WO2022054897A1 - Curing agent composition for epoxy resins, epoxy resin composition, and coating material - Google Patents

Curing agent composition for epoxy resins, epoxy resin composition, and coating material Download PDF

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Publication number
WO2022054897A1
WO2022054897A1 PCT/JP2021/033260 JP2021033260W WO2022054897A1 WO 2022054897 A1 WO2022054897 A1 WO 2022054897A1 JP 2021033260 W JP2021033260 W JP 2021033260W WO 2022054897 A1 WO2022054897 A1 WO 2022054897A1
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WIPO (PCT)
Prior art keywords
epoxy resin
curing agent
agent composition
component
water
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PCT/JP2021/033260
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French (fr)
Japanese (ja)
Inventor
大輔 佐藤
洋一 綾
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株式会社Adeka
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Priority to JP2022548348A priority Critical patent/JPWO2022054897A1/ja
Priority to CN202180062663.4A priority patent/CN116601236A/en
Publication of WO2022054897A1 publication Critical patent/WO2022054897A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/60—Amines together with other curing agents with amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to a curing agent composition for an epoxy resin, an epoxy resin composition, and a coating material. More specifically, the present invention relates to an epoxy resin curing agent composition containing two or more kinds of amine compounds having a specific skeleton, an epoxy resin composition containing the epoxy resin curing agent composition, and a coating material containing the epoxy resin composition. ..
  • Epoxy resin exhibits excellent properties when used as an adhesive, paint, electrical insulation material, and civil engineering and building material. Among them, because of its excellent water resistance, chemical resistance, and corrosion resistance, it is often used for paints for automobiles, railroad vehicles, buildings, ships, electric machines, coatings on the inside of drinking water cans, and the like.
  • Epoxy resins and curing agents used in paints have often used solvents in order to reduce the viscosity from the viewpoint of workability.
  • volatile solvents such as toluene and xylene
  • Patent Document 1 discloses a modified amine obtained by reacting a polyamine with methyl acrylate. This modified amine has an amide bond and has good compatibility with water, but when the epoxy resin is cured with this modified amine alone, there is a problem in the water resistance of the cured product.
  • the cured agent composition becomes turbid due to the combined amine compound, or the amine compound crystallizes.
  • the compatibility between the amine compounds used in the curing agent composition is insufficient, and there are problems in the storage stability of the curing agent composition and the workability when used as the curing agent composition.
  • Patent Document 2 discloses a curing agent for an aqueous epoxy resin containing a reaction composition containing a reaction product of styrene and an amine compound. This curing agent had good compatibility with the water-based epoxy resin, but there was a problem in the water resistance and corrosion resistance of the epoxy cured product obtained by using this curing agent.
  • the problem to be solved by the present invention is that the curing agent composition maintains transparency, has good workability, and has good compatibility with an aqueous epoxy resin, and can be obtained by reacting with an epoxy resin. It is an object of the present invention to provide a curing agent composition for an epoxy resin having excellent water resistance and corrosion resistance.
  • the present inventors have diligently studied, and a curing agent composition containing a specific amine compound (A) component and (B) component in a specific mass ratio range has become the (A) component and the (B) component. It has transparency due to good compatibility between the amine compounds used, and also has good compatibility with water-based epoxy resins. It is obtained by curing an epoxy resin composition containing this curing agent composition and an epoxy resin. We have found that the cured product is excellent in water resistance and corrosion resistance, and have reached the present invention. That is, the present invention is selected from the group consisting of the component (A), which is a compound represented by the following general formula (1), and the compounds represented by the following general formulas (2) and (3).
  • a curing agent composition for an epoxy resin which comprises at least one component (B) and has a mass ratio of the component (A) to the component (B) of 7: 3 to 9: 1.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • X 1 to X 3 each independently represent a residue obtained by removing two amino groups from a polyamine compound
  • n represents a residue. Represents an integer from 0 to 10.
  • X 4 represents a residue obtained by removing two amino groups from the polyamine compound.
  • x represents an integer of 1 to 6
  • y represents an integer of 1 to 40
  • z represents an integer of 1 to 6.
  • the curing agent composition of the present invention has good workability and compatibility with a water-based epoxy resin while maintaining transparency, and is excellent in water resistance and corrosion resistance of a cured product obtained by curing an epoxy resin. Therefore, it is useful as a curing agent composition for epoxy resins with reduced burden on the environment. Further, the epoxy resin composition obtained from the curing agent composition of the present invention and the epoxy resin is particularly useful as a paint used for vehicles such as automobiles and railways, buildings, ships, and electric machines.
  • the curing agent composition of the present invention that can be used as a curing agent composition for an epoxy resin contains the component (A) and the component (B) described below.
  • the component (A) is a compound represented by the following general formula (1).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • X 1 to X 3 each independently represent a residue obtained by removing two amino groups from a polyamine compound
  • n represents a residue. Represents an integer from 0 to 10.
  • R 1 and R 2 in the general formula (1) a hydrogen atom is preferable from the viewpoint of easy production of this compound.
  • the residues represented by X 1 to X 3 in the general formula (1) obtained by removing two amino groups from the polyamine compound are particularly limited as long as the polyamine compound is a compound having two or more amino groups.
  • aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine; aromatic ring-containing fats such as m-xylylene diamine and p-xylylene diamine.
  • Aromatic polyamines such as biphenylenediamine, mensendiamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) ) -2,4,8,10-Tetraoxaspiro [5.5] Alicyclic polyamines such as undecane; m-phenylenediamine, p-phenylenediamine, tolylen-2,4-diamine, tolylen-2,6- Mononuclear polyamines such as diamine, mesityylene-2,4-diamine, mesitylen-2,6-diamine, 3,5-diethyltolylen-2,4-diamine, 3,5-diethyltrilen-2,6-diamine Aromatic polyamines such as bipheny
  • the carbon number of the polyamine compound is not particularly limited, but it is preferably a compound having 2 to 30 carbon atoms, more preferably a compound having 2 to 20 carbon atoms, and a compound having 4 to 12 carbon atoms. It is more preferable to have.
  • aliphatic polyamines aromatic ring-containing aliphatic polyamines, and alicyclic polyamines are preferable from the viewpoint of water resistance and corrosion resistance of the cured product obtained by using the curing agent composition of the present invention.
  • -Xylylene diamine and isophorone diamine are more preferable, and m-xylylene diamine is particularly preferable.
  • a single compound may be used, or two or more kinds may be reacted in combination.
  • X 1 to X 3 may all be the same, any one of X 1 to X 3 may be different, or all may be different, but the water resistance and corrosion resistance of the obtained cured product and the general formula (1). ), It is preferable that they are all the same from the viewpoint of facilitating the production of the compounds represented by).
  • a compound in which n is an integer of 0 to 10 represented by the general formula (1) is usually a mixture containing compounds having different numerical values of n.
  • the average value of n in the mixture is preferably 0 to 5, more preferably 0 to 3, and 0 to 1 from the viewpoints that the viscosity of the curing agent composition is lowered and the workability is improved and the curability is improved. More preferably, 1 is particularly preferable.
  • a plurality of X 2 and R 2 existing may be the same or different from each other, but from the viewpoint of facilitating the production of this compound, X 2 and R 2 are It is preferable that they are the same.
  • the compound represented by the general formula (1) can be produced by a known method, and for example, (meth) acrylic acid, (meth) acrylic acid ester, or (meth) acrylic acid may be produced with respect to the polyamine compound. ) It can be obtained by reacting with a halide of acrylic acid (hereinafter referred to as (meth) acrylic acid-based compound).
  • (meth) acrylic acid means methacrylic acid or acrylic acid.
  • the average value of n can be determined by adjusting the molar ratio of each compound when the polyamine compound and the (meth) acrylic acid compound are reacted.
  • the molar ratio is preferably 0.1 to 0.9 mol, more preferably 0.2 to 0.8 mol, still more preferably 0.5 to 0.75 mol, relative to 1 mol of the polyamine compound.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate.
  • Examples thereof include tridecyl acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and isobonyl (meth) acrylate.
  • halogen in the above-mentioned (meth) acrylic acid halide examples include fluorine, chlorine, bromine, and iodine.
  • the above (meth) acrylic acid-based compound may be used alone or in combination of two or more. From the viewpoint of low cost and easy production, it is preferable to use one (meth) acrylic acid compound alone, more preferably (meth) acrylic acid ester, and particularly preferably methyl acrylate.
  • component (B) is at least one compound selected from the group consisting of the compounds represented by the following general formulas (2) and (3).
  • X 4 represents a residue obtained by removing two amino groups from the polyamine compound.
  • x represents an integer of 1 to 6
  • y represents an integer of 1 to 40
  • z represents an integer of 1 to 6.
  • the polyamine compound at the residue of the polyamine compound represented by X4 in the general formula ( 2 ) excluding two amino groups is a compound having two or more amino groups.
  • the polyamine compounds exemplified in the above description of X 1 to X 3 are not particularly limited, and examples thereof include polyamine compounds. From the viewpoint of water resistance and corrosion resistance of the cured product obtained by using the curing agent composition of the present invention, aliphatic polyamines, aromatic ring-containing aliphatic polyamines, and alicyclic polyamines are preferable, and m-xylylene diamine and isophorone diamine are preferable. More preferably, m-xylylene diamine is particularly preferable.
  • the compound represented by the general formula (2) can be obtained by reacting styrene with the above polyamine compound using a basic catalyst, if necessary.
  • the molar ratio of styrene to the polyamine compound in the reaction is preferably 0.5 to 1.5, more preferably 0.8 to 1.2.
  • the compounds in which x in the general formula (3) represents a number from 1 to 6, y represents a number from 1 to 40, and z represents a number from 1 to 6 are usually x, y,. It is a mixture of compounds having different numerical values of z.
  • the average values of x and z are preferably 1 to 4 independently from the viewpoint of the balance between the physical properties of the cured product obtained by using the curing agent composition and the water solubility.
  • the average value of the total value of x + z is preferably 3 to 5.
  • the average value of y is preferably 5 to 15 from the viewpoint of the balance between the physical properties of the cured product obtained by using the curing agent composition and the water solubility.
  • the component (B) is represented by the general formula (2) in that a curing agent composition having better compatibility with the component (A) and excellent in transparency in appearance and storage condition can be obtained. Compounds are preferred.
  • component (B) a commercially available product may be used, and examples thereof include Gascamin 240 manufactured by Mitsubishi Gas Chemical Company, Inc., Jeffamine ED-600 manufactured by Huntsman, and the like.
  • the curing agent composition of the present invention is characterized in that the mass ratio of the component (A) to the component (B) is 7: 3 to 9: 1. From the viewpoint of further improving the performance of the cured product obtained by using it as a curing agent composition, the mass ratio is more preferably 7.5: 2.5 to 8.5: 1.5. When the mass ratio of the component (A) to the component (B) is outside the range of 7: 3 to 9: 1, when the component (A) and the component (B) are mixed, they do not dissolve in each other and become turbid. It is not preferable because the performance such as water resistance and corrosion resistance of the cured product is significantly deteriorated.
  • the curing agent composition of the present invention may contain an amine-based curing agent other than the component (A) and the component (B).
  • examples of such an amine-based curing agent include polyamine compounds exemplified in the above explanations of X 1 to X 3 .
  • the amine-based curing agent also corresponds to the unreacted polyamine compound at the time of production of the component (A) and the component (B).
  • the curing agent composition of the present invention contains an amine-based curing agent other than the component (A) and the component (B), the content of the amine-based curing agent other than the component (A) and the component (B) is the curing.
  • 1 to 20 parts by mass is preferable with respect to 100 parts by mass of the total mass of the component (A) and the component (B), and 1 to 10 parts are preferable. Parts by mass are more preferred.
  • the curing agent composition of the present invention may contain a curing accelerator from the viewpoint of improving curability.
  • the curing accelerator include trimethylamine, ethyldimethylamine, propyldimethylamine, N, N'-dimethylpiperazine, pyridine, picolin, 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), and benzyl.
  • Tertiary amines such as dimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol; butylphenol, phenol novolac, o-cresol novolak, p-cresolnovolac, t-butylphenol Pphenols such as novolak and dicyclopentadiencresol; p-toluenesulfonic acid, 1-aminopyrrolidine salt of thiocyanic acid (manufactured by Otsuka Chemical Co., Ltd .; NR-S), salicylic acid, thiourea and the like can be mentioned.
  • the content of the curing accelerator when the curing agent composition of the present invention contains the above-mentioned curing accelerator is the component (A) from the viewpoint of the balance between the curability of the curing agent composition and the transparent appearance.
  • the component (B) With respect to 100 parts by mass of the total mass of the components (B), 1 to 20 parts by mass is preferable, and 1 to 10 parts by mass is more preferable.
  • the curing agent composition of the present invention may be diluted with a solvent. It is preferable not to use the above solvent in consideration of the environment as much as possible, but when it is used, it is preferable to use a solvent having low volatility in order to reduce the viscosity of the curing agent composition and improve workability. ..
  • a solvent include an alcohol solvent such as methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, an ester solvent such as propylene glycol monomethyl ether acetate, and a nitrogen atom such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
  • examples thereof include a solvent and a solvent containing a sulfur atom such as dimethyl sulfoxide.
  • the content is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, based on the total mass of the curing agent composition. preferable.
  • the total content of the component (A) and the component (B) is the total mass of the curing agent composition from the viewpoint of transparency, workability and curability of the curing agent composition. It is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 75 to 100% by mass.
  • the components (A) and (B), and other optionally used amine-based curing agents, curing accelerators, solvents, etc. are mixed together, and the like. There are no particular restrictions on the manufacturing method.
  • the epoxy resin composition of the present invention contains the above-mentioned curing agent composition and an epoxy resin.
  • the epoxy resin include polyglycidyl ether compounds of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, and fluoroglucosinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), and the like.
  • Echilidene bisphenol isopropylidene bisphenol (bisphenol A), isopropyridenebis (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, Polyglycidyl ether compounds of polynuclear polyvalent phenolic compounds such as ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinnovolak, terpenphenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, dicycl
  • Polyglycidyl ethers of polyhydric alcohols such as dimethanol, 2,2-bis (4-hydroxycyclohexylpropane (bisphenol A hydride), glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-alkylene oxide adduct; Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyro Monopolymers or copolymers of aliphatic, aromatic or alicyclic polybasic acids such as merit acids, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid and glycidyl methacrylates; N, N -
  • epoxy resins listed above polyglycidyl ether compounds of polynuclear polyhydric phenol compounds and polyglycidyl ethers of polyhydric alcohols are preferable, and bisphenol type, from the viewpoint of improving the water resistance and corrosion resistance of the obtained cured product.
  • Epoxy resins are more preferred. One type of these epoxy resins may be used, or two or more types may be used in combination.
  • the above epoxy resin may be used as it is, or may be dispersed in water or emulsified (hereinafter, the epoxy resin dispersed or emulsified in water is referred to as a water-based epoxy resin).
  • the method of dispersing and emulsifying in water include a method of putting an epoxy resin in water, adding a surfactant, and dispersing or emulsifying by a known method using a disper, a homomixer or the like.
  • surfactant examples include general anionic and nonionic surfactants, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts and pyridinium salts.
  • Cationic surfactants such as, betaine type, sulfate ester type, sulfonic acid type and the like can be used.
  • anionic surfactant examples include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium dodecyl sulfate, and polyoxyethylene ether sulfates such as sodium dodecyl polyglycol ether sulfate and ammonium polyoxyethylene alkyl ether sulfate.
  • Alkyl sulfonates such as sodium sulforicinolate, alkali metal salt of sulfonated paraffin, ammonium salt of sulfonated paraffin; fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine aviatete; sodium benzenesulfonate, Alkali aryl sulfonates such as alkali metal sulfates of alkaliphenol hydroxyethylene can be used.
  • examples thereof include salts, N-acylamino acid salts, N-acylmethyltaurine salts and the like.
  • nonionic surfactant for example, fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monoolate, polyoxyethylene glycol fatty acid esters, and polyglycerin fatty acid esters can be used. Further, ethylene oxide and / or propylene oxide adduct of alcohol having 1 to 18 carbon atoms, ethylene oxide and / or propylene oxide adduct of alkylphenol, ethylene oxide and / or propylene oxide adduct of alkylene glycol and / or alkylenediamine may be used. Can be mentioned.
  • the alcohols having 1 to 18 carbon atoms constituting the nonionic surfactant are, for example, methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, 3rd butanol, amyl alcohol, isoamyl alcohol, 3rd amyl alcohol, and the like.
  • the alkylphenol is, for example, phenol, methylphenol, 2,4-dithiary butylphenol, 2,5-dithary butylphenol, 3,5-dithirth butylphenol, 4- (1,3-tetramethylbutyl) phenol. , 4-isooctylphenol, 4-nonylphenol, 4-third octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, And bisphenol F and the like.
  • the alkylene glycol is, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, and the like.
  • the alkylene diamine is, for example, a compound in which the alcoholic hydroxyl group of the alkylene glycol described above is replaced with an amino group.
  • ethylene oxide and the propylene oxide adduct either a random adduct or a block adduct can be used.
  • Examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, alkylpyridinium bromide and imidazole. Examples include ammonium laurate.
  • amphoteric tenside examples include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylaminomino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, and lauroylamide ethyl.
  • Betain-type amphoteric tenside agents such as hydroxyethylcarboxymethyl betaine and metal salts of hydroxypropyl phosphate, amino acid-type amphoteric tenside agents such as ⁇ -laurylaminopropionic acid metal salts, sulfate ester-type amphoteric tenside agents and sulfonic acids. Examples thereof include amphoteric tenside agents.
  • the content of the epoxy resin in the water-based epoxy resin is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total mass of the water-based epoxy resin.
  • water-based epoxy resin for example, jER series W2801, W2821R70, W3435R67, W8735R70, W1155R55, W5654R45 manufactured by Mitsubishi Chemical Corporation, ADEKA Resin EM-101-50 manufactured by ADEKA Corporation, DIC ( EPICLON EXA-8610 manufactured by Huntsman, Araldite series PZ 3901, PZ 3921, PZ 3961-1 made by Huntsman, DER 915, DER 917 made by Olin, EPIREZ series Resin 3520-WY-55, Resin 6520 made by Hexion. 53 etc. can be used.
  • jER series W2801, W2821R70, W3435R67, W8735R70, W1155R55, W5654R45 manufactured by Mitsubishi Chemical Corporation
  • ADEKA Resin EM-101-50 manufactured by ADEKA Corporation DIC ( EPICLON EXA-8610 manufactured by Huntsman, Araldite series PZ 3901, PZ 3921, PZ 3961-1
  • the content of water in the epoxy resin composition is preferably 10 to 60% by mass from the viewpoint of achieving both workability and reduction of environmental load. It is more preferably 15 to 50% by mass.
  • the compounding amount of the curing agent composition of the present invention and the epoxy resin is such that the active hydrogen equivalent in the curing agent composition is 0. It is preferably 4 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents, and even more preferably 0.6 to 1.0 equivalents.
  • the active hydrogen equivalent in the curing agent composition with respect to 1 equivalent of the epoxy group in the epoxy resin is less than 0.4 equivalent, or more than 2.0 equivalent, or when the epoxy resin composition does not cure. There is.
  • the method for producing the epoxy resin composition of the present invention is not particularly limited, for example, the curing agent composition and the water-based epoxy resin are mixed together.
  • the paint of the present invention contains the epoxy resin composition of the present invention, that is, the curing agent composition of the present invention and the epoxy resin as essential components, but contains additives as necessary to improve the performance as a paint.
  • additives include, for example, inorganic fillers, wetting agents, dispersants, defoaming agents, viscosity modifiers, thickeners, leveling agents, anti-dripping agents, pH regulators, cross-linking agents, stabilizers, anti-corrosion agents. Examples thereof include a force viscous agent, an antifreeze agent, a film forming aid, an antioxidant, a flash last inhibitor, a coupling agent, a chelating agent, and a wetting improver.
  • the curing agent composition of the present invention As the coating material of the present invention, the curing agent composition of the present invention, the epoxy resin, and the epoxy resin composition containing an additive used optionally may be used as they are, but water, a solvent, etc. may be used in order to improve workability. You may dilute the paint with. When the epoxy resin composition is diluted to form a paint, it is preferable to dilute it with water from the viewpoint of environmental friendliness.
  • the total mass of the curing agent composition and the epoxy resin when diluted is preferably 10 to 50% by mass, more preferably 15 to 40% by mass.
  • the paint of the present invention is a paint capable of protecting a base material by applying it to a base material such as metal, wood, plastic, stone, slate, concrete, and mortar. Further, the paint of the present invention can also be used as an anticorrosive paint for preventing corrosion of the base material. Among these, when the paint of the present invention is used as an anticorrosive paint for a base material containing a metal, it is preferable that the paint contains a rust preventive pigment.
  • Examples of the rust preventive pigment include zinc powder, scaly zinc powder, zinc alloy powder, zinc phosphate compound, calcium phosphate compound, aluminum phosphate compound, magnesium phosphate compound, zinc phosphite compound, and the like.
  • zinc-based rust preventive pigments such as zinc powder, scaly zinc powder, zinc alloy powder, and zinc phosphate-based compounds are preferable from the viewpoint of high rust preventive ability.
  • the content of the rust preventive pigment is preferably 1 to 100 parts by mass, more preferably 5 to 90 parts by mass, based on 100 parts by mass of the total mass of the curing agent composition and the epoxy resin. It is more preferably 10 to 80 parts by mass.
  • the above-mentioned curing agent composition, epoxy resin, optionally used additive, rust-preventive pigment, water, solvent and the like may be mixed together, and the curing agent composition or the curing agent composition may be mixed in advance.
  • the epoxy resin may be diluted with water and then the remaining components may be added, and there is no limitation on the production method.
  • additives and rust preventive pigments used in the paints listed above decompose when exposed to water for a long period of time, and some generate hydrogen gas. Therefore, when these additives or rust preventive pigments are used in a water-containing system, such as when a water-based epoxy resin is used as the epoxy resin, it is desirable to add them immediately before using the paint.
  • the curing agent composition of the present invention does not contain water substantially, the above-mentioned additives and rust preventive pigments are added in advance to the curing agent composition and stored, and the curing agent composition is added at once immediately before using the paint. It is preferable because a paint can be produced.
  • a curing agent composition containing an additive and a rust preventive pigment can be prepared in advance improves workability because of the ease of weighing at the time of manufacturing the paint.
  • the painting means when the paint of the present invention is used as an anticorrosion paint is not particularly limited, and known painting means such as spray painting, roller painting, brush painting, iron painting, spatula painting and the like can be used. Further, the dry film thickness formed from the anticorrosion coating material is not particularly limited, and can exemplify the range of 30 to 300 ⁇ m.
  • ⁇ Curing agent composition> (A) Component [Production Example 1] 522.5 g of m-xylylenediamine and 219.7 g of methyl acrylate were added to a 2 L glass flask and reacted at 90 to 100 ° C. for 1 hour. Then, the mixture was heated to 150 to 160 ° C., and was subjected to normal pressure and reduced pressure to remove methanol generated during the reaction to obtain a curing agent A-1.
  • X 1 to X 3 are residues obtained by removing two amino groups from the m-xylylenediamine, and R 1 and R 2 are hydrogen atoms, and n. Is 0 to 3, and the average value of n is 1.0.
  • Component G-240 Gascamine 240 (a reaction product of styrene and m-xylylenediamine, in which X4 is a compound obtained by removing two amino groups from m-xylylenediamine in the above general formula (2). Active hydrogen equivalent: 103 g / eq., Manufactured by Mitsubishi Gas Chemical Company, Inc.)
  • ED-600 Jeffamine ED-600 (in the general formula (3), x and z are 1 to 6, respectively, the average value of the sum of x and z is 3.6, and y is 5 to 15.
  • D-400 Jeffamine D-400 (polypropylene oxide-added polyether polyamine, manufactured by Huntsman).
  • M-1000 Jeffamine M-1000 (polyethylene oxide-polyethylene oxide-added polyether monoamine, manufactured by Huntsman)
  • EHC-30 ADEKA HANDNER EHC-30 (aromatic tertiary amine, manufactured by ADEKA Corporation)
  • P-1000 Epomin P-1000 (polyethyleneimine, manufactured by Nippon Shokubai Co., Ltd.)
  • Examples 1 to 4, Comparative Examples 1 to 6 With the compounding ratio as shown in Table 1, in Examples 1 to 4, the mass ratio of the curing agent A-1 as the component (A) and the amine compound as the component (B) is 7: 3 to 9: 1.
  • the curing agent composition was prepared by mixing so as to be within the range of. Further, as Comparative Examples 1 to 4, the curing agent A-1 was mixed with an amine compound or an imine compound other than the components (A) and (B), and as Comparative Examples 5 and 6, the curing agent A-1 and the curing agent A-1 were mixed. , The amine compound which is the component (B) was mixed at a mass ratio outside the above range to prepare a curing agent composition. The appearance of each curing agent composition was confirmed, and those having a transparent appearance were evaluated as acceptable, and those showing separation, crystallization, turbidity, etc. in the curing agent composition were evaluated as rejected.
  • the curing agent compositions of Examples 1 to 4 have excellent compatibility between the amine compounds used as the component (A) and the component (B), have a transparent appearance, and are preserved. It was found that the state was also good, but the curing agent compositions of Comparative Examples 1 to 6 caused separation, crystallization, and turbidity between the amine compounds or between the amine compound and the imine compound, and the work in the storage state and use. It turned out to be problematic in sex.
  • Example 5 The epoxy resin composition of Example 5 was prepared as follows. [Example 5] To a 200 mL beaker, add 64 g of the curing agent A-1 as the component (A), 16 g of G-240 as the component (B), and 20 g of propylene glycol monomethyl ether as the diluting solvent, and stir for 5 minutes to obtain the curing agent composition X. Prepared. The theoretical value of the active hydrogen equivalent of the curing agent composition X is 110 g / eq. Is.
  • epoxy resin adecaredin EM-101-50 (solid BPA type epoxy resin emulsion, epoxy equivalent: 1075 g / eq., Epoxy resin content 47% by mass, manufactured by ADEKA Co., Ltd.) and the above-mentioned curing agent composition X are used.
  • the ratio of the active hydrogen equivalent in the curing agent composition X to the epoxy equivalent in the epoxy resin (active hydrogen equivalent / epoxy equivalent) was 0.8, and the mixture was mixed to prepare an epoxy resin composition.
  • ⁇ Tack free time> The epoxy resin composition was applied to a glass plate to a thickness of 100 ⁇ m and then stored at 25 ° C., and the time during which the epoxy resin composition did not adhere to the finger was measured by the tactile sensation with a finger.
  • ⁇ Pencil hardness> The epoxy resin composition is applied to a steel sheet (SPCC-SB) to a thickness of 100 ⁇ m, allowed to stand at 25 ° C. for 4 days, dried to form a cured product, and then coated according to JIS K 5600-5-4.
  • the lead of the pencil was applied to the surface of the (cured product) at an angle of about 45 °, and the lead was strongly pressed against the surface of the test coating plate so as not to break, and the lead was moved forward at a uniform speed by about 10 mm.
  • the hardness symbol of the hardest pencil that did not tear the coating film was defined as pencil hardness.
  • the epoxy resin composition is applied to a steel plate (SPCC-SB) to a thickness of 100 ⁇ m, allowed to stand at 25 ° C. for 4 days, and dried to form a cured product. A cut was made in the shape of a mesh with a cutter, the adhesive tape was crimped, and the mixture was allowed to stand for 5 minutes. Then, the adhesive tape was peeled off and the number of peeled squares out of 25 squares was measured.
  • the epoxy resin composition is applied to a glass plate to a thickness of 100 ⁇ m, allowed to stand at 25 ° C. for 4 days, dried to form a cured product, and then immersed in water at 25 ° C. for 1 day to obtain a coating film (cured). I checked the appearance of the thing). Those without bleaching were rejected, and those with bleaching were rejected.
  • the epoxy resin composition was applied to a pre-weighed glass plate to a thickness of 100 ⁇ m, allowed to stand at 25 ° C. for 4 days, dried to form a cured product, and then a coating film (cured product) was formed.
  • the glass plate (test piece) was weighed. Then, the test piece was immersed in water at 50 ° C. for one day, and the test piece after wiping off the water droplets on the surface was weighed. Then, the water absorption rate was calculated from each weighing value by the following formula.
  • ⁇ Corrosion resistance> The epoxy resin composition was applied to a sandblasted steel sheet (SS400) to a thickness of 100 ⁇ m, allowed to stand at 25 ° C. for 4 days, dried to form a cured product, and then the coating film (cured product) was cross-cut. Then, in accordance with JIS Z 2371, a salt spray test was conducted at 35 ° C. for 72 hours, and the occurrence of red rust on the coated surface was confirmed and evaluated as follows. ⁇ : Almost no red rust is seen except in the cross-cut part ⁇ : Red rust is seen on a part of the coated surface ⁇ : Red rust is seen on the entire coated surface
  • the epoxy resin composition of Example 5 using the curing agent composition of the present invention had good evaluations including water resistance and corrosion resistance of the cured product. It was found that the cured products of the epoxy resin compositions of Comparative Examples 7 to 9 in which the curing agent composition of the present invention was not used were not satisfactory in any of the evaluations.

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Abstract

The present invention provides: a curing agent composition for epoxy resins, said curing agent composition containing a component (A) that is a compound represented by general formula (1), and a component (B) that is at least one compound selected from the group consisting of compounds represented by general formula (2) and compounds represented by general formula (3), wherein the mass ratio of the component (A) to the component (B) is from 7:3 to 9:1; an epoxy resin composition which contains this curing agent composition for epoxy resins; and a coating material.　(In formula (1), each of R1 and R2 independently represents a hydrogen atom or a methyl group; each of X1 to X3 independently represents a residue that is obtained by removing two amino groups from a polyamine compound; and n represents an integer from 0 to 10.) (In formula (2), X4 represents a residue that is obtained by removing two amino groups from a polyamine compound.) (In formula (3), x represents an integer from 1 to 6; y represents an integer from 1 to 40; and z represents an integer from 1 to 6.)

Description

エポキシ樹脂用硬化剤組成物、エポキシ樹脂組成物及び塗料Hardener composition for epoxy resin, epoxy resin composition and paint
　本発明は、エポキシ樹脂用硬化剤組成物、エポキシ樹脂組成物及び塗料に関する。より詳しくは、特定の骨格を有する２種以上のアミン化合物を含む、エポキシ樹脂用硬化剤組成物、該エポキシ樹脂用硬化剤組成物を含むエポキシ樹脂組成物、該エポキシ樹脂組成物を含む塗料に関する。 The present invention relates to a curing agent composition for an epoxy resin, an epoxy resin composition, and a coating material. More specifically, the present invention relates to an epoxy resin curing agent composition containing two or more kinds of amine compounds having a specific skeleton, an epoxy resin composition containing the epoxy resin curing agent composition, and a coating material containing the epoxy resin composition. ..
　エポキシ樹脂は、接着剤、塗料、電気絶縁材料、土木建築材料として使用した場合に優れた特性を発揮する。中でも耐水性、耐薬品性、及び耐食性に優れるという特性から、自動車、鉄道車両、建築物、船舶、電気機械向けの塗料、飲料水の缶の内側のコーティングなどに用いられることが多い。 Epoxy resin exhibits excellent properties when used as an adhesive, paint, electrical insulation material, and civil engineering and building material. Among them, because of its excellent water resistance, chemical resistance, and corrosion resistance, it is often used for paints for automobiles, railroad vehicles, buildings, ships, electric machines, coatings on the inside of drinking water cans, and the like.
　塗料に用いられるエポキシ樹脂、及び硬化剤は、作業性の観点から粘度を下げるために、これまでは溶剤を用いることが多かった。しかし、近年の環境への影響の問題から、樹脂を希釈するためのトルエンやキシレン等の揮発性溶剤をなるべく使用しないことが検討されてきており、溶剤系塗料から水系塗料への移行が望まれている。 Epoxy resins and curing agents used in paints have often used solvents in order to reduce the viscosity from the viewpoint of workability. However, due to the problem of environmental impact in recent years, it has been considered to avoid using volatile solvents such as toluene and xylene for diluting the resin as much as possible, and it is desired to shift from solvent-based paints to water-based paints. ing.
　水系塗料に用いられるエポキシ樹脂には、エポキシ樹脂が水に分散、又は乳化された水系エポキシ樹脂が使用される。水系エポキシ樹脂中のエポキシ樹脂を硬化させるための硬化剤としては、水系エポキシ樹脂への相溶性及び反応性の観点から、水溶性、又は水に分散、乳化されたものが好まれる。水系エポキシ樹脂に好適な硬化剤としては、例えば、特許文献１に、ポリアミンにアクリル酸メチルを反応させた変性アミンが開示されている。この変性アミンはアミド結合を有しており、水との相溶性が良いが、この変性アミン単独でエポキシ樹脂を硬化させた場合、硬化物の耐水性に課題があった。また、硬化物の耐水性を改善するため、この変性アミンに対して、他のアミン化合物などを併用すると、併用したアミン化合物により硬化剤組成物に濁りが生じる、又はアミン化合物が結晶化するなど、硬化剤組成物に用いられるアミン化合物同士の相溶性が不十分であり、硬化剤組成物の貯蔵安定性や硬化剤組成物として用いる際の作業性に課題があった。 As the epoxy resin used for water-based paint, a water-based epoxy resin in which the epoxy resin is dispersed or emulsified in water is used. As the curing agent for curing the epoxy resin in the water-based epoxy resin, one that is water-soluble or dispersed and emulsified in water is preferable from the viewpoint of compatibility and reactivity with the water-based epoxy resin. As a curing agent suitable for an aqueous epoxy resin, for example, Patent Document 1 discloses a modified amine obtained by reacting a polyamine with methyl acrylate. This modified amine has an amide bond and has good compatibility with water, but when the epoxy resin is cured with this modified amine alone, there is a problem in the water resistance of the cured product. Further, in order to improve the water resistance of the cured product, when another amine compound or the like is used in combination with this modified amine, the cured agent composition becomes turbid due to the combined amine compound, or the amine compound crystallizes. , The compatibility between the amine compounds used in the curing agent composition is insufficient, and there are problems in the storage stability of the curing agent composition and the workability when used as the curing agent composition.
　また、特許文献２にはスチレンとアミン化合物との反応物を含む反応組成物を含有する水系エポキシ樹脂用硬化剤が開示されている。この硬化剤は水系エポキシ樹脂との相溶性は良好であったが、この硬化剤を用いて得られるエポキシ硬化物の耐水性及び耐食性に課題があった。 Further, Patent Document 2 discloses a curing agent for an aqueous epoxy resin containing a reaction composition containing a reaction product of styrene and an amine compound. This curing agent had good compatibility with the water-based epoxy resin, but there was a problem in the water resistance and corrosion resistance of the epoxy cured product obtained by using this curing agent.
特開２００６－７０１２５号公報Japanese Unexamined Patent Publication No. 2006-70125 国際公開２０１８／０９６８６８号International Publication No. 2018/096868
　従って、本発明が解決しようとする課題は、硬化剤組成物として、透明性を保ち、作業性が良好であるとともに、水系エポキシ樹脂との相溶性が良好であり、エポキシ樹脂と反応させて得られる硬化物においては耐水性及び耐食性に優れたエポキシ樹脂用硬化剤組成物を提供することである。 Therefore, the problem to be solved by the present invention is that the curing agent composition maintains transparency, has good workability, and has good compatibility with an aqueous epoxy resin, and can be obtained by reacting with an epoxy resin. It is an object of the present invention to provide a curing agent composition for an epoxy resin having excellent water resistance and corrosion resistance.
　本発明者等は鋭意検討し、特定のアミン化合物である（Ａ）成分と（Ｂ）成分とを特定の質量比の範囲で含む硬化剤組成物が、（Ａ）成分と（Ｂ）成分に用いられるアミン化合物同士の良好な相溶性による透明性を有するとともに、水系エポキシ樹脂との相溶性が良好であり、この硬化剤組成物とエポキシ樹脂とを含むエポキシ樹脂組成物を硬化して得られた硬化物が、耐水性及び耐食性に優れていることを見出し、本発明に至った。即ち、本発明は、下記一般式（１）で表される化合物である（Ａ）成分と、及び下記一般式（２）及び一般式（３）で表される化合物からなる群から選択される少なくとも１種である（Ｂ）成分と、を含み、(Ａ)成分と（Ｂ）成分の質量比が、７：３～９：１である、エポキシ樹脂用硬化剤組成物である。 The present inventors have diligently studied, and a curing agent composition containing a specific amine compound (A) component and (B) component in a specific mass ratio range has become the (A) component and the (B) component. It has transparency due to good compatibility between the amine compounds used, and also has good compatibility with water-based epoxy resins. It is obtained by curing an epoxy resin composition containing this curing agent composition and an epoxy resin. We have found that the cured product is excellent in water resistance and corrosion resistance, and have reached the present invention. That is, the present invention is selected from the group consisting of the component (A), which is a compound represented by the following general formula (1), and the compounds represented by the following general formulas (2) and (3). A curing agent composition for an epoxy resin, which comprises at least one component (B) and has a mass ratio of the component (A) to the component (B) of 7: 3 to 9: 1.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式中、Ｒ1、Ｒ2はそれぞれ独立して、水素原子又はメチル基を表し、Ｘ1～Ｘ3はそれぞれ独立して、ポリアミン化合物から２つのアミノ基を除いた残基を表し、ｎは０～１０の整数を表す。 In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, X 1 to X 3 each independently represent a residue obtained by removing two amino groups from a polyamine compound, and n represents a residue. Represents an integer from 0 to 10.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式中、Ｘ4はポリアミン化合物から２つのアミノ基を除いた残基を表す。 In the formula, X 4 represents a residue obtained by removing two amino groups from the polyamine compound.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式中、ｘは１～６の整数を表し、ｙは１～４０の整数を表し、ｚは１～６の整数を表す。 In the formula, x represents an integer of 1 to 6, y represents an integer of 1 to 40, and z represents an integer of 1 to 6.
　本発明の硬化剤組成物は、透明性を保ちながら、作業性、及び水系エポキシ樹脂との相溶性が良好であり、エポキシ樹脂を硬化させて得られる硬化物の耐水性及び耐食性に優れていることから、環境への負荷を軽減させたエポキシ樹脂用硬化剤組成物として有用である。また、本発明の硬化剤組成物とエポキシ樹脂により得られたエポキシ樹脂組成物は、特に自動車、鉄道などの車両、建築物、船舶、電気機械などに用いられる塗料として有用である。 The curing agent composition of the present invention has good workability and compatibility with a water-based epoxy resin while maintaining transparency, and is excellent in water resistance and corrosion resistance of a cured product obtained by curing an epoxy resin. Therefore, it is useful as a curing agent composition for epoxy resins with reduced burden on the environment. Further, the epoxy resin composition obtained from the curing agent composition of the present invention and the epoxy resin is particularly useful as a paint used for vehicles such as automobiles and railways, buildings, ships, and electric machines.
＜硬化剤組成物＞
　エポキシ樹脂用硬化剤組成物として用いることができる本発明の硬化剤組成物は、以下に説明する（Ａ）成分と、（Ｂ）成分と、を含む。 <Curing agent composition>
The curing agent composition of the present invention that can be used as a curing agent composition for an epoxy resin contains the component (A) and the component (B) described below.
　（Ａ）成分は、下記一般式（１）で表される化合物である。 The component (A) is a compound represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式中、Ｒ1及びＲ2はそれぞれ独立して、水素原子又はメチル基を表し、Ｘ1～Ｘ3はそれぞれ独立して、ポリアミン化合物から２つのアミノ基を除いた残基を表し、ｎは０～１０の整数を表す。 In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, X 1 to X 3 each independently represent a residue obtained by removing two amino groups from a polyamine compound, and n represents a residue. Represents an integer from 0 to 10.
　一般式（１）中のＲ1及びＲ2は、この化合物の製造が容易であるという観点から水素原子が好ましい。 As R 1 and R 2 in the general formula (1), a hydrogen atom is preferable from the viewpoint of easy production of this compound.
　一般式（１）中のＸ1～Ｘ3で表される、ポリアミン化合物から２つのアミノ基を除いた残基において、ポリアミン化合物としては、２つ以上のアミノ基を有する化合物であれば特に制限されず、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン等の脂肪族ポリアミン；ｍ－キシリレンジアミン、ｐ－キシリレンジアミンなどの芳香環含有脂肪族ポリアミン；イソホロンジアミン、メンセンジアミン、ビス（４－アミノ－３－メチルジシクロヘキシル）メタン、ジアミノジシクロヘキシルメタン、ビス（アミノメチル）シクロヘキサン、Ｎ－アミノエチルピペラジン、３，９－ビス（３－アミノプロピル）－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン等の脂環式ポリアミン；ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、トリレン－２，４－ジアミン、トリレン－２，６－ジアミン、メシチレン－２，４－ジアミン、メシチレン－２，６－ジアミン、３，５－ジエチルトリレン－２，４－ジアミン、３，５－ジエチルトリレン－２，６－ジアミン等の単核ポリアミン；ビフェニレンジアミン、４，４－ジアミノジフェニルメタン、２，５－ナフチレンジアミン、２，６－ナフチレンジアミン等の芳香族ポリアミン；あるいは、これらポリアミン群から得られる、エポキシ付加変性物、アミド化変性物、イソシアネート変性物、マンニッヒ化変性物等変性ポリアミンを使用することができる。
　また、上記ポリアミン化合物の炭素数は特に限定されないが、炭素数が２～３０の化合物であることが好ましく、炭素数２～２０の化合物であることがより好ましく、炭素数４～１２の化合物であることが更に好ましい。 The residues represented by X 1 to X 3 in the general formula (1) obtained by removing two amino groups from the polyamine compound are particularly limited as long as the polyamine compound is a compound having two or more amino groups. Not, for example, aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine; aromatic ring-containing fats such as m-xylylene diamine and p-xylylene diamine. Group polyamines; isophoronediamine, mensendiamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) ) -2,4,8,10-Tetraoxaspiro [5.5] Alicyclic polyamines such as undecane; m-phenylenediamine, p-phenylenediamine, tolylen-2,4-diamine, tolylen-2,6- Mononuclear polyamines such as diamine, mesityylene-2,4-diamine, mesitylen-2,6-diamine, 3,5-diethyltolylen-2,4-diamine, 3,5-diethyltrilen-2,6-diamine Aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, 2,6-naphthylenediamine; or epoxy-added modified or amidated modified products obtained from these polyamine groups. , Isocyanate-modified products, Mannig-modified products, and other modified polyamines can be used.
The carbon number of the polyamine compound is not particularly limited, but it is preferably a compound having 2 to 30 carbon atoms, more preferably a compound having 2 to 20 carbon atoms, and a compound having 4 to 12 carbon atoms. It is more preferable to have.
　これらのポリアミン化合物の中では、本発明の硬化剤組成物を用いて得られる硬化物の耐水性及び耐食性の観点から、脂肪族ポリアミン、芳香環含有脂肪族ポリアミン、脂環式ポリアミンが好ましく、ｍ－キシリレンジアミン、イソホロンジアミンがより好ましく、ｍ－キシリレンジアミンが特に好ましい。これらの化合物は単独化合物を使用してもよく、２種以上を併用して反応させてもよい。なお、Ｘ1～Ｘ3は、すべて同一でもよく、Ｘ1～Ｘ3のいずれかが異なるものでもよく、すべて異なるものでもよいが、得られる硬化物の耐水性及び耐食性と、一般式（１）で表される化合物の製造を容易にする観点から、すべて同一であることが好ましい。 Among these polyamine compounds, aliphatic polyamines, aromatic ring-containing aliphatic polyamines, and alicyclic polyamines are preferable from the viewpoint of water resistance and corrosion resistance of the cured product obtained by using the curing agent composition of the present invention. -Xylylene diamine and isophorone diamine are more preferable, and m-xylylene diamine is particularly preferable. As these compounds, a single compound may be used, or two or more kinds may be reacted in combination. It should be noted that X 1 to X 3 may all be the same, any one of X 1 to X 3 may be different, or all may be different, but the water resistance and corrosion resistance of the obtained cured product and the general formula (1). ), It is preferable that they are all the same from the viewpoint of facilitating the production of the compounds represented by).
　一般式（１）で表されるｎが０～１０の整数である化合物は、通常、ｎの数値が異なる化合物を含む混合物である。混合物中のｎの平均値は、硬化剤組成物の粘度が低くなり作業性が向上する点と硬化性が向上する点から、０～５が好ましく、０～３がより好ましく、０～１がさらに好ましく、１が特に好ましい。 A compound in which n is an integer of 0 to 10 represented by the general formula (1) is usually a mixture containing compounds having different numerical values of n. The average value of n in the mixture is preferably 0 to 5, more preferably 0 to 3, and 0 to 1 from the viewpoints that the viscosity of the curing agent composition is lowered and the workability is improved and the curability is improved. More preferably, 1 is particularly preferable.
　なお、ｎが２～１０の場合、複数存在するＸ2及びＲ2は、それぞれ同一であっても異なっていてもよいが、この化合物の製造を容易に行えるという観点からＸ2及びＲ2はそれぞれ同一であることが好ましい。 When n is 2 to 10, a plurality of X 2 and R 2 existing may be the same or different from each other, but from the viewpoint of facilitating the production of this compound, X 2 and R 2 are It is preferable that they are the same.
　一般式（１）で表される化合物の製造方法については、公知の方法で製造することができ、例えば、上記ポリアミン化合物に対し、（メタ）アクリル酸、（メタ）アクリル酸エステル、又は（メタ）アクリル酸のハロゲン化物（以下、（メタ）アクリル酸系化合物という）と反応させることによって得ることができる。ここで（メタ）アクリル酸とは、メタクリル酸又はアクリル酸のことを示す。 The compound represented by the general formula (1) can be produced by a known method, and for example, (meth) acrylic acid, (meth) acrylic acid ester, or (meth) acrylic acid may be produced with respect to the polyamine compound. ) It can be obtained by reacting with a halide of acrylic acid (hereinafter referred to as (meth) acrylic acid-based compound). Here, (meth) acrylic acid means methacrylic acid or acrylic acid.
　上記ｎの平均値は、上記ポリアミン化合物と（メタ）アクリル酸系化合物を反応させる際の、それぞれの化合物のモル比を調整することにより決定することができる。モル比は、ポリアミン化合物１モルに対して、０．１～０．９モルが好ましく、０．２～０．８モルがより好ましく、０．５～０．７５モルがさらに好ましい。 The average value of n can be determined by adjusting the molar ratio of each compound when the polyamine compound and the (meth) acrylic acid compound are reacted. The molar ratio is preferably 0.1 to 0.9 mol, more preferably 0.2 to 0.8 mol, still more preferably 0.5 to 0.75 mol, relative to 1 mol of the polyamine compound.
　上記（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボニルなどが挙げられる。 Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate. Examples thereof include tridecyl acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and isobonyl (meth) acrylate.
　上記（メタ）アクリル酸のハロゲン化物におけるハロゲンとしては、フッ素、塩素、臭素、ヨウ素が挙げられる。 Examples of the halogen in the above-mentioned (meth) acrylic acid halide include fluorine, chlorine, bromine, and iodine.
　上記（メタ）アクリル酸系化合物は１種を単独で用いてもよく、２種以上を併用してもよい。安価で製造が容易であるという観点から、（メタ）アクリル酸系化合物は１種を単独で用いることが好ましく、（メタ）アクリル酸エステルがより好ましく、アクリル酸メチルが特に好ましい。 The above (meth) acrylic acid-based compound may be used alone or in combination of two or more. From the viewpoint of low cost and easy production, it is preferable to use one (meth) acrylic acid compound alone, more preferably (meth) acrylic acid ester, and particularly preferably methyl acrylate.
　上記ポリアミン化合物と（メタ）アクリル酸エステルを反応させる場合は、反応後に（メタ）アクリル酸エステル由来のアルコールが発生することから、反応後に上記アルコールを除去することが好ましい。 When the polyamine compound is reacted with the (meth) acrylic acid ester, alcohol derived from the (meth) acrylic acid ester is generated after the reaction, so it is preferable to remove the alcohol after the reaction.
　また、（Ｂ）成分は、下記一般式（２）及び一般式（３）で表される化合物からなる群から選択される少なくとも１種の化合物である。 Further, the component (B) is at least one compound selected from the group consisting of the compounds represented by the following general formulas (2) and (3).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　一般式（２）中、Ｘ4はポリアミン化合物から２つのアミノ基を除いた残基を表す。 In the general formula (2), X 4 represents a residue obtained by removing two amino groups from the polyamine compound.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　一般式（３）中、ｘは１～６の整数を表し、ｙは１～４０の整数を表し、ｚは１～６の整数を表す。 In the general formula (3), x represents an integer of 1 to 6, y represents an integer of 1 to 40, and z represents an integer of 1 to 6.
　（Ｂ）成分において、一般式（２）中のＸ4で表される、ポリアミン化合物から２つのアミノ基を除いた残基におけるポリアミン化合物としては、２つ以上のアミノ基を有する化合物であれば特に制限されず、上記Ｘ1～Ｘ3の説明で例示したポリアミン化合物が挙げられる。本発明の硬化剤組成物を用いて得られる硬化物の耐水性及び耐食性の観点から、脂肪族ポリアミン、芳香環含有脂肪族ポリアミン、脂環式ポリアミンが好ましく、ｍ－キシリレンジアミン、イソホロンジアミンがより好ましく、ｍ－キシリレンジアミンが特に好ましい。 In the component (B), the polyamine compound at the residue of the polyamine compound represented by X4 in the general formula ( 2 ) excluding two amino groups is a compound having two or more amino groups. The polyamine compounds exemplified in the above description of X 1 to X 3 are not particularly limited, and examples thereof include polyamine compounds. From the viewpoint of water resistance and corrosion resistance of the cured product obtained by using the curing agent composition of the present invention, aliphatic polyamines, aromatic ring-containing aliphatic polyamines, and alicyclic polyamines are preferable, and m-xylylene diamine and isophorone diamine are preferable. More preferably, m-xylylene diamine is particularly preferable.
　一般式（２）で表される化合物は、スチレンと上記ポリアミン化合物を、必要に応じて塩基性触媒を用いて反応させることによって得ることができる。反応させる際のスチレンとポリアミン化合物のモル比としては、ポリアミン化合物１モルに対するスチレンのモル比が、０．５～１．５が好ましく、０．８～１．２がより好ましい。 The compound represented by the general formula (2) can be obtained by reacting styrene with the above polyamine compound using a basic catalyst, if necessary. As the molar ratio of styrene to the polyamine compound in the reaction, the molar ratio of styrene to 1 mol of the polyamine compound is preferably 0.5 to 1.5, more preferably 0.8 to 1.2.
　（Ｂ）成分において、一般式（３）のｘが１～６の数を表し、ｙが１～４０の数を表し、ｚが１～６の数を表す化合物は、通常、ｘ、ｙ、ｚの数値がそれぞれ異なる化合物の混合物である。上記混合物において、ｘ及びｚの平均値は、それぞれ独立して、硬化剤組成物を用いて得られる硬化物の物性と水溶性のバランスの観点から１～４が好ましい。また、ｘ＋ｚの合計値の平均値は３～５が好ましい。ｙの平均値は、硬化剤組成物を用いて得られる硬化物の物性と水溶性のバランスの観点から５～１５が好ましい。 In the component (B), the compounds in which x in the general formula (3) represents a number from 1 to 6, y represents a number from 1 to 40, and z represents a number from 1 to 6 are usually x, y,. It is a mixture of compounds having different numerical values of z. In the above mixture, the average values of x and z are preferably 1 to 4 independently from the viewpoint of the balance between the physical properties of the cured product obtained by using the curing agent composition and the water solubility. Further, the average value of the total value of x + z is preferably 3 to 5. The average value of y is preferably 5 to 15 from the viewpoint of the balance between the physical properties of the cured product obtained by using the curing agent composition and the water solubility.
　（Ｂ）成分においては、（Ａ）成分との相溶性がより良好であり、外観の透明性及び保存状態に優れる硬化剤組成物が得られるという点で、一般式（２）で表される化合物が好ましい。 The component (B) is represented by the general formula (2) in that a curing agent composition having better compatibility with the component (A) and excellent in transparency in appearance and storage condition can be obtained. Compounds are preferred.
　（Ｂ）成分は市販品を用いてもよく、例えば、三菱ガス化学（株）製のガスカミン２４０、Ｈｕｎｔｓｍａｎ製のジェファーミンＥＤ－６００などが挙げられる。 As the component (B), a commercially available product may be used, and examples thereof include Gascamin 240 manufactured by Mitsubishi Gas Chemical Company, Inc., Jeffamine ED-600 manufactured by Huntsman, and the like.
　本発明の硬化剤組成物は（Ａ）成分と（Ｂ）成分の質量比が、７：３～９：１であることを特徴とする。硬化剤組成物として用いて得られる硬化物の性能をより向上させるという観点から、上記質量比は７.５：２．５～８．５：１．５であることがより好ましい。（Ａ）成分と（Ｂ）成分の質量比が７：３～９：１の範囲外においては、（Ａ）成分と（Ｂ）成分を混合した際に相溶せず濁りが生じたり、上記硬化物の耐水性及び耐食性などの性能が著しく低下したりするので好ましくない。 The curing agent composition of the present invention is characterized in that the mass ratio of the component (A) to the component (B) is 7: 3 to 9: 1. From the viewpoint of further improving the performance of the cured product obtained by using it as a curing agent composition, the mass ratio is more preferably 7.5: 2.5 to 8.5: 1.5. When the mass ratio of the component (A) to the component (B) is outside the range of 7: 3 to 9: 1, when the component (A) and the component (B) are mixed, they do not dissolve in each other and become turbid. It is not preferable because the performance such as water resistance and corrosion resistance of the cured product is significantly deteriorated.
　本発明の硬化剤組成物は、（Ａ）成分及び（Ｂ）成分以外のアミン系硬化剤を含んでもよい。このようなアミン系硬化剤としては、上記Ｘ1～Ｘ3の説明で例示したポリアミン化合物等が挙げられる。上記アミン系硬化剤には、（Ａ）成分及び（Ｂ）成分の製造時における未反応のポリアミン化合物も該当する。本発明の硬化剤組成物が（Ａ）成分及び（Ｂ）成分以外のアミン系硬化剤を含む場合の、（Ａ）成分及び（Ｂ）成分以外のアミン系硬化剤の含有量としては、硬化剤組成物の硬化性と外観を透明に保持することのバランスの観点から、（Ａ）成分と（Ｂ）成分の合計質量１００質量部に対して、１～２０質量部が好ましく、１～１０質量部がより好ましい。 The curing agent composition of the present invention may contain an amine-based curing agent other than the component (A) and the component (B). Examples of such an amine-based curing agent include polyamine compounds exemplified in the above explanations of X 1 to X 3 . The amine-based curing agent also corresponds to the unreacted polyamine compound at the time of production of the component (A) and the component (B). When the curing agent composition of the present invention contains an amine-based curing agent other than the component (A) and the component (B), the content of the amine-based curing agent other than the component (A) and the component (B) is the curing. From the viewpoint of the balance between the curability of the agent composition and the transparency of the appearance, 1 to 20 parts by mass is preferable with respect to 100 parts by mass of the total mass of the component (A) and the component (B), and 1 to 10 parts are preferable. Parts by mass are more preferred.
　本発明の硬化剤組成物は、硬化性の向上の観点から、硬化促進剤を含んでもよい。硬化促進剤としては、例えば、トリメチルアミン、エチルジメチルアミン、プロピルジメチルアミン、Ｎ，Ｎ’－ジメチルピペラジン、ピリジン、ピコリン、１，８－ジアザビスシクロ（５，４，０）ウンデセン－１（ＤＢＵ）、ベンジルジメチルアミン、２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジメチルアミノメチル）フェノール等の第三アミン類；ブチルフェノール、フェノールノボラック、ｏ－クレゾールノボラック、ｐ－クレゾールノボラック、ｔ－ブチルフェノールノボラック、ジシクロペンタジエンクレゾール等のフェノール類；ｐ－トルエンスルホン酸、チオシアン酸の１－アミノピロリジン塩（大塚化学（株）製；ＮＲ－Ｓ）、サリチル酸、チオ尿素等が挙げられる。
　本発明の硬化剤組成物が上記硬化促進剤を含む場合の硬化促進剤の含有量としては、硬化剤組成物の硬化性と外観を透明に保持することのバランスの観点から、（Ａ）成分と（Ｂ）成分の合計質量１００質量部に対して、１～２０質量部が好ましく、１～１０質量部がより好ましい。 The curing agent composition of the present invention may contain a curing accelerator from the viewpoint of improving curability. Examples of the curing accelerator include trimethylamine, ethyldimethylamine, propyldimethylamine, N, N'-dimethylpiperazine, pyridine, picolin, 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), and benzyl. Tertiary amines such as dimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol; butylphenol, phenol novolac, o-cresol novolak, p-cresolnovolac, t-butylphenol Pphenols such as novolak and dicyclopentadiencresol; p-toluenesulfonic acid, 1-aminopyrrolidine salt of thiocyanic acid (manufactured by Otsuka Chemical Co., Ltd .; NR-S), salicylic acid, thiourea and the like can be mentioned.
The content of the curing accelerator when the curing agent composition of the present invention contains the above-mentioned curing accelerator is the component (A) from the viewpoint of the balance between the curability of the curing agent composition and the transparent appearance. With respect to 100 parts by mass of the total mass of the components (B), 1 to 20 parts by mass is preferable, and 1 to 10 parts by mass is more preferable.
　本発明の硬化剤組成物は溶剤で希釈されていてもよい。上記溶剤は環境に配慮する点でなるべく使用しないことが好ましいが、使用する場合は、硬化剤組成物の粘度を下げて作業性を向上させるために、揮発性の少ない溶剤を使用することが好ましい。そのような溶剤としては、例えば、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等の窒素原子含有溶媒、ジメチルスルホキシド等の硫黄原子含有溶媒等が挙げられる。 The curing agent composition of the present invention may be diluted with a solvent. It is preferable not to use the above solvent in consideration of the environment as much as possible, but when it is used, it is preferable to use a solvent having low volatility in order to reduce the viscosity of the curing agent composition and improve workability. .. Examples of such a solvent include an alcohol solvent such as methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, an ester solvent such as propylene glycol monomethyl ether acetate, and a nitrogen atom such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Examples thereof include a solvent and a solvent containing a sulfur atom such as dimethyl sulfoxide.
　本発明の硬化剤組成物が溶剤を含有する場合の含有量としては、硬化剤組成物の総質量に対して１～３０質量％であることが好ましく、５～２５質量％であることがより好ましい。 When the curing agent composition of the present invention contains a solvent, the content is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, based on the total mass of the curing agent composition. preferable.
　本発明の硬化剤組成物は、硬化剤組成物の透明性、作業性及び硬化性の観点からは、（Ａ）成分と（Ｂ）成分の含有量の合計が硬化剤組成物の全量に対して６０～１００質量％であることが好ましく、７０～１００質量％であることがより好ましく、７５～１００質量％であることが更により好ましい。 In the curing agent composition of the present invention, the total content of the component (A) and the component (B) is the total mass of the curing agent composition from the viewpoint of transparency, workability and curability of the curing agent composition. It is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 75 to 100% by mass.
　本発明の硬化剤組成物の製造方法としては、（Ａ）成分及び（Ｂ）成分、並びに任意で使用されるその他のアミン系硬化剤、硬化促進剤、及び溶剤等を一括で混合する等、製造方法に特に制限はない。 As a method for producing the curing agent composition of the present invention, the components (A) and (B), and other optionally used amine-based curing agents, curing accelerators, solvents, etc. are mixed together, and the like. There are no particular restrictions on the manufacturing method.
＜エポキシ樹脂組成物＞
　本発明のエポキシ樹脂組成物は、上記硬化剤組成物と、エポキシ樹脂と、を含有する。エポキシ樹脂としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール、フロログルクシノール等の単核多価フェノール化合物のポリグリシジルエーテル化合物；ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック、テルペンフェノール等の多核多価フェノール化合物のポリグリシジルエーテル化合物；エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサンジオール、ポリグリコール、チオジグリコール、ジシクロペンタジエンジメタノール、２，２－ビス（４－ヒドロキシシクロヘキシルプロパン（水素化ビスフェノールＡ）、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ビスフェノールＡ－アルキレンオキシド付加物などの多価アルコール類のポリグリシジルエーテル；マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、トリマー酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、ピロメリット酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸等の脂肪族、芳香族又は脂環族多塩基酸のグリシジルエステル類及びグリシジルメタクリレートの単独重合体又は共重合体；Ｎ，Ｎ－ジグリシジルアニリン、ビス（４－（Ｎ－メチル－Ｎ－グリシジルアミノ）フェニル）メタン、ジグリシジルオルトトルイジン、Ｎ，Ｎ－ビス（２，３－エポキシプロピル）－４－（２，３－エポキシプロポキシ）－２－メチルアニリン、Ｎ，Ｎ－ビス（２，３－エポキシプロピル）－４－（２，３－エポキシプロポキシ）アニリン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラ（２，３－エポキシプロピル）－４，４’－ジアミノジフェニルメタン等のグリシジルアミノ基を有するエポキシ化合物；ビニルシクロヘキセンジエポキシド、ジシクロペンタンジエンジエポキサイド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－６－メチルシクロヘキシルメチル－６－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート等の環状オレフィン化合物のエポキシ化物；エポキシ化ポリブタジエン、エポキシ化スチレン－ブタジエン共重合物等のエポキシ化共役ジエン重合体、トリグリシジルイソシアヌレート等の複素環化合物が挙げられる。 <Epoxy resin composition>
The epoxy resin composition of the present invention contains the above-mentioned curing agent composition and an epoxy resin. Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, and fluoroglucosinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), and the like. Echilidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropyridenebis (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, Polyglycidyl ether compounds of polynuclear polyvalent phenolic compounds such as ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinnovolak, terpenphenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, dicyclopentadiene. Polyglycidyl ethers of polyhydric alcohols such as dimethanol, 2,2-bis (4-hydroxycyclohexylpropane (bisphenol A hydride), glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-alkylene oxide adduct; Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyro Monopolymers or copolymers of aliphatic, aromatic or alicyclic polybasic acids such as merit acids, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylene tetrahydrophthalic acid and glycidyl methacrylates; N, N -Diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxy) Propoxy) -2-methylaniline, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropyl) Lopoxy) Epoxide compounds having a glycidylamino group such as aniline, N, N, N', N'-tetra (2,3-epoxypropyl) -4,4'-diaminodiphenylmethane; vinylcyclohexene epoxides, dicyclopentanedi Endiepoxide, 3,4-epoxide cyclohexylmethyl-3,4-epoxide cyclohexanecarboxylate, 3,4-epoxide-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxide-6-methyl) Epoxides of cyclic olefin compounds such as cyclohexylmethyl) adipates; epoxidized conjugated diene polymers such as epoxidized polybutadienes, epoxidized styrene-butadiene copolymers, and heterocyclic compounds such as triglycidyl isocyanurate.
　上記に挙げたエポキシ樹脂の中では、得られる硬化物の耐水性及び耐食性が向上するという点から、多核多価フェノール化合物のポリグリシジルエーテル化合物、多価アルコール類のポリグリシジルエーテルが好ましく、ビスフェノール型エポキシ樹脂がより好ましい。これらのエポキシ樹脂は１種を用いてもよく、２種以上を併用してもよい。 Among the epoxy resins listed above, polyglycidyl ether compounds of polynuclear polyhydric phenol compounds and polyglycidyl ethers of polyhydric alcohols are preferable, and bisphenol type, from the viewpoint of improving the water resistance and corrosion resistance of the obtained cured product. Epoxy resins are more preferred. One type of these epoxy resins may be used, or two or more types may be used in combination.
　上記エポキシ樹脂はそのまま用いてもよいが、水に分散されたもの、若しくは乳化されたものであってもよい（以下、水に分散、若しくは乳化されたエポキシ樹脂を水系エポキシ樹脂という）。水に分散、乳化する方法としては、エポキシ樹脂を水に入れ、界面活性剤を添加して、ディスパー、ホモミキサー等を用いて公知の方法で分散、若しくは乳化する方法が挙げられる。 The above epoxy resin may be used as it is, or may be dispersed in water or emulsified (hereinafter, the epoxy resin dispersed or emulsified in water is referred to as a water-based epoxy resin). Examples of the method of dispersing and emulsifying in water include a method of putting an epoxy resin in water, adding a surfactant, and dispersing or emulsifying by a known method using a disper, a homomixer or the like.
　上記界面活性剤としては、例えば、一般的なアニオン性界面活性剤及びノニオン性界面活性剤、第一級アミン塩、第二級アミン塩、第三級アミン塩、第四級アミン塩及びピリジニウム塩等のカチオン性界面活性剤、ベタイン型、硫酸エステル型及びスルホン酸型等の両性界面活性剤等を使用することができる。 Examples of the surfactant include general anionic and nonionic surfactants, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts and pyridinium salts. Cationic surfactants such as, betaine type, sulfate ester type, sulfonic acid type and the like can be used.
　上記アニオン性界面活性剤としては、例えば、ナトリウムドデシルサルフェート、カリウムドデシルサルフェート、アンモニウムドデシルサルフェート等のアルキルサルフェート類、ナトリウムドデシルポリグリコールエーテルサルフェート及びアンモニウムポリオキシエチレンアルキルエーテルサルフェート等のポリオキシエチレンエーテルサルフェート類；ナトリウムスルホリシノレート、スルホン化パラフィンのアルカリ金属塩、スルホン化パラフィンのアンモニウム塩等のアルキルスルホン酸塩類；ナトリウムラウレート、トリエタノールアミンオレート、トリエタノールアミンアビエテート等の脂肪酸塩類；ナトリウムベンゼンスルホネート、アルカリフェノールヒドロキシエチレンのアルカリ金属サルフェート等のアルキルアリールスルホネート類を使用することができる。さらに、高アルキルナフタレンスルホン酸塩、ナフタレンスルホン酸ホルマリン縮合物、ジアルキルスルホコハク酸塩、ポリオキシエチレンアルキルサルフェート塩、ポリオキシエチレンアルキルアリールサルフェート塩、ポリオキシエチレンエーテルリン酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、Ｎ－アシルアミノ酸塩、及びＮ－アシルメチルタウリン塩等が挙げられる。 Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium dodecyl sulfate, and polyoxyethylene ether sulfates such as sodium dodecyl polyglycol ether sulfate and ammonium polyoxyethylene alkyl ether sulfate. Alkyl sulfonates such as sodium sulforicinolate, alkali metal salt of sulfonated paraffin, ammonium salt of sulfonated paraffin; fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine aviatete; sodium benzenesulfonate, Alkali aryl sulfonates such as alkali metal sulfates of alkaliphenol hydroxyethylene can be used. In addition, high alkylnaphthalene sulfonate, naphthalenesulfonic acid formarin condensate, dialkylsulfosuccinate, polyoxyethylenealkylsulfate salt, polyoxyethylenealkylarylsulfate salt, polyoxyethylene ether phosphate, polyoxyethylenealkylether acetate. Examples thereof include salts, N-acylamino acid salts, N-acylmethyltaurine salts and the like.
　上記ノニオン性界面活性剤としては、例えば、ソルビタンモノラウレート、ソルビタンモノオレート等の多価アルコールの脂肪酸部分エステル類、ポリオキシエチレングリコール脂肪酸エステル類、ポリグリセリン脂肪酸エステル類を使用することができる。さらに炭素数１～１８のアルコールのエチレンオキサイド及び／又はプロピレンオキサイド付加物、アルキルフェノールのエチレンオキサイド及び／又はプロピレンオキサイド付加物、アルキレングリコール及び／又はアルキレンジアミンのエチレンオキサイド及び／又はプロピレンオキサイド付加物等が挙げられる。 As the nonionic surfactant, for example, fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monoolate, polyoxyethylene glycol fatty acid esters, and polyglycerin fatty acid esters can be used. Further, ethylene oxide and / or propylene oxide adduct of alcohol having 1 to 18 carbon atoms, ethylene oxide and / or propylene oxide adduct of alkylphenol, ethylene oxide and / or propylene oxide adduct of alkylene glycol and / or alkylenediamine may be used. Can be mentioned.
　上記ノニオン性界面活性剤を構成する炭素数１～１８のアルコールは例えば、メタノール、エタノール、プロパノール、２－プロパノール、ブタノール、２－ブタノール、第３ブタノール、アミルアルコール、イソアミルアルコール、第３アミルアルコール、ヘキサノール、オクタノール、デカンアルコール、ラウリルアルコール、ミリスチルアルコール、パルミチルアルコール、及びステアリルアルコール等である。 The alcohols having 1 to 18 carbon atoms constituting the nonionic surfactant are, for example, methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, 3rd butanol, amyl alcohol, isoamyl alcohol, 3rd amyl alcohol, and the like. Hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like.
　上記アルキルフェノールは、例えば、フェノール、メチルフェノール、２，４－ジ第３ブチルフェノール、２，５－ジ第３ブチルフェノール、３，５－ジ第３ブチルフェノール、４－（１，３－テトラメチルブチル）フェノール、４－イソオクチルフェノール、４－ノニルフェノール、４－第３オクチルフェノール、４－ドデシルフェノール、２－（３，５－ジメチルヘプチル）フェノール、４－（３，５－ジメチルヘプチル）フェノール、ナフトール、ビスフェノールＡ、及びビスフェノールＦ等である。 The alkylphenol is, for example, phenol, methylphenol, 2,4-dithiary butylphenol, 2,5-dithary butylphenol, 3,5-dithirth butylphenol, 4- (1,3-tetramethylbutyl) phenol. , 4-isooctylphenol, 4-nonylphenol, 4-third octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, And bisphenol F and the like.
　上記アルキレングリコールは、例えば、エチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、２－メチル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，４－ブタンジオール、ネオペンチルグリコール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、２，４－ジエチル－１，５－ペンタンジオール、及び１，６－ヘキサンジオール等である。 The alkylene glycol is, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, and the like. 1,4-Butandiol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, etc. Is.
　上記アルキレンジアミンは、例えば先に説明したアルキレングリコールのアルコール性水酸基がアミノ基に置換された化合物である。上記エチレンオキサイド及びプロピレンオキサイド付加物としては、ランダム付加物とブロック付加物のいずれも使用することができる。 The alkylene diamine is, for example, a compound in which the alcoholic hydroxyl group of the alkylene glycol described above is replaced with an amino group. As the ethylene oxide and the propylene oxide adduct, either a random adduct or a block adduct can be used.
　上記カチオン性界面活性剤としては、例えば、ラウリルトリメチルアンモニウムクロライド、ステアリルトリメチルアンモニウムクロライド、ジステアリルジメチルアンモニウムクロライド、ジデシルジメチルアンモニウムクロライド、ラウリルベンジルジメチルアンモニウムクロライド、ジデシルジメチルアンモニウムクロライド、アルキルピリジニウムブロマイド及びイミダゾリニウムラウレート等が挙げられる。 Examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, alkylpyridinium bromide and imidazole. Examples include ammonium laurate.
　上記両性界面活性剤としては、例えば、ヤシ油脂肪酸アミドプロピルジメチル酢酸ベタイン、ラウリルジメチルアミノ酸ベタイン、２－アルキル－Ｎ－カルボキシメチル－Ｎ－ヒドロキシメチルイミダゾリニウムベタイン、ラウリルヒドロキシスルホベタイン、ラウロイルアミドエチルヒドロキシエチルカルボキシメチルベタイン、ヒドロキシプロピルリン酸の金属塩等のベタイン型両性界面活性剤、β－ラウリルアミノプロピオン酸の金属塩等のアミノ酸型両性界面活性剤、硫酸エステル型両性界面活性剤及びスルホン酸型両性界面活性剤等が挙げられる。 Examples of the amphoteric tenside include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylaminomino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, and lauroylamide ethyl. Betain-type amphoteric tenside agents such as hydroxyethylcarboxymethyl betaine and metal salts of hydroxypropyl phosphate, amino acid-type amphoteric tenside agents such as β-laurylaminopropionic acid metal salts, sulfate ester-type amphoteric tenside agents and sulfonic acids. Examples thereof include amphoteric tenside agents.
　上記水系エポキシ樹脂におけるエポキシ樹脂の含有量は、水系エポキシ樹脂の全質量に対して２０～８０質量％が好ましく、３０～７０質量％がより好ましい。 The content of the epoxy resin in the water-based epoxy resin is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total mass of the water-based epoxy resin.
　水系エポキシ樹脂は市販品を用いてもよく、例えば、三菱ケミカル（株）製のｊＥＲシリーズ　Ｗ２８０１、Ｗ２８２１Ｒ７０、Ｗ３４３５Ｒ６７、Ｗ８７３５Ｒ７０、Ｗ１１５５Ｒ５５、Ｗ５６５４Ｒ４５、（株）ＡＤＥＫＡ製のアデカレジン　ＥＭ－１０１－５０、ＤＩＣ（株）製のＥＰＩＣＬＯＮ　ＥＸＡ－８６１０、Ｈｕｎｔｓｍａｎ製のＡｒａｌｄｉｔｅシリーズ　ＰＺ　３９０１、ＰＺ　３９２１、ＰＺ　３９６１－１、Ｏｌｉｎ製のＤＥＲ　９１５、ＤＥＲ９１７、Ｈｅｘｉｏｎ製のＥＰＩＲＥＺシリーズ　Ｒｅｓｉｎ　３５２０－ＷＹ－５５、Ｒｅｓｉｎ　６５２０－ＷＨ－５３等を使用することができる。 Commercially available products may be used as the water-based epoxy resin, for example, jER series W2801, W2821R70, W3435R67, W8735R70, W1155R55, W5654R45 manufactured by Mitsubishi Chemical Corporation, ADEKA Resin EM-101-50 manufactured by ADEKA Corporation, DIC ( EPICLON EXA-8610 manufactured by Huntsman, Araldite series PZ 3901, PZ 3921, PZ 3961-1 made by Huntsman, DER 915, DER 917 made by Olin, EPIREZ series Resin 3520-WY-55, Resin 6520 made by Hexion. 53 etc. can be used.
　本発明のエポキシ樹脂組成物が水系エポキシ樹脂を含む場合、作業性と環境負荷低減の両立の観点からは、エポキシ樹脂組成物中の水の含有量が１０～６０質量％であることが好ましく、１５～５０質量％であることがより好ましい。 When the epoxy resin composition of the present invention contains a water-based epoxy resin, the content of water in the epoxy resin composition is preferably 10 to 60% by mass from the viewpoint of achieving both workability and reduction of environmental load. It is more preferably 15 to 50% by mass.
　本発明のエポキシ樹脂組成物における、本発明の硬化剤組成物と上記エポキシ樹脂の配合量は、エポキシ樹脂中のエポキシ基１当量に対して、上記硬化剤組成物中の活性水素当量が０．４～２．０当量であることが好ましく、０．５～１．５当量であることがより好ましく、０．６～１．０当量であることがさらに好ましい。エポキシ樹脂組成物における、エポキシ樹脂中のエポキシ基１当量に対する硬化剤組成物中の活性水素当量が０．４当量より少ない場合、若しくは２．０当量より多い場合、エポキシ樹脂組成物が硬化しない場合がある。 In the epoxy resin composition of the present invention, the compounding amount of the curing agent composition of the present invention and the epoxy resin is such that the active hydrogen equivalent in the curing agent composition is 0. It is preferably 4 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents, and even more preferably 0.6 to 1.0 equivalents. In the epoxy resin composition, when the active hydrogen equivalent in the curing agent composition with respect to 1 equivalent of the epoxy group in the epoxy resin is less than 0.4 equivalent, or more than 2.0 equivalent, or when the epoxy resin composition does not cure. There is.
　本発明のエポキシ樹脂組成物の製造方法としては、硬化剤組成物と水系エポキシ樹脂とを一括で混合する等、製造方法に特に制限はない。 The method for producing the epoxy resin composition of the present invention is not particularly limited, for example, the curing agent composition and the water-based epoxy resin are mixed together.
＜塗料＞
　本発明の塗料は、本発明のエポキシ樹脂組成物、即ち本発明の硬化剤組成物とエポキシ樹脂を必須成分として含むが、塗料としての性能を向上させるために必要に応じて添加剤を含有してもよい。そのような添加剤としては、例えば、無機充填剤、湿潤剤、分散剤、消泡剤、粘性調整剤、増粘剤、レベリング剤、垂れ防止剤、ｐＨ調整剤、架橋剤、安定剤、防力ビ剤、凍結防止剤、成膜助剤、酸化防止剤、フラッシュラスト防止剤、カップリング剤、キレート剤、濡れ向上剤等が挙げられる。 <Paint>
The paint of the present invention contains the epoxy resin composition of the present invention, that is, the curing agent composition of the present invention and the epoxy resin as essential components, but contains additives as necessary to improve the performance as a paint. You may. Such additives include, for example, inorganic fillers, wetting agents, dispersants, defoaming agents, viscosity modifiers, thickeners, leveling agents, anti-dripping agents, pH regulators, cross-linking agents, stabilizers, anti-corrosion agents. Examples thereof include a force viscous agent, an antifreeze agent, a film forming aid, an antioxidant, a flash last inhibitor, a coupling agent, a chelating agent, and a wetting improver.
　本発明の塗料は、本発明の硬化剤組成物、エポキシ樹脂、及び任意で使用される添加剤を含むエポキシ樹脂組成物をそのまま用いてもよいが、作業性を向上させるために水や溶剤等で塗料を希釈してもよい。エポキシ樹脂組成物を希釈して塗料とする場合は、環境に配慮する観点から、水で希釈することが好ましい。希釈する場合の塗料全質量に対する硬化剤組成物とエポキシ樹脂の合計質量は１０～５０質量％が好ましく、１５～４０質量％がより好ましい。 As the coating material of the present invention, the curing agent composition of the present invention, the epoxy resin, and the epoxy resin composition containing an additive used optionally may be used as they are, but water, a solvent, etc. may be used in order to improve workability. You may dilute the paint with. When the epoxy resin composition is diluted to form a paint, it is preferable to dilute it with water from the viewpoint of environmental friendliness. The total mass of the curing agent composition and the epoxy resin when diluted is preferably 10 to 50% by mass, more preferably 15 to 40% by mass.
　本発明の塗料は、例えば、金属、木材、プラスチック、石材、スレート、コンクリート、モルタル等の基材に塗布することにより基材を保護することが可能な塗料である。また、本発明の塗料は、基材の腐食を防止する防食塗料としても使用することができる。これらの中でも、本発明の塗料を金属を含む基材の防食塗料として使用する場合は、塗料中に防錆顔料を含むことが好ましい。 The paint of the present invention is a paint capable of protecting a base material by applying it to a base material such as metal, wood, plastic, stone, slate, concrete, and mortar. Further, the paint of the present invention can also be used as an anticorrosive paint for preventing corrosion of the base material. Among these, when the paint of the present invention is used as an anticorrosive paint for a base material containing a metal, it is preferable that the paint contains a rust preventive pigment.
　上記防錆顔料としては、例えば、亜鉛粉末、鱗片状亜鉛粉末、亜鉛合金粉末、リン酸亜鉛系化合物、リン酸カルシウム系化合物、リン酸アルミニウム系化合物、リン酸マグネシウム系化合物、亜リン酸亜鉛系化合物、亜リン酸カルシウム系化合物、亜リン酸アルミニウム系化合物、亜リン酸ストロンチウム系化合物、トリポリリン酸アルミニウム系化合物、モリブデン酸塩系化合物、シアナミド亜鉛系化合物、ホウ酸塩化合物、ニトロ化合物、複合酸化物を挙げることができる。これらの中でも防錆能が高いという観点から、亜鉛粉末、鱗片状亜鉛粉末、亜鉛合金粉末、リン酸亜鉛系化合物等の亜鉛系防錆顔料が好ましい。 Examples of the rust preventive pigment include zinc powder, scaly zinc powder, zinc alloy powder, zinc phosphate compound, calcium phosphate compound, aluminum phosphate compound, magnesium phosphate compound, zinc phosphite compound, and the like. Examples of calcium phosphite compounds, aluminum phosphite compounds, strontium phosphite compounds, aluminum tripolyphosphate compounds, molybdenate compounds, cyanamide zinc compounds, borate compounds, nitro compounds, and composite oxides. Can be done. Among these, zinc-based rust preventive pigments such as zinc powder, scaly zinc powder, zinc alloy powder, and zinc phosphate-based compounds are preferable from the viewpoint of high rust preventive ability.
　上記防錆顔料の含有量としては、上記硬化剤組成物とエポキシ樹脂の合計質量１００質量部に対して、１～１００質量部であることが好ましく、５～９０質量部であることがより好ましく、１０～８０質量部であることがさらに好ましい。 The content of the rust preventive pigment is preferably 1 to 100 parts by mass, more preferably 5 to 90 parts by mass, based on 100 parts by mass of the total mass of the curing agent composition and the epoxy resin. It is more preferably 10 to 80 parts by mass.
　本発明の塗料の製造方法においては、上記硬化剤組成物、エポキシ樹脂、任意で使用される添加剤、防錆顔料、水、溶剤等を一括で混合してもよく、あらかじめ硬化剤組成物やエポキシ樹脂を水で希釈してから残りの成分を添加してもよく、製造方法に制限はない。 In the method for producing a coating material of the present invention, the above-mentioned curing agent composition, epoxy resin, optionally used additive, rust-preventive pigment, water, solvent and the like may be mixed together, and the curing agent composition or the curing agent composition may be mixed in advance. The epoxy resin may be diluted with water and then the remaining components may be added, and there is no limitation on the production method.
　なお、上記に挙げた塗料に使用される添加剤や防錆顔料は、水に長期触れさせておくと分解するものや、水素ガスが発生するものがある。そのため、エポキシ樹脂として水系エポキシ樹脂を用いる場合など、水を含んだ系でこれらの添加剤や防錆顔料を使用する場合は、塗料を使用する直前に添加することが望ましい。 Note that some of the additives and rust preventive pigments used in the paints listed above decompose when exposed to water for a long period of time, and some generate hydrogen gas. Therefore, when these additives or rust preventive pigments are used in a water-containing system, such as when a water-based epoxy resin is used as the epoxy resin, it is desirable to add them immediately before using the paint.
　本発明の硬化剤組成物は実質的に水を含まないことが、硬化剤組成物中に上記添加剤や防錆顔料をあらかじめ添加して保存し、塗料を使用する直前に一度に添加して塗料を製造することができるため好ましい。添加剤や防錆顔料を含む硬化剤組成物をあらかじめ準備できることは、塗料製造時の計量の簡便さから作業性が良好となる。 Since the curing agent composition of the present invention does not contain water substantially, the above-mentioned additives and rust preventive pigments are added in advance to the curing agent composition and stored, and the curing agent composition is added at once immediately before using the paint. It is preferable because a paint can be produced. The fact that a curing agent composition containing an additive and a rust preventive pigment can be prepared in advance improves workability because of the ease of weighing at the time of manufacturing the paint.
　本発明の塗料を防食塗料として使用する場合の塗装手段としては、特に限定されず、既知の塗装手段、例えば、スプレー塗装、ローラー塗装、刷毛塗装、コテ塗装、ヘラ塗装等が利用できる。また、上記防食塗料から形成される乾燥膜厚は、特に制限されるものではなく、３０～３００μｍの範囲を例示することができる。 The painting means when the paint of the present invention is used as an anticorrosion paint is not particularly limited, and known painting means such as spray painting, roller painting, brush painting, iron painting, spatula painting and the like can be used. Further, the dry film thickness formed from the anticorrosion coating material is not particularly limited, and can exemplify the range of 30 to 300 μm.
　以下本発明を実施例により、具体的に説明する。なお、以下の実施例等において％は特に記載が無い限り質量基準である。 Hereinafter, the present invention will be specifically described with reference to Examples. In the following examples and the like,% is based on mass unless otherwise specified.
＜硬化剤組成物＞
・（Ａ）成分
［製造例１］
　２Ｌガラスフラスコにメタキシリレンジアミンを５２２．５ｇ、アクリル酸メチルを２１９．７ｇ加え９０～１００℃で１時間反応させた。その後、１５０～１６０℃まで加温を行い、常圧にて、及び減圧することにより、反応時に生成するメタノールを除去し、硬化剤Ａ－１を得た。硬化剤Ａ－１は、上記一般式（１）において、Ｘ1～Ｘ3がメタキシリレンジアミンから２つのアミノ基を除いた残基であり、Ｒ1及びＲ2が水素原子であり、ｎが０～３であり、ｎの平均値が１．０である化合物である。 <Curing agent composition>
(A) Component [Production Example 1]
522.5 g of m-xylylenediamine and 219.7 g of methyl acrylate were added to a 2 L glass flask and reacted at 90 to 100 ° C. for 1 hour. Then, the mixture was heated to 150 to 160 ° C., and was subjected to normal pressure and reduced pressure to remove methanol generated during the reaction to obtain a curing agent A-1. In the curing agent A-1, in the above general formula (1), X 1 to X 3 are residues obtained by removing two amino groups from the m-xylylenediamine, and R 1 and R 2 are hydrogen atoms, and n. Is 0 to 3, and the average value of n is 1.0.
・（Ｂ）成分
Ｇ－２４０：ガスカミン２４０（スチレンとメタキシリレンジアミンの反応生成物であって、上記一般式（２）においてＸ4がメタキシリレンジアミンから２つのアミノ基を除いた化合物、活性水素当量：１０３ｇ／ｅｑ．、三菱ガス化学（株）製）
ＥＤ－６００：ジェファーミン　ＥＤ－６００（一般式（３）において、ｘとｚがそれぞれ１～６であり、ｘとｚの和の平均値が３．６であり、ｙが５～１５であり、ｙの平均値が９であるポリエーテルポリアミン、活性水素当量：１３２ｇ／ｅｑ．、Ｈｕｎｔｓｍａｎ製） (B) Component G-240: Gascamine 240 (a reaction product of styrene and m-xylylenediamine, in which X4 is a compound obtained by removing two amino groups from m-xylylenediamine in the above general formula (2). Active hydrogen equivalent: 103 g / eq., Manufactured by Mitsubishi Gas Chemical Company, Inc.)
ED-600: Jeffamine ED-600 (in the general formula (3), x and z are 1 to 6, respectively, the average value of the sum of x and z is 3.6, and y is 5 to 15. , A polyether polyamine having an average value of y of 9, active hydrogen equivalent: 132 g / eq., Huntsman)
・（Ａ）成分及び（Ｂ）成分以外のアミン化合物又はイミン化合物
　Ｄ－４００：ジェファーミン　Ｄ－４００（ポリプロピレンオキシド付加型ポリエーテルポリアミン、Ｈｕｎｔｓｍａｎ製）
　Ｍ－１０００：ジェファーミン　Ｍ－１０００（ポリエチレンオキシド－ポリプロピレンオキシド付加型ポリエーテルモノアミン、Ｈｕｎｔｓｍａｎ製）
　ＥＨＣ－３０：アデカハードナー　ＥＨＣ－３０（芳香族３級アミン、（株）ＡＤＥＫＡ製）
　Ｐ－１０００：エポミン　Ｐ－１０００（ポリエチレンイミン、（株）日本触媒製） Amine compounds or imine compounds other than the components (A) and (B) D-400: Jeffamine D-400 (polypropylene oxide-added polyether polyamine, manufactured by Huntsman).
M-1000: Jeffamine M-1000 (polyethylene oxide-polyethylene oxide-added polyether monoamine, manufactured by Huntsman)
EHC-30: ADEKA HANDNER EHC-30 (aromatic tertiary amine, manufactured by ADEKA Corporation)
P-1000: Epomin P-1000 (polyethyleneimine, manufactured by Nippon Shokubai Co., Ltd.)
［実施例１～４、比較例１～６］
　表１に示す通りの配合比で、実施例１～４として、（Ａ）成分である硬化剤Ａ－１と、（Ｂ）成分であるアミン化合物とを質量比が７：３～９：１の範囲となるように混合し、硬化剤組成物を調製した。また、比較例１～４として、硬化剤Ａ－１と、（Ａ）成分及び（Ｂ）成分以外のアミン化合物又はイミン化合物とを混合し、比較例５及び６として、硬化剤Ａ－１と、（Ｂ）成分であるアミン化合物とを上記範囲外の質量比で混合して、硬化剤組成物をそれぞれ調製した。各硬化剤組成物について、外観を確認し、外観が透明であるものを合格とし、硬化剤組成物に分離、結晶化、濁りなどが見られるものを不合格と評価した。 [Examples 1 to 4, Comparative Examples 1 to 6]
With the compounding ratio as shown in Table 1, in Examples 1 to 4, the mass ratio of the curing agent A-1 as the component (A) and the amine compound as the component (B) is 7: 3 to 9: 1. The curing agent composition was prepared by mixing so as to be within the range of. Further, as Comparative Examples 1 to 4, the curing agent A-1 was mixed with an amine compound or an imine compound other than the components (A) and (B), and as Comparative Examples 5 and 6, the curing agent A-1 and the curing agent A-1 were mixed. , The amine compound which is the component (B) was mixed at a mass ratio outside the above range to prepare a curing agent composition. The appearance of each curing agent composition was confirmed, and those having a transparent appearance were evaluated as acceptable, and those showing separation, crystallization, turbidity, etc. in the curing agent composition were evaluated as rejected.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　表１の結果から分かる通り、実施例１～４の硬化剤組成物は、（Ａ）成分及び（Ｂ）成分として用いられるアミン化合物同士の相溶性に優れており、外観が透明であり、保存状態も良好であることが分かったが、比較例１～６の硬化剤組成物はアミン化合物同士又はアミン化合物とイミン化合物とにおいて分離、結晶化、濁りが生じてしまい、保存状態や使用における作業性において問題が生じるものであることが分かった。 As can be seen from the results in Table 1, the curing agent compositions of Examples 1 to 4 have excellent compatibility between the amine compounds used as the component (A) and the component (B), have a transparent appearance, and are preserved. It was found that the state was also good, but the curing agent compositions of Comparative Examples 1 to 6 caused separation, crystallization, and turbidity between the amine compounds or between the amine compound and the imine compound, and the work in the storage state and use. It turned out to be problematic in sex.
＜エポキシ樹脂組成物＞
　以下のように、実施例５のエポキシ樹脂組成物を調製した。
［実施例５］
　２００ｍＬビーカーに、（Ａ）成分として硬化剤Ａ－１を６４ｇ、（Ｂ）成分としてＧ－２４０を１６ｇ、希釈溶剤として、プロピレングリコールモノメチルエーテルを２０ｇ加え５分間攪拌して硬化剤組成物Ｘを調製した。硬化剤組成物Ｘの活性水素当量の理論値は１１０ｇ／ｅｑ．である。
　エポキシ樹脂として、アデカレジン　ＥＭ－１０１－５０（固形ＢＰＡ型エポキシ樹脂エマルション、エポキシ当量：１０７５ｇ／ｅｑ．、エポキシ樹脂含有量４７質量％、（株）ＡＤＥＫＡ製）と、上記硬化剤組成物Ｘとを、硬化剤組成物Ｘ中の活性水素当量とエポキシ樹脂中のエポキシ当量の比（活性水素当量／エポキシ当量）が０．８となるように、混合し、エポキシ樹脂組成物を調製した。 <Epoxy resin composition>
The epoxy resin composition of Example 5 was prepared as follows.
[Example 5]
To a 200 mL beaker, add 64 g of the curing agent A-1 as the component (A), 16 g of G-240 as the component (B), and 20 g of propylene glycol monomethyl ether as the diluting solvent, and stir for 5 minutes to obtain the curing agent composition X. Prepared. The theoretical value of the active hydrogen equivalent of the curing agent composition X is 110 g / eq. Is.
As the epoxy resin, adecaredin EM-101-50 (solid BPA type epoxy resin emulsion, epoxy equivalent: 1075 g / eq., Epoxy resin content 47% by mass, manufactured by ADEKA Co., Ltd.) and the above-mentioned curing agent composition X are used. , The ratio of the active hydrogen equivalent in the curing agent composition X to the epoxy equivalent in the epoxy resin (active hydrogen equivalent / epoxy equivalent) was 0.8, and the mixture was mixed to prepare an epoxy resin composition.
［比較例７］
　２００ｍＬビーカーに硬化剤Ａ－１を７０ｇ、水を３０ｇ加え５分間攪拌して硬化剤組成物Ａ－２を得た。硬化剤組成物Ａ－２の活性水素当量の理論値は１２１ｇ／ｅｑ．である。上記硬化剤組成物Ｘの代わりに、硬化剤組成物Ａ－２を用いた以外は、実施例５と同様に、エポキシ樹脂組成物を調製した。 [Comparative Example 7]
70 g of the curing agent A-1 and 30 g of water were added to a 200 mL beaker and stirred for 5 minutes to obtain a curing agent composition A-2. The theoretical value of the active hydrogen equivalent of the curing agent composition A-2 is 121 g / eq. Is. An epoxy resin composition was prepared in the same manner as in Example 5 except that the curing agent composition A-2 was used instead of the curing agent composition X.
［比較例８］
　上記硬化剤組成物Ｘの代わりに、Ｇ－２４０（活性水素当量：１０３ｇ／ｅｑ．）を用いた以外は、実施例５と同様に、エポキシ樹脂組成物を調製した。 [Comparative Example 8]
An epoxy resin composition was prepared in the same manner as in Example 5 except that G-240 (active hydrogen equivalent: 103 g / eq.) Was used instead of the curing agent composition X.
［比較例９］
　上記硬化剤組成物Ｘの代わりに、ＥＤ－６００（活性水素当量：１３２ｇ／ｅｑ．）を用いた以外は、実施例５と同様に、エポキシ樹脂組成物を調製した。 [Comparative Example 9]
An epoxy resin composition was prepared in the same manner as in Example 5 except that ED-600 (active hydrogen equivalent: 132 g / eq.) Was used instead of the curing agent composition X.
　得られた各エポキシ樹脂組成物について、タックフリータイム（硬化性）、鉛筆硬度、付着性、耐水性、吸水率、及び耐食性について、下記の方法に従いそれぞれ評価を行った。結果を表２に示す。 Each of the obtained epoxy resin compositions was evaluated for tack-free time (curability), pencil hardness, adhesiveness, water resistance, water absorption rate, and corrosion resistance according to the following methods. The results are shown in Table 2.
＜タックフリータイム＞
　エポキシ樹脂組成物をガラス板に厚さ１００μｍで塗布した後２５℃にて保管をし、指による触感においてエポキシ樹脂組成物が指に付着しなくなった時間を測定した。 <Tack free time>
The epoxy resin composition was applied to a glass plate to a thickness of 100 μm and then stored at 25 ° C., and the time during which the epoxy resin composition did not adhere to the finger was measured by the tactile sensation with a finger.
＜鉛筆硬度＞
　エポキシ樹脂組成物を鋼板（ＳＰＣＣ－ＳＢ）に厚さ１００μｍで塗布し、２５℃で４日間静置、乾燥させて硬化物を形成した後、ＪＩＳ　Ｋ　５６００－５－４に準拠し、塗膜（硬化物）の表面に対し約４５°の角度に鉛筆の芯を当て、芯が折れない程度に強く試験塗板面に押し付けながら前方に均一な速さで約１０ｍｍ動かした。塗膜が破れなかったもっとも硬い鉛筆の硬度記号を鉛筆硬度とした。 <Pencil hardness>
The epoxy resin composition is applied to a steel sheet (SPCC-SB) to a thickness of 100 μm, allowed to stand at 25 ° C. for 4 days, dried to form a cured product, and then coated according to JIS K 5600-5-4. The lead of the pencil was applied to the surface of the (cured product) at an angle of about 45 °, and the lead was strongly pressed against the surface of the test coating plate so as not to break, and the lead was moved forward at a uniform speed by about 10 mm. The hardness symbol of the hardest pencil that did not tear the coating film was defined as pencil hardness.
　＜付着性＞
　エポキシ樹脂組成物を鋼板（ＳＰＣＣ－ＳＢ）に厚さ１００μｍで塗布し、２５℃で４日間静置、乾燥させて硬化物を形成した後、塗膜（硬化物）に２ｍｍ幅２５マスの碁盤目状にカッターで切れ目を入れ、粘着テープを圧着させ５分間静置した。その後、粘着テープを引き剥がし２５マスのうち剥がれたマス目の数を計測した。 <Adhesiveness>
The epoxy resin composition is applied to a steel plate (SPCC-SB) to a thickness of 100 μm, allowed to stand at 25 ° C. for 4 days, and dried to form a cured product. A cut was made in the shape of a mesh with a cutter, the adhesive tape was crimped, and the mixture was allowed to stand for 5 minutes. Then, the adhesive tape was peeled off and the number of peeled squares out of 25 squares was measured.
　＜耐水性＞
　エポキシ樹脂組成物をガラス板に厚さ１００μｍで塗布し、２５℃で４日間静置、乾燥させて硬化物を形成した後、２５℃の水に１日浸漬させ、浸漬後の塗膜（硬化物）の外観を確認した。白化がないものを合格とし、白化があるものを不合格とした。 <Water resistance>
The epoxy resin composition is applied to a glass plate to a thickness of 100 μm, allowed to stand at 25 ° C. for 4 days, dried to form a cured product, and then immersed in water at 25 ° C. for 1 day to obtain a coating film (cured). I checked the appearance of the thing). Those without bleaching were rejected, and those with bleaching were rejected.
　＜吸水率＞
　エポキシ樹脂組成物を予め秤量しておいたガラス板に厚さ１００μｍで塗布し、２５℃で４日間静置、乾燥させて、硬化物を形成した後、塗膜（硬化物）が形成されたガラス板（試験片）を秤量した。その後、試験片を５０℃の水に１日浸漬させ、表面の水滴をふき取った後の試験片を秤量した。そして、各秤量値から以下の式により、吸水率を計算した。
〔{（浸漬後の試験片の秤量値－ガラス板の秤量値）／（浸漬前の試験片の秤量値－ガラス板の秤量値）｝×１００〕－１００（％）
　吸水率が０％に近い程、良好な結果であると評価した。なお、吸水率がマイナス表記である場合は、硬化物中の成分がブリードアウトしたことにより質量が減少したと考えられる。 <Water absorption rate>
The epoxy resin composition was applied to a pre-weighed glass plate to a thickness of 100 μm, allowed to stand at 25 ° C. for 4 days, dried to form a cured product, and then a coating film (cured product) was formed. The glass plate (test piece) was weighed. Then, the test piece was immersed in water at 50 ° C. for one day, and the test piece after wiping off the water droplets on the surface was weighed. Then, the water absorption rate was calculated from each weighing value by the following formula.
[{(Weighing value of test piece after immersion-Weighing value of glass plate) / (Weighing value of test piece before immersion-Weighing value of glass plate)} × 100] -100 (%)
The closer the water absorption rate was to 0%, the better the result was evaluated. If the water absorption rate is expressed as a minus, it is considered that the mass decreased due to the bleeding out of the components in the cured product.
　＜耐食性＞
　エポキシ樹脂組成物をサンドブラスト処理した鋼板（ＳＳ４００）に厚さ１００μｍで塗布し、２５℃で４日間静置、乾燥させて硬化物を形成した後、塗膜（硬化物）をクロスカットした。その後、ＪＩＳ　Ｚ　２３７１に準拠し、３５℃、７２時間塩水噴霧試験を行い、塗布表面における赤錆の発生を下記の通りに確認、評価を行った。
　〇：クロスカット部以外にほとんど赤錆が見られない
　△：塗布面の一部に赤錆が見られる
　×：塗布面全体に赤錆が見られる <Corrosion resistance>
The epoxy resin composition was applied to a sandblasted steel sheet (SS400) to a thickness of 100 μm, allowed to stand at 25 ° C. for 4 days, dried to form a cured product, and then the coating film (cured product) was cross-cut. Then, in accordance with JIS Z 2371, a salt spray test was conducted at 35 ° C. for 72 hours, and the occurrence of red rust on the coated surface was confirmed and evaluated as follows.
〇: Almost no red rust is seen except in the cross-cut part △: Red rust is seen on a part of the coated surface ×: Red rust is seen on the entire coated surface
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表２で示された結果の通り、本発明の硬化剤組成物を用いた実施例５のエポキシ樹脂組成物は硬化物の耐水性及び耐食性を含むすべての評価が良好なものであった。本発明の硬化剤組成物を用いない比較例７～９のエポキシ樹脂組成物の硬化物においてはいずれかの評価において満足するものではないことが分かった。 As shown in the results shown in Table 2, the epoxy resin composition of Example 5 using the curing agent composition of the present invention had good evaluations including water resistance and corrosion resistance of the cured product. It was found that the cured products of the epoxy resin compositions of Comparative Examples 7 to 9 in which the curing agent composition of the present invention was not used were not satisfactory in any of the evaluations.

Claims (11)

  1. 　下記一般式（１）で表される化合物である（Ａ）成分と、下記一般式（２）及び一般式（３）で表される化合物からなる群から選択される少なくとも１種である（Ｂ）成分と、を含み、(Ａ)成分と（Ｂ）成分の質量比が、７：３～９：１である、エポキシ樹脂用硬化剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     　（式中、Ｒ1、Ｒ2はそれぞれ独立して、水素原子又はメチル基を表し、Ｘ1～Ｘ3はそれぞれ独立して、ポリアミン化合物から２つのアミノ基を除いた残基を表し、ｎは０～１０の整数を表す。）
    Figure JPOXMLDOC01-appb-C000002
     　（式中、Ｘ4はポリアミン化合物から２つのアミノ基を除いた残基を表す。）
    Figure JPOXMLDOC01-appb-C000003
     　（式中、ｘは１～６の整数を表し、ｙは１～４０の整数を表し、ｚは１～６の整数を表す。）     It is at least one selected from the group consisting of the component (A) which is a compound represented by the following general formula (1) and the compounds represented by the following general formulas (2) and (3) (B). ), And the mass ratio of the component (A) to the component (B) is 7: 3 to 9: 1. A curing agent composition for an epoxy resin.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and X 1 to X 3 each independently represent a residue obtained by removing two amino groups from the polyamine compound, and n Represents an integer from 0 to 10.)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, X 4 represents a residue obtained by removing two amino groups from the polyamine compound.)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, x represents an integer of 1 to 6, y represents an integer of 1 to 40, and z represents an integer of 1 to 6.)
  2. 　前記一般式（１）中、Ｘ1～Ｘ3がメタキシレンジアミンから２つのアミノ基を除いた残基である、請求項１に記載のエポキシ樹脂用硬化剤組成物。 The curing agent composition for an epoxy resin according to claim 1, wherein X 1 to X 3 are residues obtained by removing two amino groups from the m-xylylenediamine in the general formula (1).
  3. 　（Ｂ）成分が前記一般式（２）で表される化合物である、請求項１又は２に記載のエポキシ樹脂用硬化剤組成物。 The curing agent composition for an epoxy resin according to claim 1 or 2, wherein the component (B) is a compound represented by the general formula (2).
  4. 　請求項１～３の何れか一項に記載のエポキシ樹脂用硬化剤組成物と、エポキシ樹脂と、を含むエポキシ樹脂組成物。 An epoxy resin composition comprising the epoxy resin curing agent composition according to any one of claims 1 to 3 and an epoxy resin.
  5. 　前記エポキシ樹脂が、水に分散又は乳化された水系エポキシ樹脂である、請求項４に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 4, wherein the epoxy resin is a water-based epoxy resin dispersed or emulsified in water.
  6. 　請求項４又は５のエポキシ樹脂組成物を硬化させて得られる硬化物。 A cured product obtained by curing the epoxy resin composition according to claim 4 or 5.
  7. 　請求項４又は５に記載のエポキシ樹脂組成物を含む塗料。 A paint containing the epoxy resin composition according to claim 4 or 5.
  8. 　請求項７に記載の塗料を基材に塗布することを含む、基材の腐食を防止する方法。 A method for preventing corrosion of a base material, which comprises applying the paint according to claim 7 to the base material.
  9. 　基材の腐食を防止するための、請求項７に記載の塗料の使用。 Use of the paint according to claim 7 to prevent corrosion of the base material.
  10. 　請求項１～３のいずれか一項に記載のエポキシ樹脂用硬化剤組成物をエポキシ樹脂に添加することを含む、前記エポキシ樹脂を硬化させて得られる硬化物の耐水性及び耐食性を向上させる方法。 A method for improving the water resistance and corrosion resistance of a cured product obtained by curing the epoxy resin, which comprises adding the epoxy resin curing agent composition according to any one of claims 1 to 3 to the epoxy resin. ..
  11. 　エポキシ樹脂を硬化させて得られる硬化物の耐水性及び耐食性を向上させるための、請求項１～３のいずれか一項に記載のエポキシ樹脂用硬化剤組成物の使用。 Use of the curing agent composition for epoxy resin according to any one of claims 1 to 3 for improving the water resistance and corrosion resistance of the cured product obtained by curing the epoxy resin.
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