Classifications

• • 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
  • C09D163/10—Epoxy resins modified by unsaturated compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • 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
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
  • C08K5/353—Five-membered rings
• • 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
  • C08L63/10—Epoxy resins modified by unsaturated compounds
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives

Definitions

• the present invention relates to a coating composition, a method for forming a coating film, a method for producing an article, and an article.
• Patent Document 1 discloses an aqueous dispersion of an acrylic-modified epoxy resin and a modified bisphenol A-type epoxy resin, which can provide a coating film having excellent properties from room temperature to forced drying conditions and has excellent paint stability.
• An aqueous coating composition containing is disclosed.
• the aqueous coating composition of Patent Document 1 can be dried by heating at a low temperature such as 20 minutes at 80 ° C., but is said to be the most severe in physical properties, particularly solvent resistance, of the formed coating film. There was room for improvement in ethanol resistance.
• Ethanol is known as a cleaning agent for industrial products.
• an organic solvent has a tendency to dissolve and swell a coating film, and particularly ethanol is known to have a large tendency. For this reason, durability against ethanol is also required for a coating film formed on the surface of an industrial product.
• plastic substrates that are relatively resistant to heat are often used for housings of electrical equipment such as home appliances.
• heat curing baking
• paint Options for articles that can be coated with the composition to form a coating are narrowed.
• an object of the present invention is to provide a coating composition capable of forming a coating film having excellent ethanol resistance even under low temperature curing conditions. Another object of the present invention is to provide an article having a coating film excellent in ethanol resistance. Another object of the present invention is to provide a coating film forming method capable of forming a coating film having excellent ethanol resistance even under low temperature curing conditions. Moreover, an object of this invention is to provide the manufacturing method of the articles
• the coating composition according to the present invention comprises: (A) an acrylic-modified epoxy resin; (B) an oxazoline-based curing agent; Including (A) (A1) an epoxy resin; (A2) a radically polymerizable unsaturated compound including an acidic group-containing radically polymerizable unsaturated compound; The reaction product of The mass ratio (a1: a2) between (a1) and (a2) is 95: 5 to 60:40. It is a coating composition. With this configuration, a coating film excellent in ethanol resistance can be formed even under low temperature curing conditions.
• the number average molecular weight of (A) is 3,000 to 30,000.
• (a1) is an aromatic epoxy resin
• the acidic group-containing radical polymerizable unsaturated compound includes a carboxyl group-containing radical polymerizable unsaturated compound.
• (a2) does not contain a nitrogen atom.
• the article according to the present invention has a coating film formed using any of the coating compositions described above. With this configuration, the article is excellent in ethanol resistance.
• the method for forming a coating film according to the present invention includes: A step of applying a coating composition according to any of the above to an object to form a film; Drying or heating the coating to form a coating; A method for forming a coating film. With this configuration, a coating film excellent in ethanol resistance can be formed even under low temperature curing conditions.
• the method for producing an article according to the present invention includes: A step of applying a coating composition according to any of the above to an object to form a film; Drying or heating the coating to form a coating; The manufacturing method of articles
• the present invention it is possible to provide a coating composition capable of forming a coating film excellent in ethanol resistance even under low temperature curing conditions.
• goods which have a coating film excellent in ethanol resistance can be provided.
• the formation method of the coating film which can form the coating film excellent in ethanol resistance under low temperature curing conditions can be provided.
• goods which have a coating film excellent in ethanol resistance can be provided.
• “even under low-temperature curing conditions” means a temperature condition equal to or lower than about 150 ° C., which is carried out in the painting process of a factory production line for industrial products, unless otherwise specified.
• the (meth) acryloyl group means one or more selected from the group consisting of an acryloyl group, a methacryloyl group, and a combination thereof.
• the number average molecular weight is calculated as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
• the article to be coated means an object before the coating composition is applied, and the article is an article in which the coating composition is applied to the article to be coated and a coating film is formed on the article to be coated.
• the thing which has the coating film formed using the coating composition is meant.
• application means an act of applying a coating composition to an object to be coated
• painting means a general term for an action of forming a coating film on the object to be coated.
• the coating composition according to the present invention comprises: (A) an acrylic-modified epoxy resin; (B) an oxazoline-based curing agent; Including (A) (A1) an epoxy resin; (A2) a radically polymerizable unsaturated compound including an acidic group-containing radically polymerizable unsaturated compound; The reaction product of The mass ratio (a1: a2) between (a1) and (a2) is 95: 5 to 60:40. It is a coating composition. With this configuration, a coating film excellent in ethanol resistance can be formed even under low temperature curing conditions.
• the coating composition according to the present invention can be cured even at a low temperature of about 80 ° C. to form a coating film having excellent ethanol resistance, it can be suitably used for plastic substrates.
• (A) an acrylic-modified epoxy resin, (B) an oxazoline-based curing agent, (a1) an epoxy resin, and (a2) a radically polymerizable unsaturated compound including an acidic group-containing radically polymerizable unsaturated compound, , (A), (B), (a1), (a2) may be abbreviated.
• (A) is an acrylic-modified epoxy resin.
• the acrylic-modified epoxy resin is a reaction product of (a1) an epoxy resin described later and (a2) a radically polymerizable unsaturated compound including an acidic group-containing radically polymerizable unsaturated compound. That is, the (A) acrylic-modified epoxy resin in the present invention is a resin obtained by modifying (a1) an epoxy resin with an acidic group-containing radically polymerizable unsaturated compound.
• (A) forms a coating film excellent in ethanol resistance even under low-temperature curing conditions by a curing reaction with (B) an oxazoline-based curing agent described later.
• the epoxy resin is not particularly limited, and a known epoxy resin can be used. Examples thereof include aromatic epoxy resins such as bisphenol type epoxy resins, novolak type epoxy resins, biphenyl type epoxy resins, and naphthalene type epoxy resins; aliphatic epoxy resins such as dicyclopentadiene type epoxy resins.
• bisphenol type epoxy resins examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, diglycidyl ethers of alkylene oxide adducts of the above bisphenol type epoxy resins, and the above.
• examples thereof include hydrogenated bisphenol type epoxy resins obtained by adding hydrogen to bisphenol type epoxy resins.
• novolak type epoxy resin examples include a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, and the like.
• biphenyl type epoxy resin, naphthalene type epoxy resin, and dicyclopentadiene type epoxy resin include resins in which one or two or more glycidyl ether groups are substituted at an arbitrary position of biphenyl, naphthalene, or dicyclopentadiene.
• Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols in addition to the above-mentioned dicyclopentadiene type epoxy resin.
• the preparation method of (a1) is not particularly limited, and a known method can be used.
• a bisphenol A type epoxy resin can be obtained by condensing a halogen-substituted product of bisphenol A with epichlorohydrin or ⁇ -methylepihalohydrin.
• (A1) may be a commercially available product.
• Commercially available products include, for example, jER (registered trademark) 1001, 1004, 1007, 1010 manufactured by Mitsubishi Chemical Corporation; YD-014U, 017, 019, 020G, 128, YDF-2004, YP-50S manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
• (a1) is an aromatic epoxy resin. In another embodiment, (a1) is a bisphenol type epoxy resin.
• (A1) may be used alone or in combination of two or more.
• (A2) is a radically polymerizable unsaturated compound including an acidic group-containing radically polymerizable unsaturated compound. That is, (a2) includes at least an acidic group-containing radically polymerizable unsaturated compound, and in addition to this, (a2) may further include or include a radically polymerizable unsaturated compound having no acidic group. It does not have to be.
• (a2) a known acidic group-containing radical polymerizable unsaturated compound or a radical polymerizable unsaturated compound having no acidic group can be used.
• Examples of the acidic group of the acidic group-containing radically polymerizable unsaturated compound include a carboxyl group, a sulfonic acid group (—SO 3 H), and a phosphoric acid group (H 2 PO 4 —).
• carboxyl group-containing radical polymerizable unsaturated compound examples include compounds containing a carboxyl group such as acrylic acid and methacrylic acid and a (meth) acryloyl group; maleic acid, itaconic acid, monoethyl maleate, monobutyl maleate, itacone Examples thereof include compounds containing at least one carboxyl group and an ethylenically unsaturated bond such as monoethyl acid and monobutyl itaconate.
• sulfonic acid group-containing radically polymerizable unsaturated compound examples include acrylamide t-butylsulfonic acid, 2-acrylamido-2-methylsulfonic acid, acrylic acid 3-sulfopropyl ester, methacrylic acid 3-sulfopropyl ester, and itaconic acid. Examples thereof include bis (3-sulfopropyl) ester.
• Examples of the phosphoric acid group-containing radical polymerizable unsaturated compound include compounds represented by the general formula CH 2 ⁇ C (R 1 ) COO— (CH 2 CHR 2 O) n —P ( ⁇ O) (OH) 2 Wherein R 1 is H or CH 3 , R 2 is H, CH 3 or CHCl, and n is 1-6.
• Examples of the radically polymerizable unsaturated compound having no acidic group include ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-methacrylic acid 2- Alkyl esters of ⁇ , ⁇ -ethylenically unsaturated aliphatic carboxylic acids such as ethylhexyl and N, N-dimethylaminoethyl acrylate; ⁇ , ⁇ -ethylenically unsaturated aliphatic carboxylic acids such as glycidyl acrylate and glycidyl methacrylate Glycidyl esters; vinyl esters of saturated aliphatic carboxylic acids such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene and vinyltoluene; 2-hydroxy
• radical polymerizable unsaturated compound having no acidic group examples include amides such as acrylamide, methacrylamide, N-methylol acrylamide, N-methoxybutyl acrylamide, diacetone acrylamide, and N, N-dimethylaminopropyl acrylamide.
• amides such as acrylamide, methacrylamide, N-methylol acrylamide, N-methoxybutyl acrylamide, diacetone acrylamide, and N, N-dimethylaminopropyl acrylamide.
• an ethylenically unsaturated compound having a group In one embodiment, the number of carbon atoms in the molecule of the ethylenically unsaturated compound having an amide group is 12 or less.
• the number of carbon atoms is not particularly limited.
• the acidic group-containing radically polymerizable unsaturated compound has 6 or less carbon atoms. By making the number of carbon atoms 6 or less, (A) can be easily made aqueous.
• (a2) does not include a nitrogen atom.
• (a2) does not contain a nitrogen atom, ethanol resistance can be further improved.
• (a2) does not contain an epoxy group.
• the acidic group-containing radical polymerizable unsaturated compound includes a carboxyl group-containing radical polymerizable unsaturated compound.
• the acidic group-containing radically polymerizable unsaturated compound is a carboxyl group-containing radically polymerizable unsaturated compound.
• (a1) is an aromatic epoxy resin
• the acidic group-containing radical polymerizable unsaturated compound contains a carboxyl group-containing radical polymerizable unsaturated compound.
• (a2) includes an acidic group-containing radical polymerizable unsaturated compound and a radical polymerizable unsaturated compound having no acidic group.
• the ratio of the mass of the acidic group-containing radically polymerizable unsaturated compound to the total mass of (a2) is 10% by mass or more, and in another embodiment, 50% by mass or more. In another embodiment, it is 60% by mass or more, in one embodiment, 100% by mass or less, in another embodiment, 80% by mass or less, and in another embodiment, 70% by mass or less. In still another embodiment, it is 60% by mass or less.
• the mass ratio (a1: a2) between (a1) and (a2) is 95: 5 to 60:40, where the total mass of (a1) and (a2) is 100. If the mass ratio of (a2) is less than 5, the resulting (A) acrylic-modified epoxy resin may not be dispersed in water. Moreover, when the mass ratio of (a2) exceeds 40, there exists a possibility that the ethanol resistance of the coating film obtained may be inferior.
• the mass ratio (a1: a2) is, in one embodiment, the mass ratio of (a2) is 10 or more, in another embodiment, 35 or less, and in another embodiment, 30 or less.
• (A2) may be used alone or in combination of two or more.
• (A) The preparation method is not particularly limited, and a known method can be used.
• (A) can be obtained by polymerizing (a2) in the presence of (a1).
• (A) can be obtained as follows, but is not limited thereto.
• the initiator acts on (a2) to generate radicals, and at the same time, hydrogen abstraction occurs from the methine or methylene group in (a1).
• the radicals generated by the hydrogen abstraction of (a1) recombine with each other to form a dimer of (a1), and finally (A) is obtained.
• an initiator having a crosslinking efficiency of 28% or more.
• the “crosslinking efficiency” of the initiator is defined by the molar amount of the dimer produced per mole of the initiator to be added, and is expressed as a percentage.
• Examples of the initiator having a crosslinking efficiency of 28% or more include benzoyl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxytrimethylhexanoate, t- Octyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxystearyl carbonate, t-amyl perbenzoate, dicumyl peroxide, t-butyl cumyl peroxide, dimethyl di-t-butylhexane, bis (t- And organic peroxides such as butylperoxyisopropyl) benzene, di-t-butyl peroxide and dimethyl-di-t-butylhexyne.
• the molecular weight of (A) is not particularly limited and may be adjusted as appropriate.
• the number average molecular weight of (A) is 3,000 or more, in another embodiment 4,000 or more, in another embodiment 5,000 or more, In a form, it is 6,000 or more, in another embodiment, 7,000 or more, in another embodiment, 8,000 or more, and in another embodiment, 15,000 or more.
• the number average molecular weight of (A) is 30,000 or less, in another embodiment, 28,000 or less, in another embodiment, 25,000 or less, In this embodiment, it is 23,000 or less, in another embodiment, it is 20,000 or less, and in another embodiment, it is 15,000 or less.
• the number average molecular weight of (A) is 3,000 to 30,000. When the number average molecular weight of (A) is 3,000 or more, the resulting coating film has improved alcohol resistance and water resistance, and when it is 30,000 or less, paint stability is improved.
• the acid value of (A) is not particularly limited, and may be adjusted as appropriate. For example, it can be 10 to 70, 15 to 65, or 20 to 60, 25 to 55, or 30 to 50. Preferably it is 15 to 65, more preferably 20 to 40.
• the acid value of (A) is 10 or more, the coating stability is improved, and when the acid value of (A) is 70 or less, the alcohol resistance and water resistance of the resulting coating film are increased.
• the acid value in this specification represents a solid content acid value, respectively, and can be measured by the method described in JIS K0070.
• the ratio between the number of moles of the acidic group (A) and the number of moles (B) described later is not particularly limited, and may be adjusted as appropriate. For example, it can be 10: 1 to 10:30, 10: 5 to 10:18. By making the ratio of the number of moles within the above range, the alcohol resistance and water resistance of the resulting coating film are increased.
• (A) does not contain a nitrogen atom in its main chain. Since (A) does not contain a nitrogen atom in its main chain, ethanol resistance can be further improved.
• (A) usually has an acidic group derived from an acidic group-containing radically polymerizable unsaturated compound in the side chain portion.
• some or all of the acidic groups contained in the side chain of (A) are neutralized with a basic substance such as organic amines or inorganic amines. It may be used as a salt.
• Organic amines are not particularly limited, and known amines can be used. Examples thereof include amine compounds such as tributylamine, triethylamine, monoethanolamine, dimethylethanolamine, methylethanolamine, morpholine, N-methylmorpholine. In one embodiment, the organic amine is a tertiary amine such as tributylamine, triethylamine, dimethylethanolamine, N-methylmorpholine.
• Inorganic amines are not particularly limited, and known amines can be used.
• An example is ammonia.
• the amount of basic substances such as organic amines used is not particularly limited, and may be appropriately adjusted so that (A) can be made aqueous or dispersed in water. For example, it may be an amount corresponding to 30 to 200% of the acidic group equivalent.
• Aqueousization of (A) may be performed simultaneously with neutralization, for example, by adding a basic substance and water to (A), or by adding (A) to water containing a basic substance, Neutralization and aqueous formation of (A) can be performed simultaneously.
• the solvent contained in the system is distilled off under reduced pressure. In this way, the aqueous dispersion (A) can be obtained.
• (A) may be used alone or in combination of two or more.
• (B) is an oxazoline-based curing agent.
• (B) is a compound having an oxazoline group, and examples of the oxazoline group include a 2-oxazoline group.
• the number of oxazoline groups possessed by (B) is not particularly limited, and may be appropriately selected. In one embodiment, (B) has two or more oxazoline groups.
• (B) may be a known oxazoline-based curing agent.
• Examples of (B) include 2,2′-bis (2-oxazoline), two 2-oxazoline groups, or 4,4-dimethyl-2-oxazoline group in which two 2-oxazoline groups are directly bonded.
• bonded by the bivalent hydrocarbon group is mentioned.
• Examples of the divalent hydrocarbon group include an aliphatic hydrocarbon group having 1 to 8 carbon atoms such as methylene, trimethylene and cyclohexylene, and an aromatic hydrocarbon group such as phenylene.
• the divalent hydrocarbon group is methylene
• (B) is 2,2'-methylenebis (2-oxazoline).
• Other examples of (B) include bis- (2-oxazolinylcyclohexane) sulfide, bis- (2-oxazolinyl norbornane) sulfide, and the like.
• the preparation method of (B) described above is not particularly limited, and a known method can be used.
• a method of dehydrating cyclization by heating amide alcohol in the presence of a catalyst a method of synthesizing from alkanolamine and nitrile, or a method of synthesizing from alkanolamine and carboxylic acid can be mentioned.
• the form of (B) is not particularly limited, and may be any of solid, organic solvent or water solution, dispersion, and emulsion.
• (B) may use a commercially available product.
• commercially available products (B) include Epocross (registered trademark) such as EPOCROSS (registered trademark) WS-300, WS-500, WS-700, K-2010E, K-2020E, K-2030E manufactured by Nippon Shokubai Co., Ltd. ) Series.
• (B) may be used alone or in combination of two or more.
• the coating composition may be used in coating compositions.
• C Film-forming aid (solvent); Film-forming resin other than (A); Pigment; Sand, etc. Drying delay aids; viscosity modifiers; antiseptics; fungicides; antiseptics; antifoaming agents; light stabilizers; antioxidants; UV absorbers; pH adjusters; You may go out.
• coating film-forming resin other than (C) and (A) will be described.
• (C) is a film-forming aid (solvent).
• (C) has the effect of further enhancing the ethanol resistance of the coating film obtained from the coating composition.
• (C) may be a known film-forming aid (solvent) used in coating compositions.
• solvent used in coating compositions.
• (C) may be used alone or in combination of two or more.
• the content of (C) is not particularly limited, and may be appropriately adjusted in consideration of desired performance, applicability, drying properties, and the like.
• the coating composition may or may not contain a known film forming resin other than (A).
• a film-forming resin include an acrylic resin, a polyester resin, a urethane resin, a butadiene resin, a phenol resin, and a xylene resin.
• the ratio of the film-forming resin other than (A) is 20% by mass or less in one embodiment with respect to the mass of the resin component contained in the coating composition. In another embodiment, it is 10% by mass or less.
• the form of the coating composition is not particularly limited and can be appropriately selected.
• the form of the coating composition may be either liquid or paste.
• the coating composition can be suitably used as an electrodeposition coating composition, particularly an anionic electrodeposition coating composition.
• the method for preparing the coating composition is not particularly limited, and a known method can be used.
• the above-described components may be mixed in an arbitrary order.
• the pigment when the coating composition contains a pigment, in order to facilitate the dispersion of the pigment, the pigment may be prepared in the form of an anionic pigment dispersion paste in which the pigment is previously dispersed in an anionic pigment dispersant.
• the method for preparing the anionic pigment dispersion paste is not particularly limited, and a known method can be appropriately selected and used. For example, after mixing an anionic pigment dispersant, a pigment, optionally a basic substance, and optionally an aqueous medium, until the particle size of the pigment in the mixture reaches a predetermined uniform particle size, It can be obtained by dispersing using a known dispersing device such as a ball mill or a sand grind mill.
• anionic pigment dispersant a known anionic dispersant can be appropriately selected and used.
• the modified acrylic resin etc. which are prepared using acrylic acid ester, acrylic acid, an azonitrile compound, etc. are mentioned.
• the pigment is not particularly limited, and a known pigment such as an inorganic pigment or an organic pigment used for electrodeposition coating can be selected and used.
• colored pigments such as titanium oxide, iron oxide, calcined pigment, carbon black and bengara; extender pigments such as kaolin, talc, aluminum silicate, calcium carbonate, mica, clay and silica; zinc phosphate, phosphorus Protection of iron oxide, aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminum tripolyphosphate, zinc molybdate, aluminum molybdate, calcium molybdate, aluminum phosphomolybdate, zinc phosphomolybdate, etc.
• examples include rust pigments.
• organic pigments examples include phthalocyanine blue, phthalocyanine green, monoazo yellow, disazo yellow, benzimidazolone yellow, quinacridone red, monoazo red, boriazo red, and berylene red.
• the pigments may be used alone or in combination of two or more.
• Examples of basic substances include diethylamine, ethylethanolamine, diethanolamine, monoethanolamine, monopropanolamine, isopropanolamine, ethylaminoethylamine, hydroxyethylamine, diethylenetriamine, triethylamine and other organic amines; ammonia and other inorganic amines; Examples include alkali metal hydroxides such as sodium and potassium hydroxide.
• aqueous medium examples include water or a mixture of water and an organic solvent such as ethanol.
• Ion exchange water may be used as water.
• the anionic pigment dispersion paste is prepared to a solid content of 35 to 70% by mass, or 40 to 65% by mass.
• the method for preparing the anionic electrodeposition coating composition can be any known method for preparing an electrodeposition coating composition, except for using (A) and (B) described above, and is not particularly limited.
• it can be prepared by dispersing (A), (B), optionally an anionic pigment dispersion paste, and optionally a basic substance in an aqueous medium.
• the amount of the basic substance may be, for example, an amount sufficient to neutralize 30% or more, 200% or less, or 50 to 120% with respect to the acidic group equivalent of (A).
• the pH of the anionic electrodeposition coating composition is 6.0 to 9.0 in one embodiment, and 7.0 to 8.5 in another embodiment.
• the method for forming a coating film according to the present invention includes: A step of applying a coating composition according to any of the above to an object to form a film; Drying or heating the coating to form a coating; A method for forming a coating film. With this configuration, a coating film excellent in ethanol resistance can be formed even under low temperature curing conditions.
• the coating composition is the above-described coating composition according to the present invention.
• the coating composition may be the electrodeposition coating composition or the anionic electrodeposition coating composition described above.
• the object to be coated is not particularly limited and can be a known object to be coated.
• the objects to be coated include household electrical appliances (household electrical appliances) and their housings, electrical devices other than homes, and housings, ornaments, furniture, building materials, vehicles, and their bodies, ships, and airplanes. Can be mentioned.
• the object to be coated is a housing of a home appliance.
• the article to be coated is plastic.
• the casing is a concept including a case, a housing, and an enclosure.
• the material of the object to be coated is not particularly limited and can be a known material of the object to be coated.
• a metal, a plastic, etc. can be mentioned.
• the metal is not particularly limited, and examples thereof include aluminum, iron, galvanized steel sheet, aluminum galvanized steel sheet, stainless steel and tinplate.
• plastic examples include acrylic, polyvinyl chloride, polycarbonate, ABS, polyethylene terephthalate, and polyolefin.
• the coating method of the coating composition is not particularly limited, and a known coating method can be used.
• coating methods such as electrodeposition, dipping, brush, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater, and die coater can be used.
• the region where the coating composition is applied to the object to be coated is not particularly limited, and may be appropriately selected and applied to a part or all of the object to be coated.
• the thickness of the coating is not particularly limited, and may be appropriately adjusted according to the thickness of the coating obtained by drying or heating, the use, the object to be coated, the desired performance, and the like.
• the thickness of the coating film obtained by curing can be set to 5 to 20 ⁇ m, or 7 to 12 ⁇ m.
• the drying or heating conditions are not particularly limited, and known conditions can be used.
• the temperature can be 30 ° C or higher, 70 ° C or higher, 80 ° C or higher, 100 ° C or higher, or 120 ° C or higher, 180 ° C or lower, 150 ° C or lower, 120 ° C or lower, 100 ° C or lower, or 90 ° C or lower.
• the curing time can be, for example, 30 seconds to 60 minutes. When the curing temperature is low, it may be 10 to 120 minutes, or 10 to 60 minutes, for example. As described above, by using the coating composition according to the present invention, it can be cured even at a low temperature of about 80 ° C.
• steps other than the steps described above may be included.
• a pretreatment process such as surface treatment or plating of an object to be coated, a multiple coating film forming process such as intermediate coating to top coating, and the like may be included.
• the method of electrodeposition coating using the anion electrodeposition coating composition is not particularly limited, and a known electrodeposition coating method can be used.
• the voltage is normally 1 to 400 V applied between the object to be coated as the anode and the cathode.
• the temperature of the bath liquid of the anionic electrodeposition coating composition at the time of electrodeposition coating can be, for example, 10 to 45 ° C, or 15 to 30 ° C.
• the electrodeposition coating process includes, for example, a step of immersing the object to be coated in the anion electrodeposition coating composition, and applying a voltage between the anode (object to be coated) and the cathode to form a film on the object to be coated.
• the object to be coated is not particularly limited, and a known electrodeposition-coated object can be used.
• a known electrodeposition-coated object can be used.
• an object to be coated similar to the method for forming the coating film can be used.
• the voltage application time may be appropriately adjusted depending on the electrodeposition conditions, and may be, for example, 30 seconds to 5 minutes.
• the drying or baking conditions can be the same as those for the coating film forming method.
• the thickness of the coating film is not particularly limited, and may be appropriately adjusted according to the use, the object to be coated, the desired performance, and the like. For example, it can be 5 to 20 ⁇ m, or 7 to 12 ⁇ m.
• the method for producing an article according to the present invention includes: A step of applying a coating composition according to any of the above to an object to form a film; Drying or heating the coating to form a coating; The manufacturing method of articles
• the coating composition is the above-described coating composition according to the present invention.
• the coating composition may be the electrodeposition coating composition or the anionic electrodeposition coating composition described above.
• the object to be coated is not particularly limited and can be a known object to be coated.
• Examples of the type and material of the object to be coated include the type and material of the object described in the method for forming a coating film.
• the object to be coated is a housing of a home appliance.
• the article to be coated is plastic.
• item is not specifically limited, It is the same as the kind demonstrated by the below-mentioned article
• the coating method of the coating composition is not particularly limited, and examples thereof include the coating method described in the coating film forming method.
• the region where the coating composition is applied to the object to be coated is not particularly limited, and may be appropriately selected and applied to a part or all of the object to be coated.
• the thickness of the coating is not particularly limited, and is the same as the thickness of the coating described in the method for forming a coating.
• the drying or heating conditions are not particularly limited, and known conditions can be used.
• the temperature can be 30 ° C or higher, 70 ° C or higher, 80 ° C or higher, 100 ° C or higher, or 120 ° C or higher, 180 ° C or lower, 150 ° C or lower, 120 ° C or lower, 100 ° C or lower, or 90 ° C or lower.
• the curing time can be, for example, 30 seconds to 60 minutes. As described above, by using the coating composition according to the present invention, it can be cured even at a low temperature of about 80 ° C.
• steps other than the steps described above may be included.
• a pretreatment process such as surface treatment or plating of an object to be coated, a multiple coating film forming process such as intermediate coating to top coating, and the like may be included.
• the article according to the present invention has a coating film formed using the coating composition. Thereby, the article is excellent in ethanol resistance.
• the article is not particularly limited, and may be an article obtained by forming a coating film on a known article to be coated.
• the article has a coating film formed by using the coating composition, and home appliances (household electrical appliances) and their housings, electrical devices other than household electrical appliances, and housings, ornaments, furniture, and building materials Vehicles and their bodies, ships, aircraft and the like.
• the article is a housing for home appliances.
• the article is plastic.
• the blending amount means parts by mass.
• Epoxy resin 1 YP-50S (Bisphenol A type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., number average molecular weight 14,000)
• Epoxy resin 2 YD-020G (Bisphenol A type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., number average molecular weight 8,000, epoxy equivalent 5,000)
• Acid group-containing radical polymerizable unsaturated compound methacrylic acid
• radical polymerizable unsaturated compound 1 ethyl acrylate
• radical polymerizable unsaturated compound 2 styrene comparison resin 1: acrylic resin (DIC Corporation) Barnock (registered trademark) WD-551 made by Comparative resin 2: alkyd resin (Watersol (registered trademark) CD-520P manufactured by DIC)
• Oxazoline-based curing agent 1 Epocross (registered trademark) WS
• Example 1 Using the materials shown in Table 1, an aqueous dispersion of (A) an acrylic-modified epoxy resin was prepared by the procedure shown below, and then a coating composition was prepared.
• (A) Preparation of acrylic-modified epoxy resin A reactor equipped with a heating device, a stirrer, and a reflux condenser was charged with 45 parts by mass of (a1) YP-50S and 45 parts by mass of (a1) YD-020G. To the reactor, 15 parts by mass of butyl carbitol, 30 parts by mass of methyl isobutyl ketone and 60 parts by mass of methoxypropanol were added. Next, the mixture was heated to 120 ° C. while being stirred, and the bisphenol A type epoxy resin (a1) was dissolved. The solution of (a1) was cooled to 110 ° C.
• a mixture of (a2) consisting of (a2) 6 parts by mass of methacrylic acid, (a2) 2 parts by mass of ethyl acrylate, (a2) 2 parts by mass of styrene and 10 parts by mass of methyl isobutyl ketone was prepared.
• dissolved 2 mass parts of benzoyl peroxide which is an initiator with 19 mass parts of methyl isobutyl ketone was prepared.
• the mixture of (a2) and the initiator solution were dropped simultaneously from separate dropping funnels over 2 hours. After completion of the dropping, the solution was kept at 110 ° C. for 30 minutes.
• the obtained water dispersion had a nonvolatile content of 34.5%, a solid content acid value of 39 mgKOH / g, and a pH of 7.54.
• Examples 2 to 10 The mass ratio of (a1) and (a2) and the number average molecular weight of (A) were changed as shown in Table 3, respectively, and the preparation of (A) and the preparation of the coating composition were conducted in the same manner as in Example 1. Went.
• Example 11 to 12 As shown in Table 4, in Example 1, except that (B) oxazoline-based curing agent 1 was replaced with oxazoline-based curing agents 2, 3, respectively, A coating composition was prepared.
• Example 13 to 17 In Example 1, the preparation and coating composition of (A) were performed in the same manner as in Example 1 except that 70 parts by mass of deionized water in Table 2 were replaced with 63 parts by mass of deionized water and 7 parts by mass of benzyl alcohol. Was prepared.
• Comparative Examples 1 to 8 As shown in Table 5, in Comparative Examples 1 and 2, the mass ratio between (a1) and (a2) was changed. In Comparative Example 3, (B) was not used. In Comparative Examples 4 and 5, Comparative Resin 1 (acrylic resin) and Comparative Resin 2 (alkyd resin) were used in place of (A), respectively. In Comparative Examples 6 to 8, comparative curing agents 1 to 3 were used in place of (B), respectively.
• the obtained coating composition was applied to an ABS resin plate subjected to chromium (Cr) plating treatment by spray coating so that the film thickness of the cured coating film was 20 ⁇ m. Then, it dried by heating at 80 degreeC for 20 minutes, and obtained the coating board which has a coating film.
• Cr chromium
• Examples 18 to 25 electrodeposition coating
• ABS resin plates subjected to chromium (Cr) plating treatment were immersed in the coating compositions of Examples 1 to 4, 6, 7, 9, and 10. And the DC voltage of the coating voltage 20V was applied for 3 minutes, and the electrodeposition coating was carried out so that the film thickness of a cured coating film might be set to 15 micrometers. Then, it baked for 30 minutes at 80 degreeC, and obtained the coating board which has a coating film.
• Ethanol resistance (appearance evaluation after immersion test) A beaker containing ethanol (reagent grade 95% or more) was adjusted to 20 ° C. The prepared coated plate was immersed in it for 1 hour and taken out. Subsequently, after 5 minutes, the coating state of the immersed portion of the coated plate was visually observed and evaluated according to the following criteria. Evaluation 1 is acceptable and evaluations 2 and 3 are unacceptable. Evaluation 1 (pass): No whitening is observed in the coating film. Evaluation 2 (failed): Part of the film is whitened. Evaluation 3 (failed): The entire coating film is whitened and the base of the coated plate is not visible.
• Ethanol resistance As described above, the coated plate was immersed in ethanol for 1 hour, taken out, and allowed to stand for 1 hour. Next, an adhesion (cross-cut method) test was performed based on JIS K 5600-5-6 for the immersed portion of the coated plate. The cut width was 1 mm. The state of the coating film was visually observed and evaluated according to the following criteria. Evaluations 0 to 2 are acceptable and evaluations 3 to 5 are unacceptable. Evaluation 0 (pass): The edge of the cut is completely smooth, and there is no peeling to the eyes of any lattice. Evaluation 1 (pass): Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
• Evaluation 2 The coating film is peeled along the edge of the cut and / or at the intersection.
• the cross-cut part is clearly affected by more than 5% but not more than 15%.
• Evaluation 3 The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eye are partially or completely peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
• Evaluation 4 The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. It is clearly not more than 35% that the cross-cut is affected.
• Evaluation 5 (failed): Any of the degree of peeling that cannot be classified even with classification 4.
• Ethanol resistance A rubbing test was performed by reciprocating 50 times at a length of 30 mm and a speed of 30 times / minute while applying a load of 1 kgf / cm2 against a coating film formed with absorbent cotton containing ethanol (reagent grade 95% or more). It was. The state of the coated film after rubbing was visually observed and evaluated according to the following criteria. Evaluations 1 to 3 are acceptable and evaluations 4 to 6 are unacceptable. Evaluation 1 (pass): There is no scratch. Evaluation 2 (pass): Scratches are slightly attached. Evaluation 3 (Pass): There are scratches but no cracks or peeling. Evaluation 4 (failed): Some cracks and peeling are observed. Evaluation 5 (failed): The peeling is seen in about half. Evaluation 6 (failed): Peeling is observed on the entire surface.
• Paint Stability The paint composition was stored at 40 ° C. for 3 months, and the state of the paint after storage was visually observed and evaluated according to the following criteria. Evaluations 1 to 3 are acceptable and evaluations 4 to 5 are unacceptable. Evaluation 1 (pass): No settling is observed after storage for 3 months. Evaluation 2 (pass): No settling is observed after storage for 2 months. Evaluation 3 (pass): No sedimentation is observed after storage for 1 month. Evaluation 4 (failed): Sedimentation is observed after storage for 1 month. Evaluation 5 (failed): Water cannot be dispersed.
• Comparative Example 1 using a comparative acrylic-modified epoxy resin in which the mass ratio of (a1) and (a2) was out of the predetermined range, an aqueous dispersion could not be obtained in the first place, and the ethanol resistance could not be evaluated.
• Comparative Example 2 using a comparative acrylic-modified epoxy resin in which the mass ratio of (a1) and (a2) is out of the predetermined range, the coating stability was good, but all the ethanol resistance evaluations failed. Met. Even in Comparative Example 3 in which (B) was not used, all the ethanol resistance evaluations failed.
• (A) In the comparative examples 4 and 5 using an acrylic resin or an alkyd resin instead of the acrylic-modified epoxy resin, all the ethanol resistance evaluations failed.
• Comparative Examples 6 to 8 using other curing agents in place of (B) the oxazoline-based curing agent, all the ethanol resistance evaluations failed.
• the ethanol resistance was acceptable.
• the mass ratio of (a1) to (a2) is 95: 5 to 70:30 (Examples 1 to 3)
• the number average molecular weight of (A) is 8,000 to 28,000 (Examples) In 1 to 3, 5 and 8 to 10
• all ethanol resistance was particularly excellent in the highest evaluation.
• the present invention it is possible to provide a coating composition capable of forming a coating film excellent in ethanol resistance even under low temperature curing conditions.
• goods which have a coating film excellent in ethanol resistance can be provided.
• the formation method of the coating film which can form the coating film excellent in ethanol resistance under low temperature curing conditions can be provided.
• goods which have a coating film excellent in ethanol resistance can be provided.

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