CN115427523A - Resin composition for powder coating material, and article having coating film of the powder coating material - Google Patents
Resin composition for powder coating material, and article having coating film of the powder coating material Download PDFInfo
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- CN115427523A CN115427523A CN202180029540.0A CN202180029540A CN115427523A CN 115427523 A CN115427523 A CN 115427523A CN 202180029540 A CN202180029540 A CN 202180029540A CN 115427523 A CN115427523 A CN 115427523A
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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- 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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09D133/24—Homopolymers or copolymers of amides or imides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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Abstract
Disclosed is a resin composition for powder coating materials, which is characterized by containing an acrylic resin (A) that is composed of an acrylic monomer (a 1) having an epoxy group and a general formula (1)) The acrylic monomer (a 2), the acrylic monomer (a 1) and an unsaturated monomer (a 3) other than the acrylic monomer (a 2) are essential raw materials. The resin composition for powder coating is suitable for powder coating because it can give a cured coating film having excellent appearance, flexibility and filiform rust resistance. Using (in the general formula (1), R 1 Represents a hydrogen atom or a methyl group, R 2 Represents a hydrogen atom or a branched or unbranched alkyl group having 1 to 8 carbon atoms, R 3 Represents a branched or unbranched alkyl group having 1 to 8 carbon atoms. ).
Description
Technical Field
The present invention relates to a resin composition for powder coating, a powder coating, and an article having a coating film of the powder coating.
Background
In recent years, restrictions on organic solvents have become severe due to problems such as air pollution, and environmentally compatible coatings have been attracting attention. Among them, powder coating materials are attracting attention as solvent-free coating materials from the viewpoint of environmental protection, and particularly acrylic powder coating materials are attracting attention for use in automobile parts such as aluminum wheels, metal exterior parts, and home appliances because of excellent coating film properties such as weather resistance and stain resistance. However, powder coating materials have a disadvantage of inferior smoothness of the coating film compared with solvent-based coating materials.
In contrast, a powder coating material has been proposed which contains an epoxy group-containing acrylic resin obtained by copolymerizing an alkyl (meth) acrylate, an epoxy group-containing acrylic monomer, and another copolymerizable vinyl monomer, and a curing agent having a functional group reactive with the epoxy group (see, for example, patent document 1). However, the cured coating film obtained from the powder coating has a problem of insufficient filiform rust resistance (Japanese: shi-resistant property), although the smoothness is improved.
Documents of the prior art
Patent literature
Patent document 1: japanese laid-open patent publication No. 2002-69368
Disclosure of Invention
Problems to be solved by the invention
The object of the present invention is to provide a method for producing a fiber having smoothness A resin composition for powder coating which is a cured coating film having excellent flexibility and filiform rust resistance, a powder coating, and an article having a coating film of the powder coating.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems and as a result, have found that a cured coating film obtained from a resin composition for powder coating which contains an acrylic resin containing an acrylic monomer having an epoxy group, an acrylic monomer having a specific structure, and another unsaturated monomer as essential raw materials is excellent in smoothness, flexibility, and filiform rust resistance, and have completed the present invention.
That is, the present invention relates to a resin composition for powder coating materials, which contains an acrylic resin (a) essentially containing an acrylic monomer (a 1) having an epoxy group, an acrylic monomer (a 2) represented by the following general formula (1), and an unsaturated monomer (a 3) other than the acrylic monomer (a 1) and the acrylic monomer (a 2). The present invention relates to a powder coating material and an article coated with the same.
[ chemical formula 1]
(in the general formula (1), R 1 Represents a hydrogen atom or a methyl group, R 2 Represents a hydrogen atom or a branched or unbranched alkyl group having 1 to 8 carbon atoms, R 3 Represents a branched or unbranched alkyl group having 1 to 8 carbon atoms. )
Effects of the invention
The resin composition for powder coating of the present invention is excellent in appearance, flexibility and filiform rust resistance, and can form a cured coating film, and therefore, can be suitably used as a coating material for coating an article such as an aluminum wheel.
Detailed Description
The resin composition for powder coating of the present invention contains an acrylic resin (a) which essentially contains an acrylic monomer (a 1) having an epoxy group, an acrylic monomer (a 2) represented by the following general formula (1), and an unsaturated monomer (a 3) other than the acrylic monomer (a 1) and the acrylic monomer (a 2).
[ chemical formula 2]
(in the general formula (1), R 1 Represents a hydrogen atom or a methyl group, R 2 Represents a hydrogen atom or a branched or unbranched alkyl group having 1 to 8 carbon atoms, R 3 Represents a branched or unbranched alkyl group having 1 to 8 carbon atoms. )
First, the acrylic resin (a) will be described. The acrylic resin (a) has an epoxy group, and can be obtained by copolymerizing the acrylic monomer (a 1), the acrylic monomer (a 2), and the unsaturated monomer (a 3).
The acrylic monomer (a 1) is an acrylic monomer having an epoxy group, and examples thereof include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, (meth) allyl glycidyl ether, (meth) allyl methyl glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate, and among them, glycidyl (meth) acrylate is preferable. These acrylic monomers (a 1) may be used alone or in combination of 2 or more.
In the present invention, "(meth) acrylic acid" means one or both of methacrylic acid and acrylic acid, "(meth) acrylate" means one or both of methacrylate and acrylate, "(meth) acrylamide" means one or both of methacrylamide and acrylamide, and "(meth) acryloyl group" means one or both of a methacryloyl group and an acryloyl group.
The acrylic monomer (a 2) is an acrylic monomer represented by the general formula (1) and examples thereof include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-tert-octyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, and the like, and among them, N-isopropyl (meth) acrylamide, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide are preferable from the viewpoint of excellent balance between flexibility and filiform rust resistance of a coating film. These acrylic monomers (a 2) may be used alone or in combination of 2 or more.
The unsaturated monomer (a 3) is an unsaturated monomer other than the acrylic monomers (a 1) and (a 2), and examples thereof include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, N-pentyl (meth) acrylate, N-hexyl (meth) acrylate, N-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylamide, (meth) acrylonitrile, N-dimethylaminoethyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and N, N-dimethylaminopropyltriethoxysilane, monofunctional monomers such as 3- (meth) acryloyloxypropylmethyldimethoxysilane, styrene, α -methylstyrene, p-methoxystyrene, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, and lactone-modified (meth) acrylate having a hydroxyl group at the terminal; 2-functional monomers such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, bisphenol a-EO-modified di (meth) acrylate, and isocyanuric acid EO-modified diacrylate; and 3-or more-functional monomers such as isocyanuric acid EO-modified triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate, and among these, styrene and/or methyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and isobornyl (meth) acrylate are preferably used from the viewpoint of excellent balance between flexibility and filiform rust resistance of the coating film. These acrylic monomers (a 3) may be used alone or in combination of 2 or more.
The amount of the acrylic monomer (a 1) used is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, of the monomer components that are the raw materials of the acrylic resin (a), from the viewpoint of improving the appearance and the filiform rust resistance of the coating film. The amount of the acrylic monomer (a 2) used is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, of the monomer components that are the raw materials of the acrylic resin (a), from the viewpoint of improving the filiform rust resistance of the coating film. The amount of the acrylic monomer (a 3) used is preferably 30 to 80% by mass, more preferably 40 to 80% by mass, of the monomer components that are the raw materials of the acrylic resin (a), from the viewpoint of improving the flexibility and the filiform rust resistance of the coating film.
The glass transition temperature of the acrylic resin (a) is preferably 20 to 120 ℃ from the viewpoint of improving the filiform rust resistance of the coating film. More preferably 40 to 100 ℃.
In the present invention, the glass transition temperature is determined according to
Formula of FOX: 1/Tg = W1/Tg1+ W2/Tg2 +. Cndot.
(Tg: the glass transition temperature to be determined, W1: the weight fraction of component 1, tg1: the glass transition temperature of the homopolymer of component 1) was determined by calculation.
The glass transition temperature values of the homopolymers of the respective components were those described in "Handbook of adhesion technology" of news of Japan Industrial Co., ltd., or "Handbook of Polymer (Polymer Handbook)" of Wiley-Interscience. Hereinafter, the glass transition temperature based on this calculation is simply referred to as "design Tg".
The number average molecular weight of the acrylic resin (a) is preferably 1,000 to 10,000 in view of excellent fluidity during melting and filiform rust resistance. More preferably 2,000 to 8,000. Here, the number average molecular weight is a value measured by gel permeation chromatography (hereinafter, abbreviated as "GPC") and converted into polystyrene.
The method for obtaining the acrylic resin (a) may be carried out by a known polymerization method using the acrylic monomer (a 1), the acrylic monomer (a 2) and the unsaturated monomer (a 3) as raw materials, and is preferred because the solution radical polymerization method is the simplest.
The solution radical polymerization method is a method of dissolving each monomer as a raw material in a solvent and performing a polymerization reaction in the presence of a polymerization initiator. Examples of the solvent that can be used in this case include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane, and octane; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol, and sec-butanol, and ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, and amyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. These solvents may be used alone, or 2 or more of them may be used in combination.
Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide and methylcyclohexanone peroxide; peroxygenated compounds such as 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 4,4-n-butyl bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-amylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-hexylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) propane, 2,2-bis (4,4-dicumylperoxycyclohexyl) propane, and the like; hydroperoxides such as cumene hydroperoxide and 2,5-dimethylhexane-2,5-hydroperoxide; 1,3 dialkyl peroxide compounds such as dimethylhexane-bis (t-butylperoxydimethylhexane-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diisopropylbenzene peroxide, t-butylcumyl peroxide, etc.; diacyl peroxide compounds such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and the like; peroxycarbonate compounds such as bis (tert-butylcyclohexyl) peroxydicarbonate; organic peroxides such as peroxy ester compounds such as t-butyl peroxy-2-ethylhexanoate, t-butylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, and azo compounds such as 2,2 '-azobisisobutyronitrile, 1,1' -azobis (cyclohexane-1-carbonitrile), and the like.
The resin composition for powder coating of the present invention contains the acrylic resin (a), and preferably contains a curing agent (B) having a functional group capable of reacting with an epoxy group, from the viewpoint of further improving the coating film properties.
The curing agent (B) is a curing agent having a functional group capable of reacting with an epoxy group, and examples thereof include polycarboxylic acid compounds such as suberic acid, azelaic acid, 2,4-diethylglutaric acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, eicosanedioic acid, 1,3-cyclohexanedicarboxylic acid, and butanetricarboxylic acid, anhydrides of these polycarboxylic acids, and polyphenol compounds. Among these, the aliphatic polycarboxylic acid compound and the acid anhydride thereof are preferable, and dodecanedioic acid is more preferable, from the viewpoint of obtaining a high-strength coating film. These curing agents (B) may be used alone or in combination of 2 or more.
In the resin composition for powder coating materials of the present invention, the ratio (a/B) of the number of equivalents of epoxy groups in the acrylic resin (a) to the number of equivalents of functional groups capable of reacting with epoxy groups in the curing agent (B) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, from the viewpoint of obtaining a high-strength coating film.
The resin composition for powder coating of the present invention may contain various known and conventional additives such as leveling agents including organic or inorganic pigments, flow control agents, light stabilizers, ultraviolet absorbers, and antioxidants, as long as the effects of the present invention are not impaired. In addition, a catalyst may be added for the purpose of promoting the curing reaction at the time of sintering.
The resin composition for powder coating of the present invention may further contain a hydrolyzable silane compound such as silica, alkoxysilane, or silane coupling agent, in order to improve the filiform rust resistance of the coating film, within a range not to impair the effects of the present invention. These compounds may be used alone, or 2 or more of them may be used in combination.
Examples of suitable silane coupling agents include glycidyl alkoxysilanes and aminoalkoxysilanes. Among these, glycidyl trialkoxysilane is preferable, and glycidyl trimethoxysilane is more preferable, from the viewpoint of obtaining a coating film excellent in filiform rust resistance.
The amount of the silane coupling agent blended is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass, of the resin composition for powder coating material, from the viewpoint of obtaining a coating film excellent in filiform rust resistance.
The powder coating material of the present invention can be prepared by various known and conventional methods, for example, a so-called mechanical pulverization method in which the acrylic resin (a), the curing agent (B), and, if necessary, various additives such as a pigment and a surface conditioner are mixed, and then they are melt-kneaded, followed by fine pulverization and classification.
The powder coating of the present invention can be applied to exterior parts, household electric appliances, automobile products, motorcycle products, guard rails, and the like, but is suitable for coating metal members such as aluminum wheel alloy members because it can provide a coating film having excellent high appearance such as weather resistance, impact resistance, chipping resistance, water resistance, and filiform rust resistance.
The coating method of the powder coating material of the present invention includes various known and conventional methods such as an electrostatic powder coating method. The method of forming a cured coating film after applying the powder coating material of the present invention may be appropriately selected depending on the type and purpose of the substrate, and it is preferable to bake at a temperature in the range of 120 to 250 ℃ for 5 to 30 minutes in order to obtain a coating film excellent in filiform rust resistance, water resistance and weather resistance. The coating film thickness is preferably in the range of 50 to 200 μm.
Examples
The present invention will be described in more detail below with reference to specific examples. The epoxy equivalent weight and the number average molecular weight of the acrylic resin were measured by the following methods.
[ method for measuring epoxy equivalent ]
The measurement was performed by a hydrochloric acid-pyridine method. 25ml of hydrochloric acid-pyridine solution was added to the resin, and after dissolving by heating at 130 ℃ for 1 hour, phenolphthalein was used as an indicator, and titration was carried out with 0.1N-potassium hydroxide alcoholic solution. The epoxy equivalent was calculated from the amount of 0.1N-KOH alcoholic solution consumed.
[ method for measuring number average molecular weight ]
Measurement was carried out by GPC.
A measuring device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh corporation)
Column: the following columns manufactured by Tosoh corporation were connected in series and used.
"TSKgel G5000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G4000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G3000" (7.8mmI.D.. Times.30 cm). Times.1 roots
"TSKgel G2000" (7.8mmI.D.. Times.30 cm). Times.1 roots
A detector: RI (differential refractometer)
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μ L (tetrahydrofuran solution with a sample concentration of 4 mg/mL)
Standard sample: the following monodisperse polystyrene was used to prepare a calibration curve.
(monodisperse polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-1 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-2, manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-4 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-20 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-40, manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-80 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-128 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-288 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-550 manufactured by Tosoh corporation "
(Synthesis example 1 Synthesis of acrylic resin (A-1))
67 parts by mass of xylene were charged into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen introduction port, and the temperature was raised to 135 ℃ under a nitrogen atmosphere. A mixture of 25 parts by mass of styrene (hereinafter, abbreviated as "St"), 45 parts by mass of methyl methacrylate (hereinafter, abbreviated as "MMA"), 28 parts by mass of glycidyl methacrylate (hereinafter, abbreviated as "GMA"), 2 parts by mass of N-isopropylacrylamide (hereinafter, abbreviated as "NIPAM"), and 6.0 parts by mass of t-butylperoxy 2-ethylhexanoate was added dropwise thereto over 6 hours, and after completion of the dropwise addition, the mixture was kept at the same temperature for 6 hours to perform a polymerization reaction, and then the solvent was removed under reduced pressure of 160 ℃ and 20mmHg to obtain a solid acrylic resin (A-1) having a number average molecular weight of 3,000, a glass transition temperature of 84 ℃ and an epoxy equivalent of 525 g/eq.
(Synthesis example 2 Synthesis of acrylic resin (A-2))
A solid acrylic resin (a-2) having a number average molecular weight of 2800, a glass transition temperature of 51 ℃, and an epoxy equivalent of 525g/eq was obtained in the same manner as in synthesis example 1 except that the monomer composition was changed to 20 parts by mass of St, 25 parts by mass of MMA, 17 parts by mass of N-butyl acrylate (hereinafter, abbreviated as "nBA"), 5 parts by mass of isobornyl methacrylate (hereinafter, abbreviated as "IBOMA"), and 28 parts by mass of GMA and 5 parts by mass of N-isopropyl methacrylamide (hereinafter, abbreviated as "NIPMAA").
(Synthesis example 3 Synthesis of acrylic resin (A-3))
A solid acrylic resin (a-3) having a number average molecular weight of 3,000, a glass transition temperature of 60 ℃, and an epoxy equivalent of 340g/eq was obtained in the same manner as in synthesis example 1, except that the monomer composition was changed to 10 parts by mass of St, 30 parts by mass of MMA, and 13 parts by mass of N-butyl methacrylate (hereinafter, abbreviated as "nBMA"), and 45 parts by mass of GMA, and 2 parts by mass of N-t-octylacrylamide (hereinafter, abbreviated as "NOAA").
Synthesis example 4 Synthesis of acrylic resin (A-4)
67 parts by mass of xylene were charged into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen introduction port, and the temperature was raised to 135 ℃ under a nitrogen atmosphere. 30 parts by mass of St, 20 parts by mass of MMA, 20 parts by mass of GMA, 20 parts by mass of nBMA, N-dimethylacrylamide (hereinafter, abbreviated as "DMAA") 10 parts by mass and 4.0 parts by mass of t-butylperoxy 2-ethylhexanoate were added dropwise over 6 hours, and after completion of the dropwise addition, polymerization was carried out by maintaining the temperature for 6 hours, and further, 0.5 part by mass of 3-glycidoxypropyltrimethoxysilane was added and stirred and mixed for 30 minutes. Then, the solvent was removed under reduced pressure at 160 ℃ and 20mmHg to obtain a solid acrylic resin (A-4) having a number average molecular weight of 5,000, a glass transition temperature of 72 ℃ and an epoxy equivalent of 750 g/eq.
(Synthesis example 5 Synthesis of acrylic resin (RA-1))
A solid acrylic resin (RA-1) having a number average molecular weight of 3,000, a glass transition temperature of 94 ℃ and an epoxy equivalent of 525g/eq was obtained in the same manner as in Synthesis example 1, except that the monomer composition was changed to 20 parts by mass of St, 30 parts by mass of MMA, 22 parts by mass of IBOMA and 28 parts by mass of GMA.
(Synthesis example 6 Synthesis of acrylic resin (RA-2))
A solid acrylic resin (RA-2) having a number average molecular weight of 3,000, a glass transition temperature of 65 ℃ and an epoxy equivalent of 900g/eq was obtained in the same manner as in Synthesis example 1, except that the monomer composition was changed to 25 parts by mass of St, 30 parts by mass of MMA, 30 parts by mass of nBMA and 15 parts by mass of GMA.
(Synthesis example 7 Synthesis of acrylic resin (RA-3))
A solid acrylic resin (RA-3) having a number average molecular weight of 3,000, a glass transition temperature of 4 ℃ and an epoxy equivalent of 525g/eq was obtained in the same manner as in Synthesis example 1, except that the monomer composition was changed to 15 parts by mass of St, 15 parts by mass of MMA, 42 parts by mass of nBA and 28 parts by mass of GMA.
The monomer compositions and property values of the acrylic resins (A-1) to (A-4) and (RA-1) to (RA-3) synthesized in the above synthesis examples 1 to 6 are shown in tables 1 and 2.
[ Table 1]
Example 1 production and evaluation of powder coating Material (1)
A resin composition containing 84 parts by mass of the acrylic resin (a-1), 16 parts by mass of dodecanedioic acid (hereinafter, abbreviated as "DDDA"), 5 parts by mass of benzoin, and 3 parts by mass of a leveling agent (Resiflow LF manufactured by ESTRON) obtained in synthesis example 1 was melt-kneaded using a twin-screw kneader ("APV · kneader MP-2015 manufactured by Tubako shozuabin co., ltd.), finely pulverized, and further classified with a 200-mesh wire gauze to obtain a powder coating material (1).
[ production of cured coating film for evaluation ]
The powder coating material obtained above was applied electrostatically to an untreated aluminum plate (A-1050P) (7 cm. Times.15 cm) so that the sintered film thickness became 80 to 120 μm, and then sintered at 170 ℃ for 20 minutes to prepare a cured coating film for evaluation.
[ smoothness test ]
The smoothness of the Powder Coating film was evaluated by visual evaluation using a PCI (Powder Coating Institute) standard plate. The standard plate had 10 sheets of 1 to 10, and the smoothness was good as the number was increased. The smoothness of the powder coating film thus produced was visually evaluated as to which standard plate. Based on the result of the determination, smoothness is determined as follows.
Good: smoothness of 8 or more
And (delta): the smoothness is 6 to 7
X: smoothness of 5 or less
[ Eleksen test ]
The film surface of the coating film for evaluation obtained above was subjected to an extrusion test using an ERICHSENGMBH & co. Model 200 "to measure the extrusion length at the time of occurrence of fracture. Based on the extrusion length, the flexibility of the coating film was determined as follows.
Good component: the extrusion length exceeds 7.0mm
And (delta): the extrusion length is 5.0-7.0 mm
X: the extrusion length is less than 5.0mm
[ evaluation of resistance to filiform rusting ]
2 linear scratches of 13cm were formed on the cured coating film for evaluation obtained above with a cutter knife, and the film was allowed to reach the base of the substrate, and the following test was carried out with a CASS tester. Test 1 in which 6-hour brine (prepared by dissolving 2.6g of copper (II) chloride hydrate, 10cc of glacial acetic acid, and 500g of common salt in 10L of ion-exchanged water) was sprayed under conditions of a temperature of 50 ℃, an amount of spray liquid of 1.2 to 1.8cc/h, and a spray pressure of 0.1MPa, and test 2 in which the mixture was left for 96 hours under conditions of a temperature of 60 ℃ and a humidity of 85% were taken as 1 cycle, and the total of 5 cycles were performed. After the CASS test was completed, the filiform rust caused by the damage of the coated plate was visually confirmed, and the filiform rust resistance was evaluated from the length of the filiform rust which grew the longest. The filiform rust resistance of the coating film was determined based on the length of the filiform rust that has grown the longest.
Good: the longest length of the filiform rust is less than 2.0mm
And (delta): the longest length of the filamentous rust exceeds 2.0mm and is 3.0mm or less
X: the longest length of the filiform rust exceeds 3.0mm
( Examples 2 to 4: production and evaluation of powder coating materials (2) to (4) )
Powder coatings (2) to (4) were prepared and evaluated for various physical properties in the same manner as in example 1 except that the acrylic resin (a-1) and DDDA blended in example 1 were changed to compositions shown in table 3.
( Comparative examples 1 to 3: production and evaluation of powder coating compositions (R1) to (R3) )
Powder coatings (R1) to (R3) were prepared and evaluated for various physical properties in the same manner as in example 1, except that the acrylic resin (a-1) and DDDA blended in example 1 were changed as shown in table 4.
The blending compositions and evaluation results of the powder coating materials (1) to (4) obtained in examples 1 to 4 and the powder coating materials (R1) to (R3) obtained in comparative examples 1 to 3 are shown in tables 3 and 4.
[ Table 2]
[ Table 3]
It was confirmed that the cured coating films obtained from the resin compositions for powder coating materials of examples 1 to 4 were excellent in smoothness, flexibility and filiform rust resistance.
On the other hand, comparative examples 1 to 3 are examples in which the acrylic monomer (a 2) represented by the general formula (1) was not used as a raw material of the acrylic resin (a) which is a component of the resin composition for powder coating of the present invention, but a material satisfying all of good smoothness, flexibility and filiform rust resistance of the coating film was not obtained.
Claims (6)
1. A resin composition for powder coating materials, which contains an acrylic resin A that requires an acrylic monomer a1 having an epoxy group, an acrylic monomer a2 represented by the following general formula (1), the acrylic monomer a1, and an unsaturated monomer a3 other than the acrylic monomer a2 as raw materials,
in the general formula (1), R 1 Represents a hydrogen atom or a methyl group, R 2 Represents a hydrogen atom or a branched or unbranched alkyl group having 1 to 8 carbon atoms, R 3 Represents a branched or unbranched alkyl group having 1 to 8 carbon atoms.
2. The resin composition for powder coating according to claim 1, wherein the acrylic monomer a1, the acrylic monomer a2, and the acrylic monomer a3 are contained in a monomer component as a raw material of the acrylic resin A in an amount of 10 to 60% by mass, 0.1 to 30% by mass, and 30 to 80% by mass, respectively.
3. The resin composition for powder coating according to claim 1 or 2, further comprising a curing agent B having a functional group capable of reacting with an epoxy group.
4. The resin composition for powder coating according to claim 3, wherein the curing agent B is an aliphatic polycarboxylic acid and/or an acid anhydride thereof.
5. A powder coating material obtained from the resin composition for powder coating materials according to any one of claims 1 to 4.
6. An article having a coating film of the powder coating material according to claim 5.
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| JP2020077319 | 2020-04-24 | ||
| JP2020-077319 | 2020-04-24 | ||
| PCT/JP2021/014843 WO2021215252A1 (en) | 2020-04-24 | 2021-04-08 | Resin composition for powder coating material, powder coating material, and article having coating film formed of said coating material |
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| JP (1) | JP7070818B2 (en) |
| KR (1) | KR20220143944A (en) |
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- 2021-04-08 WO PCT/JP2021/014843 patent/WO2021215252A1/en active Application Filing
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| JP7070818B2 (en) | 2022-05-18 |
| KR20220143944A (en) | 2022-10-25 |
| WO2021215252A1 (en) | 2021-10-28 |
| JPWO2021215252A1 (en) | 2021-10-28 |
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