glycidyl ether; monoglycidyl ester compounds such as versatic acid glycidyl ester; polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, phloroglucinol; dihydroxynaphthalene, Biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, iso Ropyridene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1 , 1,3-Tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, butylene Polyglycidyl ethers of polyhydric alcohols such as glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid Acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as acids, endomethylenetetrahydrophthalic acid, and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) epoxy compounds having a glycidylamino group such as methane and diglycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3, Epoxidized products of cyclic olefin compounds such as 4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; Examples include epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate. Among these, bisphenol A diglycidyl ether, phenyl glycidyl ether, and hexamethylene diglycidyl ether are preferably used.

  The epoxy adduct of the above cyclic polyamine, which is the component (b) used in the present invention, is 0.1 to 1.8 mol of the above (d) epoxy compound with respect to 1 mol of the above (c) cyclic polyamine. It is preferable to be obtained by reacting 0.4 to 1.2 mol. When an epoxy adduct of a cyclic polyamine obtained at this reaction ratio is used, a curable epoxy resin composition having excellent curability and further excellent coating properties such as weather resistance can be obtained.

  In the present invention, the ratio (b) / (b) of the epoxy adduct of the modified polyamine as component (a) and the cyclic polyamine as component (b) is 30/70 to 80/20 in mass ratio. Is more preferable, and 50/50 to 80/20 is more preferable. When the amount of component (a) is small, there is a risk that a product having satisfactory adhesion and anticorrosion properties may not be obtained, and when the amount of component (b) is small, the drying property may decrease.

  The epoxy resin curing agent composition of the present invention can contain various organic solvents for easy handling. Examples of the organic solvent include ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane; iso- or n-butanol, iso- or n-propanol, amyl alcohol, benzyl alcohol, Examples include alcohols such as furyl alcohol and tetrahydrofurfuryl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; ether alcohols such as propylene glycol monomethyl ether; aniline, triethylamine, pyridine, dioxane, acetonitrile and the like.

  Moreover, it is preferable that the hardening | curing agent composition for epoxy resins of this invention is 70 mass% or more of solid content, especially 80 mass% or more. If the solid content is not 70% by mass or more, the solid content of the paint is low when used in a paint, and if the paint is not applied twice or three times, the flesh of the paint tends to deteriorate. In satisfying the solid content, the amount of the organic solvent used is preferably 0 to 40 parts by weight, more preferably 100 parts by weight based on the total amount of solids in the curing agent composition for epoxy resin of the present invention. 0 to 25 parts by mass.

  The hardening | curing agent composition for epoxy resins of this invention is used as a curable epoxy resin composition of this invention in combination with the main ingredient which has a (A) polyepoxy compound as a main component.

  Examples of the polyepoxy compound (A) include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4 -Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobis Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as enol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, Hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyglycidyl ethers of polyhydric alcohols such as bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, Glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer Of aliphatic, aromatic or alicyclic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Glycidyl esters and glycidyl methacrylate homopolymers or copolymers; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, glycidylamino groups such as diglycidyl orthotoluidine An epoxy compound having: vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclone Epoxidized products of cyclic olefin compounds such as rhohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, Examples include heterocyclic compounds such as triglycidyl isocyanurate. These polyepoxy compounds may be those internally crosslinked by a prepolymer of terminal isocyanate, or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, polyphosphate ester, etc.).

  In addition, the (A) polyepoxy compound preferably has an epoxy equivalent of 100 to 2000, particularly 150 to 1500. If the epoxy equivalent is less than 100, the curability may be lowered, and if it is greater than 2000, sufficient film properties may not be obtained.

  The (A) polyepoxy compound can be used by dissolving in various organic solvents in order to facilitate handling. Examples of the organic solvent include the above-mentioned organic solvents that can be used for the epoxy resin curing agent composition of the present invention, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate. , Ketones such as cyclohexanone; esters such as ethyl acetate and n-butyl acetate; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Examples include high-boiling paraffinic solvents such as Solvesso # 100 (Exxon Chemical Co., Ltd.).

  As for the usage-amount of the said organic solvent, 0-40 mass parts is preferable with respect to 100 mass parts of (A) polyepoxy compounds, More preferably, it is 0-20 mass parts. When the amount used exceeds 40 parts by weight, it volatilizes and generates danger, harm, etc., which is not preferable.

  Moreover, a reactive diluent or a non-reactive diluent can also be used for the main ingredient which has the said (A) polyepoxy compound as a main component. Examples of the reactive diluent include phenol, cresol, ethylphenol, propylphenol, p-tert-butylphenol, p-tert-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol and terpenephenol. Examples include monoglycidyl ether compounds such as monoglycidyl ether, and examples of the non-reactive diluent include dioctyl phthalate, dibutyl phthalate, and benzyl alcohol.

  In the curable epoxy resin composition of the present invention, the amount of the (A) polyepoxy compound and (B) the epoxy resin curing agent composition of the present invention is equal to the former epoxy equivalent and the latter active hydrogen equivalent. It is preferable to use it in an amount, and the amount can be changed in an arbitrary range as required. However, (A) a polyepoxy compound and (B) a main component in the curing agent composition for epoxy resin of the present invention. It is preferable that the ratio of use to the components (component (A) and component (B)) (the former: the latter, based on mass) is selected in the range of 90 to 10:10 to 90.

  In the curable epoxy resin composition of the present invention, it is preferable to use a curing accelerator in combination because improvement in curability is observed. Examples of the curing accelerator include trimethylamine, ethyldimethylamine, propyldimethylamine, N, N′-dimethylpiperazine, pyridine, picoline, 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), Tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol (DMP-10), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30); phenol novolac, o-cresol novolak And phenols such as p-cresol novolak, t-butylphenol novolak and dicyclopentadiene cresol; 1-aminopyrrolidine salt of p-toluenesulfonic acid and thiocyanic acid (manufactured by Otsuka Chemical Co., Ltd .; NR-S), and the like. .

  The amount of these curing accelerators used is preferably 1 to 30% by mass, particularly preferably 2 to 20% by mass, based on the solid content in the curable epoxy resin composition.

  In the curable epoxy resin composition of the present invention, a commonly used curing agent for epoxy resins can be used together with the curing agent for epoxy resins of the present invention. Examples of the curing agent include polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; fats such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and isophoronediamine. Cyclic polyamines; organic polyamines such as aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Also, amidation-modified products produced by reacting these organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid by a conventional method; these organic polyamines and aldehydes such as formaldehyde And a modified Mannich product produced by reacting a phenol having at least one aldehyde-reactive site with a nucleus such as phenol, cresol, xylenol, tert-butylphenol, resorcin, and the like by a conventional method. Further, dicyandiamide; acid anhydride; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4- Latent curing agents such as imidazoles such as methylimidazole can also be used.

  The use amount of these curing agents other than the curing agent composition for epoxy resin of the present invention is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the main component of the curing agent composition for epoxy resin of the present invention. .

  In order to improve the weather resistance, a piperidine compound can be used in combination with the curable epoxy resin composition of the present invention. Examples of the piperidine compound include N-nitrooxy-2,2,6,6-tetramethyl-4-piperidinol, N-nitrooxy-2,2,6,6-tetramethyl-4-methoxypiperidine, N-nitrooxy. -2,2,6,6-tetramethyl-4-butoxypiperidine, N-nitrooxy-2,2,6,6-tetramethyl-4-octyloxypiperidine, 2,2,6,6-tetramethyl-4 -Piperidinol, 1,2,2,6,6-pentamethyl-4-piperidinol, 1-hydroxy-2,2,6,6-pentamethyl-4-piperidinol, 2,2,6,6-tetramethyl-4- Piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 1-oxyl-2,2,6,6-pentamethyl-4-pipe Distearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, 1-oxyl-2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) Sebacate, bis (1-oxyl-2,2,6,6-tetramethylpiperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl- Piperidyl methacrylate, 1-oxyl-2,2,6,6-tetramethyl-piperidyl methacrylate, tetrakis (2,2,6,6-tetramethyl- -Piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1-oxyl-2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) .Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,2,3 4-butanetetracarboxylate, bis (1-oxyl-2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5 .5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2, 4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1-oxyl-2,2,6,6-pentamethyl-4-piperidyl] Oxycarbo Ruoxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6 Tertiary octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) Amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2) , 2,6,6-pentamethyl-4-piperidi ) Amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,2) 6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2) , 6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / succinic acid Examples include diethyl polycondensate and 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate.

  The amount of these piperidyl compounds used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin solid content contained in the epoxy resin curing agent composition of the present invention. Part by mass. If the amount is less than 0.01 parts by mass, the effect cannot be exhibited sufficiently, and even if the amount exceeds 20 parts by mass, the effect of increasing the weight cannot be obtained, and the physical properties of the cured product may be reduced. is there.

  The curing accelerator, the curing agent other than the curing agent composition for epoxy resin of the present invention, and the piperidyl compound may be used by being previously contained in the curing agent composition for epoxy resin of the present invention. In addition, each of the curing agent composition for epoxy resin and the curable epoxy resin composition of the present invention can be blended with other components that can be usually used for each as required.

  The curable epoxy resin composition of the present invention, which combines the curing agent composition for epoxy resin of the present invention and the main agent mainly composed of a polyepoxy compound, is, for example, concrete, cement mortar, various metals, leather, glass, Paints or adhesives for rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive labels, frozen food labels, removable labels, POS labels, adhesive wallpaper, adhesives for adhesive flooring; art paper, lightweight coated paper , Cast coated paper, coated paperboard, carbonless copying machine, impregnated paper and other processed paper; natural fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers and other converging agents, fraying inhibitors, processing agents and other fiber treatments Agents: Can be used for a wide range of applications such as building materials such as sealing materials, cement admixtures and waterproofing materials, and among these, they are particularly suitable for paints.

  Hereinafter, although a manufacture example, an Example, etc. are shown and the hardening | curing agent composition for epoxy resins and curable epoxy resin composition of this invention are demonstrated in detail, this invention is not limited to these.

[Production Example 1] Production 1 of modified polyamine
To 272 g (2 mol) of metaxylenediamine (MXDA), 74 g (1 mol) of methyl acrylate (Ac-Me) was added dropwise at 40-60 ° C. and aged at 90 ° C. for 1 hour to complete the Michael addition reaction. I let you. The mixture was further heated to 160 ° C. and reacted at normal pressure for 2 hours, and further subjected to reduced methanol removal at 160 ° C. and 50 torr. 1 (amine number: 795) was obtained.

[Production Example 2] Production 2 of modified polyamine
74 g (1 mol) of methyl acrylate (Ac-Me) was added to a mixture of 136 g (1 mol) of metaxylenediamine (MXDA) and 142 g (1 mol) of 1,3-diaminocyclohexane (1,3-BAC). The mixture was dropped at 40 to 60 ° C. and aged at 90 ° C. for 1 hour to complete the Michael addition reaction. The mixture was further heated to 160 ° C. and reacted at normal pressure for 2 hours, and further subjected to reduced methanol removal at 160 ° C. and 50 torr. 2 (amine number: 780) was obtained.

[Production Example 3] Production of cyclic polyamine epoxy adduct 1
With respect to 142 g (1 mol) of 1,3-diaminocyclohexane (1,3-BAC), Adeka Resin EP-4100E (Asahi Denka Kogyo Co., Ltd .; bisphenol A diglycidyl ether, epoxy equivalent 190) 190 g (0.5 Mol) at 40 to 60 ° C. and aged at 90 ° C. for 1 hour. 1 (amine number: 337) was obtained.

[Production Examples 4 to 8] Production of cyclic polyamine epoxy adducts 2 to 6
In the same manner as in Production Example 3, except that the types and amounts of the polyamine compound and the epoxy compound used were as shown in Table 1, the polyamine adduct No. 2 to 6 were produced respectively.
In addition, the abbreviation in Table 1 shows the following compounds, respectively.
MXDA: metaxylene diamine, NBDA: norbornene diamine, IPDA: isophorone diamine, PGE: phenyl glycidyl ether, ED-503: hexamethylene diglycidyl ether (Asahi Denka Kogyo Co., Ltd., Adekaglycilol ED-503, epoxy equivalent 165 )

[Production Example 9] Production of epoxy adduct of acyclic polyamine 1
In the same manner as in Production Example 3, except that triethylenetetramine (TTA) was used instead of 1,3-diaminocyclohexane (1,3-BAC), polyamine adduct No. 7 was produced.

[Examples 1 to 7 and Comparative Examples 1 to 3] Preparation of curing agent composition for epoxy resin Modified polyamine Nos. Obtained by the above production examples. 1-2 and polyamine adduct no. 1 to 7 were used and dissolved in propylene glycol monomethyl ether (solv) according to the formulation shown in Table 2 below to prepare curing agent compositions of Examples 1 to 7 and Comparative Examples 1 to 3, respectively.

Example 8
Modified polyamine No. obtained by the above production example. 1 and polyamine adduct No. 1 1 were dissolved in propylene glycol monomethyl ether (solv) according to the formulation shown in Table 3 below, and then cooled to 80 to 90 ° C. and blended with 5% by mass of p-toluenesulfonic acid. The curing agent composition of Example 8 was obtained.

Example 9
Modified polyamine No. obtained by the above production example. 1 and polyamine adduct No. 1 1 were dissolved in propylene glycol monomethyl ether (solv) according to the formulation shown in Table 3 below, and then cooled to 80 to 90 ° C., and NR-S (manufactured by Otsuka Chemical Co., Ltd .; thiocyanic acid) Of 1-aminopyrrolidine salt) was blended to obtain a curing agent composition of Example 9.

Example 10
Modified polyamine No. obtained by the above production example. 1 and polyamine adduct No. 1 1 were dissolved in propylene glycol monomethyl ether (solv) according to the formulation shown in Table 3 below, and then cooled to 80 to 90 ° C., and NR-S (manufactured by Otsuka Chemical Co., Ltd .; thiocyanic acid) 1-aminopyrrolidine salt) 5% by mass and Adekastab LA-7RD (Asahi Denka Kogyo Co., Ltd .; N-nitrooxy-2,2,6,6-tetramethyl-4-piperidinol) 1% by mass were blended. The curing agent composition of Example 10 was obtained.

Example 11
Modified polyamine No. obtained by the above production example. 2 and polyamine adduct no. 1 were dissolved in propylene glycol monomethyl ether (solv) according to the formulation shown in Table 3 below, and then cooled to 80 to 90 ° C., and NR-S (manufactured by Otsuka Chemical Co., Ltd .; thiocyanic acid) 1-aminopyrrolidine salt) 5% by mass and Adekastab LA-7RD (Asahi Denka Kogyo Co., Ltd .; N-nitrooxy-2,2,6,6-tetramethyl-4-piperidinol) 1% by mass were blended. The curing agent composition of Example 11 was obtained.

[Examples 12 to 22, Comparative Examples 4 to 6]
The following curability evaluation, appearance evaluation, b value measurement, recoatability evaluation, and temperature gradient test were performed using the curing agent compositions obtained as described above. The results are shown in Tables 4 and 5.

(Curability evaluation)
An epoxy resin (Adeka Resin EP-4100G, manufactured by Asahi Denka Kogyo Co., Ltd.) and a curing agent composition were mixed in an amount of epoxy equivalent / active hydrogen equivalent = 1/1 at 5 ° C. and a humidity of 85%. Then, it apply | coated so that it might become a film thickness of 200 micrometers on a mild steel plate on a mild steel plate, and this was cured at room temperature for 18 hours. The presence or absence of tack on the surface of the coating after curing was confirmed, and the results were evaluated in 10 stages. An evaluation result of 1 indicates that no gelation has occurred. The larger the numerical value, the better the curing, and 10 indicates a state in which no tack remains.

(Appearance evaluation)
An epoxy resin (Adeka Resin EP-4100G, manufactured by Asahi Denka Kogyo Co., Ltd.) and a curing agent composition were mixed in an amount of epoxy equivalent / active hydrogen equivalent = 1/1 at 5 ° C. and a humidity of 85%. Then, it apply | coated so that it might become a film thickness of 200 micrometers on a mild steel plate on the mild steel plate, and this was cured at room temperature for 1 week. The appearance of the coating surface after curing was visually confirmed and evaluated according to the following evaluation criteria.
A: Glossy and very good, ◯: Good, Δ: Glossy and slightly uneven, X: Glossy and unevenly large.

(B value measurement)
An epoxy resin (Adeka Resin EP-4100G, manufactured by Asahi Denka Kogyo Co., Ltd.) and a curing agent composition are mixed in an amount of epoxy equivalent / active hydrogen equivalent = 1/1 at 25 ° C. and 45% humidity. To obtain a mixture. This mixture was applied on a mild steel plate in a wet state so as to have a film thickness of 200 μm, and this was cured at room temperature for 1 week. After curing, the coating film was accelerated for 50 hours with a sunshine weatherometer (WOM), and then the b value of the coating film was measured.

(Recoatability evaluation)
On the coating film after the deterioration promotion in the b value measurement, the mixture used for the coating film preparation in the b value measurement was applied to a film thickness of 200 μm in a wet state and cured at 40 ° C. for 3 hours. . 100 cross-cuts were put on this coating film, and a peel test was performed with a gum tape, and the number of cross-cuts remaining without peeling was counted.

(Temperature gradient test)
An epoxy resin (Adeka Resin EP-4100G, manufactured by Asahi Denka Kogyo Co., Ltd.) and a curing agent composition were mixed at an amount of epoxy equivalent / active hydrogen equivalent = 1/1 at 25 ° C. and 45% humidity. Then, it was applied on a mild steel plate so as to have a film thickness of 200 μm in a wet state, and the coating film was immersed in a water bath adjusted to 20 ° C./40° C. (coating surface: 40 ° C.). The time (days) until was confirmed.

As is apparent from Table 4, when a modified amine curing agent is used together with the polyepoxy compound (Comparative Example 5), the curability and weather resistance are poor, and together with the polyepoxy compound, the polyamine compound and acrylic acid. When the modified polyamine obtained by reacting with methyl was used alone (Comparative Example 4), it was difficult to be compatible with the epoxy resin, so that it was difficult to apply and it was difficult to form a good coating film. .
Further, as apparent from Table 2, when a cyclic polyamine adduct is used alone (Comparative Example 3), or a modified polyamine obtained by reacting a polyamine compound and methyl acrylate, and an acyclic polyamine adduct, When combined (Comparative Example 1), when a curing agent having a high solid content concentration was prepared, it was difficult to use as a curing agent because of high viscosity.

  On the other hand, as is clear from Tables 2 and 3, when a modified polyamine obtained by reacting a polyamine compound and methyl acrylate and a cyclic polyamine adduct are combined (Examples 1 to 11). It was possible to obtain a curing agent having a high solid content concentration. Moreover, when these hardening | curing agents were combined with a polyepoxy compound clearly from Table 4 and Table 5 (Examples 12-22), hardening at low temperature progressed favorably, appearance, weather resistance, recoat A coating film having excellent properties and a temperature gradient could be formed.

Claims (8)

(A) An epoxy resin curing agent composition comprising as a main component an epoxy adduct of a modified polyamine represented by the following general formula (I) and (b) a cyclic polyamine.

  2. The epoxy according to claim 1, wherein the modified polyamine which is the component (a) is a modified polyamine obtained by reacting (a) a polyamine compound and (b) an ester compound of acrylic acid or methacrylic acid. Hardener composition for resin.   The epoxy resin curing agent composition according to claim 2, wherein the (a) polyamine compound is at least one selected from meta-xylenediamine and 1,3-bis (aminomethyl) cyclohexane.   The epoxy resin curing agent composition according to claim 2 or 3, wherein the ester compound of (b) acrylic acid or methacrylic acid is methyl acrylate.   (C) The cyclic polyamine which provides an epoxy adduct of the cyclic polyamine which is the component (b) is at least one selected from 1,3-diaminocyclohexane, metaxylenediamine, norbornenediamine and isophoronediamine. The hardening | curing agent composition for epoxy resins in any one of Claims 1-4.   Solid content is 70 mass% or more, The hardening | curing agent composition for epoxy resins in any one of Claims 1-5 characterized by the above-mentioned.   A curable epoxy resin composition comprising (A) a polyepoxy compound and (B) the epoxy resin curing agent composition according to any one of claims 1 to 6.   The curable epoxy resin composition according to claim 7, which is used for a paint.