JP2007204532A - Curing agent composition for epoxy resin and curable epoxy resin composition containing the curing agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing agent for an epoxy resin being excellent in reactivity with a polyepoxy compound and not emitting a pungent odor and to provide a curable epoxy resin composition excellent in curability, water resistance, and decorativeness. <P>SOLUTION: An epoxy resin curing agent composition comprising an active-hydrogen-containing amine compound and a curable epoxy resin composition containing the same are provided. The amine compound comprises 30 to 60 mass% (a) adduct-modified amine being an adduct between 1 mol of m-xyllenediamine and not less than 0.8 equivalent of a monoglycidyl ether and/or a monoglycidyl ester compound, 2 to 15 mass% (b) adduct-modified amine being an adduct between 1 mol of m-xyllenediamine and not less than 0.8 equivalent of a diglycidyl ether compound, 20 to 50 mass% (c) polypropylene glycol polyamine of an average molecular weight of 200 to 500, and 2 to 10 mass% (d) polyamine having at least one alicyclic group in the molecule. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a curing agent composition for epoxy resin and a curable epoxy resin composition, and in particular, there is no irritating odor and excellent reactivity with a polyepoxy compound, and for the epoxy resin. The present invention relates to a curable epoxy resin composition using a curing agent and having excellent curability, water resistance of a cured product, and beauty.

  Epoxy resins have excellent adhesion to various substrates, and cured products obtained by curing them with a curing agent are relatively excellent in terms of heat resistance, chemical resistance, electrical properties, mechanical properties, etc. For this reason, it has been used in a wide range of fields, particularly in the field of paints and adhesives.

  Conventionally, amine-based curing agents mainly composed of m-xylenediamine have been used as solvent-free room-temperature curing amine-based curing agents used for epoxy resin-based paints and adhesives. However, since m-xylenediamine is slightly decomposed during storage of the curing agent to generate ammonia gas, an amine-based curing agent containing a large amount of m-xylenediamine in a free state is used during handling operations. There was a drawback of generating odor. In addition, cured coatings obtained using these amine-based curing agents also have the disadvantage that the remaining amine absorbs carbon dioxide gas and whitens (brushing) or leathers under low temperature and high humidity. It was.

Therefore, in order to eliminate these disadvantages, phenol compounds such as phenol and alkylphenol are usually blended as amine blocking agents and curing accelerators.
However, amine-based curing agents containing phenolic compounds as amine blocking agents and curing accelerators not only cause the weather resistance and water resistance of the cured product to decrease, but also contribute to ammonia odor and amine odor that cause sick house. In addition, there were various problems such as generation of odor peculiar to phenol compounds.
Therefore, without using the phenolic compound, it is excellent in low temperature curability and weatherability of the cured product, and does not have various problems such as reduction in water resistance, etc. Development of a curable amine curing agent has been demanded.

In order to solve the problem of whitening without using a phenol compound as an amine blocking agent, a resin curing agent containing xylenediamine or a modified product thereof and an aliphatic amine compound is disclosed, There existed a fault, such as the intensity | strength of a coating film falling (patent document 1).
JP-A-8-104738

Accordingly, a first object of the present invention is to provide a curing agent for epoxy resins that is not only excellent in reactivity with a polyepoxy compound but does not generate an irritating odor such as an ammonia odor or a phenol odor. .
The second object of the present invention is to provide a curable epoxy resin composition excellent in curability, water resistance of a cured coating film, and cosmetics.

  As a result of intensive studies to achieve the above objects, the present inventors have obtained a curing agent composition obtained by combining a specific epoxy adduct-modified amine and a specific amine compound. As a result, the present invention was reached.

  That is, the present invention relates to a curing agent composition for an epoxy resin containing an amine compound having active hydrogen, wherein the amine compound having active hydrogen is mono (m) per mole of m-xylenediamine. 30 to 60% by mass of at least one amine compound selected from adduct-modified amines obtained by adding 0.8 equivalent or more of glycidyl ether and / or monoglycidyl ester compound, and (b) 1 mol of m-xylenediamine. 2 to 15% by mass of at least one amine compound selected from adduct-modified amines obtained by adding 0.8 equivalent or more of a diglycidyl ether compound, and (c) a polypropylene glycol polyamine having an average molecular weight of 200 to 500 20 to 50% by mass of at least one amine compound selected from: and (d) in the molecule A curing agent composition for epoxy resins, comprising 2 to 10% by mass of at least one amine compound selected from polyamines having at least one alicyclic group, and the curing agent composition for epoxy resins It is a curable epoxy resin composition containing a product and a polyepoxy compound.

  Particularly in the present invention, the adduct-modified amine as the component (a) is obtained by adding 0.9 to 1.1 equivalents of monoglycidyl ether and / or monoglycidyl ester compound to 1 mol of m-xylenediamine. In particular, the amine compound is preferably an amine compound obtained by adding 0.8 equivalent or more of monophenyl glycidyl ether to 1 mol of m-xylenediamine. The adduct-modified amine as the component (b) is preferably an amine compound obtained by adding 0.9 to 1.1 equivalents of a diglycidyl ether compound to 1 mol of m-xylenediamine. The adduct-modified amine as the component (b) is preferably an amine compound obtained by adding 0.8 equivalent or more of diglycidyl ether of a bisphenol compound to 1 mol of m-xylenediamine. Furthermore, the alicyclic group-containing polyamine as the component (d) is preferably isophoronediamine or 1,3-bis (aminomethyl) cyclohexane.

  The curing agent composition for epoxy resin according to the present invention does not have an irritating odor, and is a curable epoxy resin composition excellent in curability, water resistance of a cured product, and appearance by combining with a polyepoxy compound. Can be provided.

  Examples of monoglycidyl ether compounds that can provide the adduct-modified amine that is component (a) used in the present invention include alkyl monoglycidyl ethers such as butyl glycidyl ether; phenyl glycidyl ether, cresyl glycidyl ether, and the like. Aryl monoglycidyl ethers such as phenol monoglycidyl ethers, butylphenyl glycidyl ether, naphthyl glycidyl ether, and the like are particularly preferable, but it is particularly preferable to use phenyl glycidyl ether because the increase in viscosity can be suppressed. On the other hand, examples of the monoglycidyl ester compound that can provide the adduct-modified amine as the component (a) used in the present invention include fatty acid monoglycidyl esters.

  The adduct-modified amine as component (a) used in the present invention is obtained by adding 0.8 equivalent or more of monoglycidyl ether and / or monoglycidyl ester compound to 1 mol of m-xylenediamine. In particular, from the viewpoint of obtaining a product having excellent curing reactivity, it is preferable to use a product obtained by adding 0.9 to 1.1 equivalents. If the amount of the monoglycidyl ether compound and / or monoglycidyl ester compound used is less than 0.8 equivalent, the residual amount of free m-xylenediamine increases, and an irritating odor tends to occur over time, which is not preferable. .

  Examples of the diglycidyl ether that can provide the adduct-modified amine as the component (b) used in the present invention include diglycidyl mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Ether compounds; 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, sulfobisphenol, oxybisphenol, terpene bisphenol and other diglycidyl ether compounds; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, bisphenol A- And diglycidyl ethers of glycols such as ethylene oxide adducts. In particular, in order to obtain a curable epoxy resin composition excellent in coating film strength, weather resistance, etc., it is preferable to use a diglycidyl ether of a bisphenol compound, particularly a diglycidyl ether of bisphenol A.

  The adduct-modified amine as component (b) used in the present invention is obtained by adding 0.8 equivalent or more of a diglycidyl ether compound to 1 mol of m-xylenediamine. In order to obtain a product having a small amount of curing reactivity, it is preferable to use a product obtained by adding 0.9 to 1.1 equivalents. When the amount of the monoglycidyl ether compound used is less than 0.8 equivalent, the residual amount of free m-xylenediamine increases, and an irritating odor tends to occur over time, which is not preferable.

  The component (a) and the component (b) may be separately produced in advance, but the production of the component (b) may be continued after the production of the component (a), or the production may be performed in one step. It is sufficient to follow normal production conditions, such as using an organic solvent such as, and there is no particular limitation.

  The polypropylene glycol polyamine having an average molecular weight of 200 to 500, which is the component (c) used in the present invention, is a compound represented by the following general formula (I). When the average molecular weight is less than 200, the gloss of the cured product may be deteriorated or the mechanical strength may be lowered. If the average molecular weight exceeds 500, curing reactivity and water resistance may be lowered, which is not preferable.

In formula (I), X represents a residue obtained by removing m hydroxyl groups from a divalent to hexavalent polyol, and A represents an alkylene group having 2 to 6 carbon atoms. B represents a 1,2-propylene group, m represents an integer of 2 to 6, and n represents an integer of 0 to 10. A plurality of A, B and n present in the same molecule may be the same or different.

  In the above formula (I), examples of the residue of the divalent to hexavalent polyol represented by X include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, benzenedimethanol, cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, sorbitol, mannitol, Examples thereof include residues obtained by removing m hydroxyl groups from a polyol such as dipentaerythritol.

Typical examples of the polypropylene glycol polyamine compound represented by the above formula (I) include the following compounds.
In the above formula, n1 represents an integer of 2 to 7, n2 and n3 represent an integer of 1 to 5, and n4, n5 and n6 represent an integer of 0 to 5.

  Examples of commercially available polypropylene glycol polyamines having an average molecular weight of 200 to 500, which are components (c) used in the present invention, include, for example, Heinz's Jeffamine D series (D-230, D-400), Jeffamine T series ( T-403) (Jefamine is a registered trademark).

  Examples of the alicyclic group-containing polyamine compound (d) used in the present invention include 1,3-bis (aminomethyl) cyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1, Examples include 4-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, norbornenediamine, and the like. From the viewpoint of obtaining a curable epoxy resin composition excellent in curability and aesthetic appearance, in the present invention, among the alicyclic polyamine compounds, in particular, 1,3-bis (aminomethyl) cyclohexane, and / or It is preferable to use isophoronediamine.

  In the curing agent component of the present invention, the curing agent component contains 30 to 60% by mass of component (a), preferably 40 to 50% by mass, and 2 to 15% by mass of component (b). Preferably 5 to 10% by mass, (c) component 20 to 50% by mass, preferably 30 to 45% by mass, (d) component 2 to 10% by mass, preferably 3 to 8% by mass It is. If the component (a) is less than 30% by mass, the low-temperature curability may be inferior, the hardness may decrease, or the water resistance may decrease. On the other hand, if it is used in an amount of more than 60% by mass, the irritating odor may become strong, or the whitening phenomenon may occur and the appearance may be deteriorated. On the other hand, when the component (b) is less than 2% by mass, there is a risk that the hardness may be lowered or the water resistance may be lowered. This is not preferable because the property may be deteriorated. Further, when the component (c) is less than 20% by mass, there is a risk that the viscosity increases and the workability is deteriorated or the smoothness of the surface of the cured product is deteriorated. If it is used more, it is not preferable because there is a possibility that the hardness is lowered or the water resistance is lowered. Furthermore, if the component (d) is less than 2% by mass, the gloss of the cured product may be lowered, or the mechanical strength may be reduced. This is not preferable because there is a possibility that the appearance of the leather may be deteriorated, such as a leather tension phenomenon or stickiness. In addition, when using other aliphatic polyamines such as metaxylylenediamine and polyalkylenepolyamine, aromatic polyamines such as diaminodiphenylmethane, and modified products thereof, it is only possible to deteriorate the appearance of whitening. In addition, the water resistance, hardness, weather resistance and the like may be remarkably impaired.

  The curing agent composition for epoxy resin of the present invention is preferably used as a solvent-free curing agent without using an organic solvent from the viewpoint of environmental and safety and health considerations. It can also be used as a curing agent. Examples of the organic solvent that can be used in this case include ethers such as tetrahydrofuran, 1,2-dimethoxyethane, and 1,2-diethoxyethane; iso- or n-butanol, iso- or n-propanol, Examples include alcohols such as amyl alcohol; aromatic hydrocarbons such as benzene, toluene, and xylene. Moreover, it can also be diluted with water by using a surfactant or the like to make a water dispersion type, an emulsion type or the like. In particular, it is preferable to use a water system instead of using a solvent from the viewpoint of environment and safety and health.

  The curable epoxy resin composition of the present invention is a resin composition comprising (B) the above-described curing agent composition for epoxy resin of the present invention together with (A) a polyepoxy compound.

  Examples of the polyepoxy compound (A) in the curable epoxy resin composition of the present invention include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; Naphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxy) Cumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) Nyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, polyglycidyl ether compounds of polyphenols such as terpene phenol; ethylene Polyglycidyl ethers of polyhydric alcohols such as glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumarate Acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipine , Azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, end methylenetetrahydrophthalic acid, etc. Homopolymers or copolymers of glycidyl esters of aromatic, aromatic or alicyclic polybasic acids 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-3,4-epoxycyclohexanecarboxylate, 3,4- Epoxidized products of cyclic olefin compounds such as epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized styrene-butadiene copolymer And epoxidized conjugated diene polymers, and heterocyclic compounds such as triglycidyl isocyanurate.

  These epoxy resins may be those internally cross-linked by a prepolymer of a terminal isocyanate, or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, polyphosphate ester, etc.). Furthermore, these epoxy resins can also be used as emulsions emulsified with a surfactant, especially when using high molecular weight epoxy resins compared to liquefaction using a solvent. Excellent in terms of environment and health and safety.

  In this invention, it is preferable to use 0.1-200 mass parts of said hardening | curing agent composition of this invention which is (B) component with respect to 100 mass parts of polyepoxy compounds of (A) component, It is preferable to use in the range of 100 parts by mass. If the amount is less than 0.1 parts by mass, the curability may not be obtained. If the amount exceeds 200 parts by mass, the physical properties of the cured product may be reduced.

  In addition, when using the curable epoxy resin composition of the present invention as a paint or an adhesive, it is preferable to use it as a solventless type that does not use an organic solvent from the viewpoint of environmental and safety and hygiene. In order to improve the property, a solvent can be blended. Examples of the solvent used in this case include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate and cyclohexanone; tetrahydrofuran, 1,2-dimethoxyethane, 1,2 Ethers such as diethoxyethane; esters such as ethyl acetate and n-butyl acetate; ether esters such as propylene glycol monomethyl ether acetate; iso- or n-butanol, iso- or n-propanol, amyl alcohol, etc. Alcohols; aromatic hydrocarbons such as benzene, toluene and xylene; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil ( ), Parasorb solvents such as Solvesso # 100 (trade name of Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; Halogenated aroma such as chlorobenzene Group hydrocarbons; aniline, triethylamine, pyridine, dioxane, acetic acid, acetonitrile, carbon disulfide and the like.

  In the curable epoxy resin composition of the present invention, a reactive or non-reactive diluent can also be used. Examples of reactive diluents include phenol, cresol, ethylphenol, propylphenol, p-tert-butylphenol, p-tert-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol or terpene monophenol. Examples thereof include monoglycidyl ether compounds, and examples of the non-reactive diluent include toluene resin, xylene resin, benzyl alcohol and the like.

  A known curing accelerator can be used in combination with the curable epoxy resin composition of the present invention. Examples of such a curing accelerator include trimethylamine, ethyldimethylamine, propyldimethylamine, N, N′-dimethylpiperazine, pyridine, picoline, 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU). ), Benzyldimethylamine, 2- (dimethylaminomethyl) phenol (DMP-10), tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30); p-toluenesulfonic acid 1-aminopyrrolidine salt of thiocyanic acid, salicylic acid, benzoic acid and the like.

  In the curable epoxy resin composition of the present invention, if necessary, glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide Fillers or pigments such as carbon black, graphite, iron oxide and bitumen substances; thickeners; thixotropic agents; flame retardants; antifoaming agents; rust preventives; colloidal silica, colloidal alumina and other conventional additives In addition, adhesive resins such as xylene resin and petroleum resin may be used in combination.

  The curable epoxy resin composition of the present invention includes, for example, paints or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; 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 copy paper, impregnated paper and other processed paper; natural fiber, synthetic It can be used for a wide range of applications such as fiber treatment agents such as fiber, glass fiber, carbon fiber, metal fiber, etc., fiber treatment agent such as fraying preventive agent, processing agent; sealing material, cement admixture, waterproofing material, etc. Although it can be used, it is particularly suitably used as a paint or adhesive for various substrates.

  Hereinafter, although a manufacture example and an Example are shown and it demonstrates still in detail about the hardening | curing agent composition for epoxy resins and curable epoxy resin composition of this invention, this invention is not limited by these. In the following, “%” means “% by mass” unless otherwise specified.

Production Example 1
After charging 136 g (1 mol) of m-xylenediamine and 293 g of isopropanol (IPA) and adjusting the internal temperature of the reaction system to 60 to 70 ° C., Epiol P (phenylglycidyl ether (PGE) manufactured by NOF Corporation) Product name) 157 g (1.0 equivalent) was added dropwise over 1 hour while cooling as necessary so that the internal temperature was in the range of 60 to 80 ° C. After completion of the dropwise addition, the mixture was further reacted at 70 to 80 ° C. for 5 hours to obtain an IPA solution (MXDA / PGE-1) having an active hydrogen equivalent in the resin content of 97.7 and a 50% adduct modification product.

Comparative production example 1
After charging 136 g (1 mol) of m-xylenediamine and 246 g of isopropanol (IPA) and adjusting the internal temperature of the reaction system to 60 to 70 ° C., Epiol P (phenylglycidyl ether (PGE) manufactured by NOF Corporation) No. 1) 110 g (0.7 equivalent) was added dropwise over 1 hour while cooling as necessary so that the internal temperature was in the range of 60 to 80 ° C. After completion of the dropwise addition, the mixture was further reacted at 70 to 80 ° C. for 5 hours to obtain an IPA solution (MXDA / PGE-2) of 50% adduct-modified product having an active hydrogen equivalent in the resin content of 74.5.

Production Example 2
After charging 136 g (1 mol) of m-xylenediamine and 266 g of isopropanol (IPA) and adjusting the internal temperature of the reaction system to 60 to 70 ° C., Epiol B (N-butyl glycidyl ether (BGE manufactured by NOF Corporation) was used. ) 130 g (1.0 equivalent) was added dropwise over 1 hour while cooling as necessary so that the internal temperature was in the range of 60 to 80 ° C. After completion of the dropwise addition, the mixture was further reacted at 70 to 80 ° C. for 5 hours to obtain an IPA solution (MXDA / BGE) of 50% adduct-modified product having an active hydrogen equivalent in the resin content of 88.7.

Production Example 3
After charging 136 g (1 mol) of m-xylenediamine and 326 g of isopropanol (IPA) and adjusting the internal temperature of the reaction system to 60 to 70 ° C., Adeka Resin EP-4100E (Bisphenol A diglycidyl manufactured by Asahi Denka Kogyo Co., Ltd.) 190 g (1.0 equivalent) of the ether trade name) was added dropwise over 1 hour while cooling as necessary so that the internal temperature was in the range of 60 to 80 ° C. After completion of the dropwise addition, the mixture was further reacted at 70 to 80 ° C. for 5 hours to obtain an IPA solution (MXDA / 4100E-1) of 50% adduct-modified product having an active hydrogen equivalent in the resin content of 108.7.

Comparative production example 2
After charging 136 g (1 mol) of m-xylenediamine and 269 g of isopropanol (IPA) and adjusting the internal temperature of the reaction system to 60 to 70 ° C., Adeka Resin EP-4100E (Bisphenol A diglycidyl manufactured by Asahi Denka Kogyo Co., Ltd.) Ether trade name) 133 g (0.7 equivalents) was added dropwise over 1 hour while cooling as necessary so that the internal temperature was in the range of 60 to 80 ° C. After completion of the dropwise addition, the mixture was further reacted at 70 to 80 ° C. for 5 hours to obtain an IPA solution (MXDA / 4100E-2) of 50% adduct-modified product having an active hydrogen equivalent in the resin content of 81.5.

Production Example 4
After charging 136 g (1 mol) of m-xylenediamine and adjusting the internal temperature of the reaction system to 60 to 70 ° C., Epiol P (trade name of phenylglycidyl ether (PGE) manufactured by NOF Corporation) 141 g (0 .9 equivalents) was added dropwise over 1 hour while cooling as necessary so that the internal temperature was in the range of 60 to 80 ° C. After completion of dropping, the reaction was further continued at 70 to 90 ° C. for 1 hour. Next, 19 g (0.1 equivalent) of Adeka Resin EP-4100E (trade name of bisphenol A diglycidyl ether manufactured by Asahi Denka Kogyo Co., Ltd.) is required so that the internal temperature falls within the range of 70 to 80 ° C. The solution was added while cooling. After completion of the addition, the mixture was further reacted at 70 to 80 ° C. for 5 hours to obtain an adduct modified product (MXDA / PG / 4100E) having an active hydrogen equivalent of 98.7.

  Curing agent compositions were prepared according to the formulations shown in Tables 1 to 4 below. In the preparation, the m-xylenediamine adduct was first mixed, then the solvent was removed at 80 to 100 ° C. and 2 to 4 MPa, and then other components were added and blended at 80 ° C. The viscosity and odor of the obtained curing agent composition were evaluated as follows.

(viscosity)
According to JIS K7233, it measured at 25 degreeC using BM type | mold rotary viscometer. The viscosity of the curing agent composition was evaluated as follows from the viewpoint of maintaining workability in a solvent-free unit with mPa · S.
A: Viscosity that is practically usable when the viscosity is 600 mPa · S / 25 ° C. or lower.
Δ: Viscosity is 600 to 1000 mPa · S / 25 ° C., and the working application temperature is limited, which is not practically preferable.
X: Since the viscosity is 1000 mPa · S / 25 ° C. or higher and the workability is poor, it is necessary to dilute with a solvent at room temperature or lower.

(Odor)
Since the odor is proportional to the ammonia gas concentration in the curing agent composition which is the main cause, the ammonia gas concentration in the sealed container was measured and evaluated. In the evaluation method, 150 g of the curing agent composition was measured in a 300 ml Erlenmeyer flask, sealed, and then allowed to stand at 23 ° C. for 72 hours. About the presence of an irritating odor, the ammonia concentration in the head space in the Erlenmeyer flask was measured using a detector tube type gas meter (GV-100S ammonia gas detector tube No. 3HM (trade name)) manufactured by Gastec Corporation. The determination was made according to the following criteria.
○: The detected amount of ammonia gas is 0 to 0.3%, and almost no irritating odor is felt.
Δ: A slight irritation is sensed when the detected amount of ammonia gas is 0.3 to 0.7%, and pain is felt in the nose after long-term suction.
X: When the detected amount of ammonia gas is 0.7% or more, the irritating odor is felt strongly and the nose is painful.

  Curable epoxy obtained by blending 200 parts by mass of the main agent obtained by kneading the mixture having the composition shown below using three rolls and 40 parts by mass of the curing agent composition prepared in Example 1. Using the resin composition, the odor, the curing reactivity, the water resistance of the cured film and the beautiful appearance were evaluated.

(Main ingredient formulation) Mass parts Adeka Resin EP-4100E 90
ADEKA GLYCIROL ED-529E 10
(Trade name of cresyl glycidyl ether manufactured by Asahi Denka Kogyo Co., Ltd., epoxy equivalent 180)
Benzyl alcohol 15
Calcium carbonate 55
Talc 9
BYK-065 0.5
(Brand name of modified siloxane defoamer manufactured by Big Chemie Japan)
BYK-354 0.5
(Brand name of acrylic leveling agent manufactured by Big Chemie Japan)
Chromium oxide (green pigment) 20

(Odor)
150 g of the curable resin composition was weighed into a 300 ml Erlenmeyer flask and measured and determined in the same manner as in Example 1.

(Curing reactivity)
A cured product obtained by pouring into a mold having a thickness of 7 mm and a diameter of 40 mm and curing at 10 ° C. for 24 hours was allowed to stand at 23 ° C. for 1 hour, and then the Shore-D hardness of the cured product was 23 ° C. Measured below and judged by the following indicators.
○: Shore-D hardness is 50 or more, and there is no practical problem. Δ: Shore-D hardness is 50 to 40, and there is a problem in practical use, and curing curing time needs to be extended. X: Shore-D hardness is 40 or less. It is practically unusable without post-heating.

(water resistant)
After casting into a metal mold having a thickness of 7 mm and a diameter of 40 mm and curing at 23 ° C. for 7 days, the product was immersed in tap water at 25 ° C. for 7 days, and the mass change rate before and after immersion was determined.
○: Mass change rate is within ± 1%, excellent in coating film durability and corrosion resistance, and practically no problem.
Δ: Mass change rate is ± 1 to 1.5%, inferior in long-term corrosion resistance and coating film durability, and somewhat problematic in practical use.
X: Mass change rate is ± 1.5% or more and cannot be used. It is easy to cause swelling and peeling phenomenon and is inferior in corrosion resistance.

(Beautiful)
Coating film when applied to a 10 × 7 cm, 3 mm thick glass plate to a film thickness of 500 μm and cured for 72 hours in a constant temperature and high humidity tank set at 10 ° C. and humidity 80-90% The surface was observed.
○: The coating film surface is glossy and satisfactory for practical use. Δ: The coating film surface is cloudy and unsatisfactory for practical use. Moreover, stickiness may remain on the surface of the cured product.
X: The coating film surface is whitened and cannot be used. Furthermore, stickiness remains on the surface of the cured product and the stain resistance is poor.

The result of each Example and a comparative example is shown to Tables 1-4.
However, a unit is a mass part and the inside of () shows solid content.
D-230: Polypropylene glycol diamine manufactured by Huntsman, average molecular weight 230, active hydrogen equivalent 60 g / eq, trade name: Jeffamine IPDA: isophorone diamine, molecular weight 170, active hydrogen equivalent 42.5 g / eq
Ancamine K-54: Tertiary amine curing catalyst, trade name of 2,4,6-tris (dimethylaminomethyl) phenol manufactured by Air Products Japan Co., Ltd.

XTJ-511: polyethylene glycol diamine manufactured by Huntsman, average molecular weight 220, active hydrogen equivalent 60 g / eq, trade name: Jeffamine D-2000: polypropylene glycol diamine manufactured by Huntsman, average molecular weight 2000, active hydrogen equivalent 500 g / eq , Product name: Jeffermin

1,3-BAC: 1,3-bis (aminomethyl) cyclohexane, molecular weight 142, active hydrogen equivalent 35.5 g / eq
TETA: triethylenetetramine, molecular weight 146, active hydrogen equivalent 24.3 g / eq
DDM: Diaminodiphenylmethane, molecular weight 198, active hydrogen equivalent 49.5 g / eq

  As is apparent from the results of Tables 1 to 4, the curing agent composition for epoxy resin of the present invention comprising two specific adduct-modified amines, a low molecular weight polypropylene glycol polyamine and an alicyclic amine in a specific ratio. It was demonstrated that the curable epoxy resin composition of the present invention obtained by combining a product and a polyepoxy compound can provide a coating film excellent in curability, water resistance, and cosmetic appearance.

The curing agent for epoxy resin of the present invention is not only excellent in reactivity with the polyepoxy compound, but also does not generate irritating odors such as ammonia odor and phenol odor, and the curable epoxy resin composition of the present invention is It is excellent in curability, water resistance of the cured coating film, and cosmetics, and can be used in a wide range of fields, particularly in the fields of paints and adhesives.

Claims (7)

  An epoxy resin curing agent composition comprising an amine compound having active hydrogen, wherein the amine compound having active hydrogen is monoglycidyl ether and / or 1 mol per 1 mol of m-xylenediamine. 30 to 60% by mass of at least one amine compound selected from adduct-modified amines obtained by adding 0.8 equivalent or more of a monoglycidyl ester compound, and (b) diglycidyl ether per 1 mol of m-xylenediamine. 2 to 15% by mass of at least one amine compound selected from adduct-modified amines obtained by adding 0.8 equivalent or more of the compound, and (c) at least one selected from polypropylene glycol polyamines having an average molecular weight of 200 to 500 20 to 50% by mass of the amine compound, and (d) at least one in the molecule At least one amine compound curing agent for epoxy resin composition characterized by comprising a 2-10 wt% selected from the polyamines having more alicyclic groups.   The adduct-modified amine of the component (a) is an amine compound obtained by adding 0.9 to 1.1 equivalents of monoglycidyl ether and / or monoglycidyl ester compound to 1 mol of m-xylenediamine. The hardening | curing agent composition for epoxy resins described in Claim 1.   The adduct-modified amine as the component (a) is an amine compound obtained by adding 0.8 equivalent or more of monophenyl glycidyl ether to 1 mol of m-xylenediamine. Curing agent composition for epoxy resin.   The adduct-modified amine as the component (b) is an amine compound obtained by adding 0.9 to 1.1 equivalents of a diglycidyl ether compound to 1 mol of m-xylenediamine. The hardening | curing agent composition for epoxy resins described in any one.   The adduct-modified amine as the component (b) is an amine compound obtained by adding 0.8 equivalent or more of diglycidyl ether of a bisphenol compound to 1 mol of m-xylenediamine. Curing agent composition for epoxy resin described in the above.   The hardening | curing agent composition for epoxy resins in any one of Claims 1-5 whose alicyclic group containing polyamine of the said (d) component is isophorone diamine or 1, 3-bis (aminomethyl) cyclohexane. A curable epoxy resin composition comprising (A) a polyepoxy compound and (B) a curing agent composition for an epoxy resin according to any one of claims 1 to 6.