Classifications

• • 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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• 2021
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