CN111492019B - Powder coating material and article having coating film of the same - Google Patents
Powder coating material and article having coating film of the same Download PDFInfo
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- CN111492019B CN111492019B CN201880082519.5A CN201880082519A CN111492019B CN 111492019 B CN111492019 B CN 111492019B CN 201880082519 A CN201880082519 A CN 201880082519A CN 111492019 B CN111492019 B CN 111492019B
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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
- 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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- 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
- C09D5/03—Powdery paints
Abstract
Disclosed is a powder coating material which is characterized by containing an acrylic resin (A) having an epoxy group and a curing agent (B) having a functional group capable of reacting with the epoxy group, wherein the acrylic resin (A) having an epoxy group has a molecular morphology parameter alpha value of 0.3-0.5 in Mark-Houwink-cherry Tian Tu. The powder coating material can form a cured coating film having excellent filiform rust resistance, and thus can be suitably used as a coating material for coating various articles such as aluminum wheels.
Description
Technical Field
The present invention relates to a powder coating material and an article having a coating film of the powder coating material.
Background
In recent years, due to problems such as air pollution, restrictions on organic solvents have become more severe, and attention has been paid to environmentally friendly coatings. Among them, powder coating materials are attracting attention as solvent-free type 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 coatings have a disadvantage of inferior coating film appearance compared with solvent-based coatings.
In view of this, a powder coating material has been proposed which comprises 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 an improved appearance, but has a problem of insufficient filiform rust resistance (Japanese: the Shi property).
Documents of the prior art
Patent document
Patent document 1 Japanese patent laid-open publication No. 2002-69368
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a powder coating material that can provide a cured coating film having excellent filiform rust resistance, and an article having a coating film of the powder coating material.
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 powder coating material containing: an acrylic resin (A) having a specific epoxy group, and a curing agent (B) having a functional group capable of reacting with the epoxy group.
That is, the present invention relates to a powder coating material and an article having a coating film of the powder coating material, the powder coating material comprising: and a curing agent (B) having a functional group capable of reacting with the epoxy group, wherein the acrylic resin (A) has a molecular morphology parameter alpha value of 0.3 to 0.5 in a Mark-Houwink-Sakurad (Mark-Houwink-Sakurad) diagram.
Effects of the invention
The powder coating of the present invention can form a cured coating film having excellent filiform rust resistance, and therefore can be suitably used as a coating material for coating an article such as an aluminum wheel.
Detailed Description
The powder coating material of the present invention is a powder coating material comprising an acrylic resin (a) having an epoxy group and a curing agent (B) having a functional group capable of reacting with the epoxy group, wherein the acrylic resin (a) having an epoxy group has a molecular morphology parameter α value of 0.3 to 0.5 in mark-houwink-cherry Tian Tu.
First, the acrylic resin (a) having an epoxy group will be described. From the viewpoint of obtaining a coating film excellent in coating film properties such as filiform rust resistance, it is important that the molecular morphology parameter α value in mark-houwink-cherry Tian Tu of the acrylic resin (a) having an epoxy group is 0.3 to 0.5.
The acrylic resin (A) in the present inventionThe value of the molecular morphology parameter α in Mark-Houwink-cherry Tian Tu was determined by GPC-MALS-VISCO measurement. Prepared from Mark-Howenke-Ying Tian Gongshi: [ eta ]]＝K·Mw α Deriving log [ eta ]]= logK + α logMw. Absolute molecular weight Mw is obtained from MALS and intrinsic viscosity [ eta ] is obtained from VISCO]Plotting logMw on the horizontal axis and log [ eta ]]The slope α was obtained by plotting the slope on the vertical axis.
The acrylic resin (a) having an epoxy group can be obtained, for example, by copolymerizing an acrylic monomer (a 1) having an epoxy group with another unsaturated monomer (a 2).
Examples of the acrylic monomer (a 1) having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, (meth) allyl glycidyl ether, (meth) allyl methyl glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate, and among these, glycidyl (meth) acrylate is preferable. These acrylic monomers (a 1) may be used alone or in combination of two or more.
In the present invention, "(meth) acrylic acid" means either or both of methacrylic acid and acrylic acid, "(meth) acrylate" means either or both of methacrylate and acrylate, and "(meth) acryloyl group" means either or both of methacryloyl group and acryloyl group.
Examples of the other unsaturated monomer (a 2) 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) acrylate, acrylamide, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, N-dimethylaminoethyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, styrene, p-methylstyrene, p-styrene, and the like, monofunctional monomers such as 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 end; 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 (Japanese: ヒドロキシピバリン acid エステルネオペンチルグリコールジ (メタ) アクリレート), bisphenol A-di (meth) acrylate, bisphenol A-EO-modified di (meth) acrylate, isocyanurate-modified diacrylate and the like 2-functional monomers; 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 it is preferable to use a monofunctional monomer and a polyfunctional monomer in combination, and it is preferable to use a monofunctional monomer and a 2-functional monomer in combination from the viewpoint that the possibility of gelation is low and an acrylic resin having a molecular morphology parameter α value of 0.3 to 0.5 can be easily obtained. These other unsaturated monomers (a 2) may be used alone or in combination of two or more. In the present invention, a monomer having 1 polymerizable double bond is referred to as a monofunctional monomer, a monomer having 2 polymerizable double bonds is referred to as a 2-functional monomer, and a monomer having 3 or more polymerizable double bonds is referred to as a 3-functional or higher monomer.
The amount of the acrylic monomer (a 1) having an epoxy group is preferably in the range of 10 to 70% by mass, more preferably in the range of 20 to 50% by mass, in terms of the mass ratio in the monomer component as a raw material of the acrylic resin (a), from the viewpoint of further improving the filiform rust resistance and the coating film properties of the obtained coating film. The amount of the polyfunctional monomer used is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.1 to 5% by mass, in terms of the mass ratio in the monomer component which is a raw material of the acrylic resin (a), from the viewpoint of further improving the filiform rust resistance of the resulting coating film.
The number average molecular weight of the acrylic resin (a) is preferably 1,000 to 5,000 from the viewpoint of further improving the filiform rust resistance and the physical properties of the resulting coating film. Here, the number average molecular weight is a value measured by gel permeation chromatography (hereinafter, sometimes simply referred to as "GPC") and converted to polystyrene.
The glass transition temperature of the acrylic resin (a) is preferably 30 to 80 ℃ from the viewpoint of further improving the filiform rust resistance and the physical properties of the resulting coating film.
The method for obtaining the acrylic resin (a) may be carried out by a known polymerization method using the acrylic monomer (a 1) and the other unsaturated monomer (a 2) as raw materials, and a solution radical polymerization method is preferred because of its simplest method.
The above-mentioned 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, octane, and the like; alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, and the like; ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and the like; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, and the like; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone, or two or more of them may be used in combination.
The polymerization initiator is preferably a polyfunctional polymerization initiator, more preferably a polymerization initiator having 3 or more functions, from the viewpoint of easily obtaining an acrylic resin having a molecular morphology parameter α of 0.3 to 0.5. Examples of the polyfunctional polymerization initiator include: 2,2-bis- (4,4-di-tert-butylperoxycyclohexyl) propane, 2,2-tert-butylperoxyoctane, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,3-bis- (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, tri- (tert-butylperoxy) triazine, 1,1-di-tert-butylperoxycyclohexane, 3754 zxft-butylperoxybutane, 4,4-di-tert-butylperoxyvaleric acid n-butyl ester, di-butyl peroxyhexahydroterephthalate, di-tert-butyl azelate, di-butyl peroxyadipate, di-tert-butyl peroxyadipate, 5272 ', 3772 ', 7945 ' -tetra-butyl peroxybenzoate, etc. have the function of initiating groups such as carbonyl peroxide 1 or more than four.
The polymerization initiator may be a monofunctional polymerization initiator or a combination of a polyfunctional polymerization initiator. Examples of monofunctional polymerization initiators include: cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide and other ketone peroxide compounds; peroxyketal 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, 1,1-bis (t-amylperoxycyclohexane); hydrogen peroxide compounds such as cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and tert-amyl hydroperoxide; 1,3-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diisopropylbenzene peroxide, t-butylcumyl peroxide, di-t-amyl peroxide and other dialkyl peroxide compounds; 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, tert-amyl peroxyisopropylcarbonate and tert-amyl peroxy-2-ethylhexylcarbonate; organic peroxides such as peroxy ester compounds such as t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-amyl peroxyneodecanoate, t-amyl peroxypivalate, t-amyl peroxy-2-ethylhexanoate, t-amyl peroxyn-octanoate, t-amyl peroxyacetate, t-amyl peroxyisononanoate, t-amyl peroxybenzoate and the like; and azo compounds such as 2,2 '-azobisisobutyronitrile, 1,1' -azobis (cyclohexane-1-carbonitrile), and the like.
The amount of the polymerization initiator used is preferably in the range of 0.5 to 15% by mass, more preferably in the range of 2 to 10% by mass, based on the monomer component as a raw material of the acrylic resin (a), from the viewpoint of further improving the filiform rust resistance and the coating film properties of the resulting coating film.
Next, the curing agent (B) will be described. 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, butanetricarboxylic acid and the like, anhydrides of these polycarboxylic acids, and polyphenol compounds. Among these, from the viewpoint of obtaining a high-strength coating film, aliphatic polycarboxylic acid compounds and anhydrides thereof are preferred, and dodecanedicarboxylic acid is more preferred. These curing agents (B) may be used alone or in combination of two or more.
The powder coating material of the present invention contains the acrylic resin (a) having an epoxy group and the curing agent (B) having a functional group capable of reacting with an epoxy group, and the amount of these components is preferably such that the equivalent ratio [ (EP)/(COOH) ] of the number of equivalents of epoxy groups (EP) in the acrylic resin (a) to the number of equivalents of carboxyl groups (COOH) in the curing agent (B) is in the range of 0.5 to 1.5, more preferably in the range of 0.8 to 1.2, from the viewpoint of obtaining a high-strength coating film.
Various known and conventional additives such as a flow control agent typified by an organic or inorganic pigment, a light stabilizer, an ultraviolet absorber, and an antioxidant may be added to the powder coating material of the present invention within a range not to impair the effects of the present invention. In addition, a catalyst may be added to accelerate the curing reaction during baking.
As a method for producing the powder coating material of the present invention, various conventional methods can be used, and for example, a so-called mechanical pulverization method can be used, which is: 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, and then finely pulverized and classified.
The powder coating of the present invention can be applied to various articles such as outdoor equipment, household electric appliances, automobile products, two-wheeled vehicle products, and guard rails, and is suitable for coating metal members such as aluminum wheel alloy members, from the viewpoint of obtaining a high-appearance coating film excellent in filiform rust resistance, weather resistance, impact resistance, chipping resistance, water resistance, and the like.
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 is preferably baked at a temperature of 120 to 250 ℃ for 5 to 30 minutes, from the viewpoint of obtaining 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 150 μm.
Examples
The present invention will be described in more detail with reference to specific examples. The epoxy equivalent, glass transition temperature, and number average molecular weight of the acrylic resin were measured by the following methods.
[ method for measuring epoxy equivalent ]
The measurement was carried out by the 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 glass transition temperature ]
Determined by a DSC method (differential scanning calorimetry).
Measurement device: differential scanning calorimeter (DSCQ-100 manufactured by TA INSTRUMENTS Co., ltd.)
Atmosphere conditions: under nitrogen atmosphere
Temperature range: -50 to 150 DEG C
Temperature rise rate: 5 ℃ per minute
[ method for measuring weight average molecular weight ]
Measured by GPC.
A measuring device: high efficiency 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-10 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))
76 parts by mass of xylene were charged into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet tube, and the temperature was raised to 135 ℃ under a nitrogen atmosphere. To this was added dropwise, over 6 hours, a mixture containing 18 parts by mass of styrene (hereinafter sometimes simply referred to as "St"), 42 parts by mass of methyl methacrylate (hereinafter sometimes simply referred to as "MMA"), 4 parts by mass of n-butyl methacrylate (hereinafter sometimes simply referred to as "nBMA"), 2 parts by mass of 2-ethylhexyl methacrylate (hereinafter sometimes simply referred to as "2 EHMA"), 32 parts by mass of glycidyl methacrylate (hereinafter sometimes simply referred to as "GMA"), 2 parts by mass of n-butyl acrylate (hereinafter sometimes simply referred to as "BA"), and 5 parts by mass of 2,2-bis- (4,4-di-tert-butylperoxycyclohexyl) propane (hereinafter sometimes simply referred to as "P-TA"), 0.3 parts by mass of t-butyl peroxy-2-ethylhexanoate (hereinafter sometimes simply referred to as "P-O"). After completion of the dropwise addition, the mixture was kept at the same temperature for 10 hours to carry out polymerization reaction, and then the solvent was removed under reduced pressure of 20mmHg at 160 ℃ to obtain a solid acrylic resin (A-1) having a molecular morphology parameter of 0.47, a number average molecular weight of 2,200, a glass transition temperature of 52 ℃ and an epoxy equivalent of 460 g/eq.
(Synthesis example 2 Synthesis of acrylic resin (A-2))
A solid acrylic resin (A-2) having a molecular morphology parameter of 0.42, a number average molecular weight of 2,100, a glass transition temperature of 52 ℃ and an epoxy equivalent of 600g/eq was obtained in the same manner as in Synthesis example 1 except that the compositions of the monomers and the polymerization initiator were changed to St 20 parts by mass, MMA 44 parts by mass, nBMA 6 parts by mass, isobutyl methacrylate (hereinafter, sometimes simply referred to as "iBMA"), GMA 24 parts by mass, ethyl acrylate (hereinafter, sometimes simply referred to as "EA") 3 parts by mass and P-TA 5.3 parts by mass.
(Synthesis example 3 Synthesis of acrylic resin (A-3))
A solid acrylic resin (A-3) having a molecular morphology parameter of 0.46, a number average molecular weight of 1,700, a glass transition temperature of 41 ℃ and an epoxy equivalent of 570g/eq was obtained in the same manner as in Synthesis example 1 except that the composition of the monomers and the polymerization initiator was changed to St 25 parts by mass, MMA 38 parts by mass, nBMA 4 parts by mass, 2EHMA 2 parts by mass, GMA 26 parts by mass, isobutyl acrylate (hereinafter, sometimes simply referred to as "iBA") 4 parts by mass, ethylene glycol dimethacrylate (hereinafter, sometimes simply referred to as "EDMA") 1 parts by mass and P-O8 parts by mass.
(Synthesis example 4 Synthesis of acrylic resin (A-4))
A solid acrylic resin (A-4) having a molecular morphology parameter of 0.40, a number average molecular weight of 2,600, a glass transition temperature of 60 ℃ and an epoxy equivalent of 490g/eq was obtained in the same manner as in Synthesis example 1 except that the compositions of the monomers and the polymerization initiator were changed to St 18 parts by mass, MMA 38 parts by mass, nBMA 8 parts by mass, GMA 30 parts by mass, nBA 1 part by mass, EDMA 5 parts by mass and P-O5.3 parts by mass.
(Synthesis example 5 Synthesis of acrylic resin (RA-1))
A solid acrylic resin (RA-1) having a molecular morphology parameter of 0.57, a number average molecular weight of 3,300, a glass transition temperature of 50 ℃ and an epoxy equivalent of 520g/eq was obtained in the same manner as in Synthesis example 1 except that the compositions of the monomers and the polymerization initiator were changed to St 20 parts by mass, MMA 30 parts by mass, nBMA 9 parts by mass, nBA 8 parts by mass, GMA 28 parts by mass, iBA 5 parts by mass and P-O3.5 parts by mass.
(Synthesis example 6 Synthesis of acrylic resin (RA-2))
A solid acrylic resin (RA-2) having a molecular morphology parameter of 0.52, a number average molecular weight of 2,200, a glass transition temperature of 50 ℃ and an epoxy equivalent of 580g/eq was obtained in the same manner as in Synthesis example 1 except that the compositions of the monomers and the polymerization initiator were changed to St 18 parts by mass, MMA 43 parts by mass, nBMA 10 parts by mass, 2EHMA 2 parts by mass, GMA 25 parts by mass, iBA 2 parts by mass and P-O5.3 parts by mass.
(Synthesis example 7 Synthesis of acrylic resin (RA-3))
A solid acrylic resin (RA-3) having a molecular morphology parameter of 0.53, a number average molecular weight of 2,200, a glass transition temperature of 56 ℃ and an epoxy equivalent of 490g/eq was obtained in the same manner as in Synthesis example 1 except that the compositions of the monomers and the polymerization initiator were changed to St 25 parts by mass, MMA 36 parts by mass, iBMA 7 parts by mass, 2EHMA 1 parts by mass, GMA 30 parts by mass, nBA 1 parts by mass and P-O6 parts by mass.
The compositions of the monomers and polymerization initiators of the acrylic resins (A-1) to (A-4) and (RA-1) to (RA-3) synthesized in the above-mentioned synthesis examples 1 to 7, and the property values are shown in Table 1.
[ Table 1]
Example 1 preparation of powder coating (1)
A composition containing 82 parts by mass of the acrylic resin (A-1) obtained in Synthesis example 1, 18 parts by mass of dodecanedioic acid (hereinafter, sometimes referred to simply as "DDDA"), 0.5 part by mass of benzoin, and 1 part by mass of a surface conditioner (hereinafter, simply referred to as "Resiflow LF" manufactured by ESTRON; hereinafter, simply referred to as "surface conditioner (1)") was melt-kneaded using a twin-screw kneader (APV kneader MP-2015 manufactured by Tubako Yokohama, ltd.), finely pulverized, and classified with a 200-mesh wire gauze to obtain a powder coating material (1).
Example 2 preparation of powder coating (2)
A powder coating material (2) was obtained in the same manner as in example 1 except that 82 parts by mass of the acrylic resin (A-1) and 18 parts by mass of DDDA were changed to 86 parts by mass of the acrylic resin (A-2) and 14 parts by mass of DDDA in example 1.
Example 3 preparation of powder coating (3)
A powder coating material (3) was obtained in the same manner as in example 1 except that 82 parts by mass of the acrylic resin (A-1) and 18 parts by mass of DDDA were changed to 85 parts by mass of the acrylic resin (A-3) and 15 parts by mass of DDDA in example 1.
Example 4 preparation of powder coating (4)
A powder coating material (4) was obtained in the same manner as in example 1 except that 82 parts by mass of the acrylic resin (A-1) and 18 parts by mass of DDDA were changed to 83 parts by mass of the acrylic resin (A-4) and 17 parts by mass of DDDA in example 1.
Comparative example 1 preparation of powder coating Material (R1)
A powder coating material (R1) was obtained in the same manner as in example 1 except that 82 parts by mass of the acrylic resin (A-1) and 18 parts by mass of DDDA were changed to 84 parts by mass of the acrylic resin (RA-1) and 16 parts by mass of DDDA in example 1.
Comparative example 2 preparation of powder coating Material (R2)
A powder coating material (R2) was obtained in the same manner as in example 1 except that 82 parts by mass of the acrylic resin (A-1) and 18 parts by mass of DDDA were changed to 85 parts by mass of the acrylic resin (RA-2) and 15 parts by mass of DDDA in example 1.
Comparative example 3 preparation of powder coating Material (R3)
A powder coating material (R3) was obtained in the same manner as in example 1 except that 82 parts by mass of the acrylic resin (A-1) and 18 parts by mass of DDDA were changed to 83 parts by mass of the acrylic resin (RA-3) and 17 parts by mass of DDDA in example 1.
[ preparation of cured coating film for evaluation ]
The powder coating material electrostatic powder obtained above was coated on an untreated aluminum plate (A-1050P) (7 cm. Times.15 cm) so that the film thickness after baking became 80 to 120 μm, and then baked at 160 ℃ for 20 minutes to prepare a cured coating film for evaluation.
[ evaluation of resistance to filiform rusting ]
Two 13 cm-straight scratches were made with a cutter knife on the cured coating film for evaluation obtained above so as to reach the base of the substrate, and the following test was carried out with a CASS tester. A total of 5 cycles were carried out by using, as 1 cycle, test 1 in which saline (prepared by dissolving 2.6g of copper (II) chloride hydrate, 10cc of glacial acetic acid, and 500g of crude salt (Japanese: salt deposit) in 10L of ion-exchanged water) was sprayed at a temperature of 50 ℃ and a spray pressure of 0.1MPa for 6 hours, and test 2 in which the mixture was left at a temperature of 60 ℃ and a humidity of 85% for 96 hours. After the CASS test was completed, the filiform rust generated from the scratch of the coated plate was visually observed, and the filiform rust resistance was evaluated according to the following criteria.
Excellent: the filamentous rust is less than 1mm in a direction perpendicular to the scribed linear scratches.
O: the filamentous rust is 1mm or more and less than 2mm in a direction perpendicular to the linear scratches.
X: the filamentous rust is 2mm or more in a direction perpendicular to the linear scratches.
The formulation compositions and evaluation results of the powder coating materials (1) to (4) prepared in examples 1 to 4 and the powder coating materials (R1) to (R3) prepared in comparative examples 1 to 3 are shown in table 2.
[ Table 2]
From the evaluation results of examples 1 to 4, it was confirmed that the coating film obtained from the powder coating material of the present invention was excellent in filiform rust resistance.
On the other hand, comparative examples 1 to 3 are examples in which the molecular morphology parameter α value of the acrylic resin (a) as a component of the powder coating material of the present invention is 0.5 or more, and it was confirmed that the obtained coating film had poor filiform rust resistance.
Claims (4)
1. A powder coating material characterized by comprising: the epoxy resin composition comprises an epoxy-containing acrylic resin A and a curing agent B, wherein the curing agent B has a functional group capable of reacting with an epoxy group, the acrylic resin A has a molecular morphology parameter alpha value in the range of 0.3-0.5 in Mark-Houwink-cherry Tian Tu, the acrylic resin A has a glass transition temperature of 30-80 ℃, the acrylic resin A has a polymer using a multifunctional polymerization initiator, and the acrylic resin A has a number average molecular weight of 1000-5000.
2. The powder coating material as claimed in claim 1, wherein the acrylic resin A having an epoxy group is obtained by using a polyfunctional monomer as an essential raw material.
3. The powder coating material according to claim 1 or 2, wherein the curing agent B having a functional group reactive with an epoxy group is an aliphatic polycarboxylic acid and/or an acid anhydride thereof.
4. An article having a coating film of the powder coating material according to any one of claims 1 to 3.
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| CN101497754A (en) * | 2008-01-29 | 2009-08-05 | 罗门哈斯公司 | Acrylic coating powders comprising hydrophobic particles and powder coatings therefrom |
| CN101525516A (en) * | 2008-03-04 | 2009-09-09 | 罗门哈斯公司 | Epoxy functional acrylic coating powders and the powder coating produced by the coating powders |
| CN106029796A (en) * | 2014-02-27 | 2016-10-12 | 阿克佐 诺贝尔国际涂料股份有限公司 | Acrylic resins and powder coating compositions and powder coated substrates including the same |
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| JPS5818951B2 (en) * | 1976-05-06 | 1983-04-15 | 日本原子力研究所 | Wet manufacturing method for thermosetting powder coatings |
| JPS5575403A (en) * | 1978-12-01 | 1980-06-06 | Japan Atom Energy Res Inst | Preparation of reactive microgel |
| JP2015054932A (en) * | 2013-09-12 | 2015-03-23 | Dic株式会社 | Powder coating and aluminum wheel alloy member coated with the powder coating |
| CN103865015B (en) * | 2014-03-24 | 2017-01-11 | 合肥工业大学 | High-Tg low-softening-point carboxyl-containing acrylic resin for weather-resisting powder coating |
| CN105462429B (en) * | 2015-12-11 | 2017-12-05 | 六安科瑞达新型材料有限公司 | A kind of modified solid epoxy radicals acrylic resin and preparation method thereof |
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| CN101497754A (en) * | 2008-01-29 | 2009-08-05 | 罗门哈斯公司 | Acrylic coating powders comprising hydrophobic particles and powder coatings therefrom |
| CN101525516A (en) * | 2008-03-04 | 2009-09-09 | 罗门哈斯公司 | Epoxy functional acrylic coating powders and the powder coating produced by the coating powders |
| CN106029796A (en) * | 2014-02-27 | 2016-10-12 | 阿克佐 诺贝尔国际涂料股份有限公司 | Acrylic resins and powder coating compositions and powder coated substrates including the same |
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