CN114149719B - Coating composition and application thereof - Google Patents
Coating composition and application thereof Download PDFInfo
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- CN114149719B CN114149719B CN202111337561.7A CN202111337561A CN114149719B CN 114149719 B CN114149719 B CN 114149719B CN 202111337561 A CN202111337561 A CN 202111337561A CN 114149719 B CN114149719 B CN 114149719B
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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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
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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
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4473—Mixture of polymers
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Abstract
The invention provides a coating composition and application thereof. The coating composition comprises a vinyl copolymer and an amino resin, wherein the vinyl copolymer is a vinyl copolymer of ethylenically unsaturated monomers, and the ethylenically unsaturated monomers comprise an ethylenically unsaturated carboxylic acid monomer, an ethylenically unsaturated monomer containing a hydroxyl group and an ethylenically unsaturated monomer containing a phosphoric acid group. Compared with the traditional acrylic acid anode electrophoretic coating, the coating film prepared by the coating composition through anode electrophoretic coating has better extinction property, smoothness and coating hardness, smooth hand feeling, good adherence, and good boiling water resistance, acid resistance, alkali resistance, organic solvent resistance and impact resistance.
Description
Technical Field
The invention belongs to the field of coatings, and relates to a coating composition and application thereof. In particular, the invention relates to a coating composition containing vinyl copolymer and application thereof, which are suitable for preparing a matt coating film by anodic electrophoretic coating.
Background
Electrodeposition coating is a new coating film forming method. The anode electrophoretic coating has low pollution and zero loss, is suitable for automatic production, can treat workpieces with complex shapes, and is widely applied to coating of hardware such as automobiles, motors, mobile phones, household appliances and the like.
The anode electrophoretic paint mainly comprises acrylic acid, polybutadiene, epoxy ester, phenolic resin and the like. The acrylic acid anode electrophoretic coating is prepared by mainly using acrylic acid and polymers of esters thereof as base resin, crosslinking and curing and then neutralizing by using a neutralizer. At present, internationalThere are acrylic anodic electrodeposition paints having good matting properties, for example, matte electrodeposition paint compositions disclosed in JPH 10-24587, which comprise (a) an acrylic polymer, (b) an aluminum complex compound represented by the formula (I), and Al (OR) t (L) 3-t (I) (wherein R represents an alkyl group having 1 or more carbon atoms, L represents a compound having a ketol type interdependence, and t represents an integer of 0. Ltoreq. T.ltoreq.3), (c) a silicon compound represented by the formula (II), and Si (X) 1 ) p (OX 2 ) 4-p (2) (wherein, X 1 Represents alkyl or phenyl, X 1 Which may be the same or different, X 2 Indicating a hydrogen atom or an alkyl group, X 2 And m is an integer of 0. Ltoreq. P.ltoreq.3) and (d) an amino resin, and the initial gloss (60 ℃) of the formed coating film is as low as 10 to 15. However, the extinction performance of the acrylic acid anode electrophoretic coating produced by domestic enterprises is still poor, so that the acrylic acid anode electrophoretic coating which has better extinction performance and good appearance hand feeling, mechanical property and corrosion resistance is needed to be developed.
Disclosure of Invention
Compared with the traditional acrylic acid anode electrophoretic coating, an anode electrophoretic coating formed by the coating composition has better extinction effect, smooth appearance, smooth hand feeling, high hardness, good adherence, and good boiling water resistance, acid resistance, alkali resistance, organic solvent resistance and impact resistance.
To achieve the above object, the present invention provides a coating composition comprising a vinyl copolymer of ethylenically unsaturated monomers, wherein the ethylenically unsaturated monomers include an ethylenically unsaturated carboxylic acid monomer, a hydroxyl group-containing ethylenically unsaturated monomer, and a vinyl copolymer of an ethylenically unsaturated monomer containing a phosphoric acid group, and an amino resin.
Preferably, the weight of the ethylenically unsaturated carboxylic acid monomer is 1-20% of the weight of the vinyl copolymer, the weight of the hydroxyl-containing ethylenically unsaturated monomer is 05-30% of the weight of the vinyl copolymer, and the weight of the phosphoric acid group-containing ethylenically unsaturated monomer is 0.05-20% of the weight of the vinyl copolymer.
Preferably, the ethylenically unsaturated monomer further comprises an acrylate monomer. Preferably, the weight of the acrylate monomer is 30 to 80%, more preferably 35 to 60%, and even more preferably 40 to 55% of the weight of the vinyl copolymer.
Preferably, the ethylenically unsaturated monomers further comprise styrenic monomers. Preferably, the weight of the styrenic monomer is 1 to 20%, more preferably 3 to 15%, and still more preferably 5 to 10% of the weight of the vinyl copolymer.
Preferably, the structure of the phosphorus acid group-containing ethylenically unsaturated monomer is shown as formula (1),
wherein m is 1 or 2,m + n =3.
Preferably, the weight ratio of the vinyl copolymer to the amino resin is 1.
Preferably, the coating composition further comprises a solvent; in the coating composition, the weight fraction of the vinyl copolymer is 20-60%, the weight fraction of the amino resin is 20-60%, and the weight fraction of the solvent is 10-50%.
Preferably, the solvent is at least one of hydrocarbon, alcohol, ketone, ether, alcohol ether, nitrile, sulfoxide, and amide, and more preferably at least two; the amino resin is at least one selected from complete alkyl methyl/butyl mixed etherified melamine resin, hydroxymethyl methyl/butyl mixed etherified melamine resin, imino methyl/butyl mixed etherified melamine resin, complete alkyl methylated melamine resin and imino methylated melamine resin.
In a second aspect, the present invention provides a use of the coating composition, specifically: it is used for anodic electrophoretic coating to produce a matte coating film.
In a third aspect, the invention also provides a matt coating film prepared from the coating composition.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional acrylic coating, the coating composition comprises the vinyl copolymer and the amino resin (particularly the mixed etherified melamine resin), and the formed anodic electrophoretic extinction coating has better extinction property, smoothness and coating hardness, smooth hand feeling, good adhesion, and good boiling water resistance, acid resistance, alkali resistance, organic solvent resistance and impact resistance.
2. The coating composition of the present invention does not contain isocyanates, alkoxysilyl group-containing acrylic copolymers, silicon, particulate components, etc., and can achieve an excellent matting effect without the addition of a conventional matting agent.
Drawings
FIG. 1 is a photograph showing comparative films of coating films formed by different anodic electrodeposition coatings, (A) a coating composition of comparative example 1 (gloss (60 ℃ C.) of 25), (B) a coating composition of example 1 (gloss (60 ℃ C.) of 13, having transparency property);
FIG. 2 is a photograph comparing an uncoated substrate (the upper part of the photograph, gloss (60 ℃ C.) 166) with an anodized black substrate coated by an electrophoretic anodic coating using the coating composition of example 2 to form a matte black coating (the lower part of the photograph, gloss (60 ℃ C.) 9).
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Herein, "vinyl copolymer" refers to a copolymer containing a vinyl group.
Herein, "ethylenically unsaturated monomer" is a generic name for monomer raw materials of the vinyl copolymer; if other qualifiers are added to the "ethylenically unsaturated monomer", they refer to certain monomeric starting materials for the vinyl copolymer.
The present invention will be described in detail below.
1. Vinyl copolymer
The vinyl copolymer used in the present invention is formed by copolymerizing specific monomers, and preferably, the specific monomers are ethylenically unsaturated monomers including ethylenically unsaturated carboxylic acid monomers, hydroxyl group-containing ethylenically unsaturated monomers, and phosphoric acid group-containing ethylenically unsaturated monomers.
Preferably, the vinyl copolymer is acrylic acid phosphide, and the acrylic acid anode electrophoretic coating formed by combining the acrylic acid phosphide with the amino resin through phosphating treatment has better extinction property, smoothness and coating hardness than the traditional acrylic acid anode electrophoretic coating, smooth hand feeling, good adhesion, and good boiling water resistance, acid resistance, alkali resistance, organic solvent resistance and impact resistance.
The ethylenically unsaturated carboxylic acid monomer may be selected from at least one of acrylic acid, methacrylic acid, and the like, but the selectable type of ethylenically unsaturated carboxylic acid monomer is not limited thereto. In some preferred embodiments, the weight of ethylenically unsaturated carboxylic acid monomer is from 1 to 20%, more preferably from 3 to 15%, such as from 5 to 15% or from 3 to 10% of the weight of the vinyl copolymer.
The hydroxyl group-containing ethylenically unsaturated monomer may be selected from at least one of hydroxystyrene (hydroxyystyrene), hydroxyacrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, neopentyltetraol tri (meth) acrylate, dineopentylenetetraol penta (meth) acrylate, and the like, but the selectable type of the hydroxyl group-containing ethylenically unsaturated monomer is not limited thereto. In some preferred embodiments, the weight of the hydroxyl-containing ethylenically unsaturated monomer is 5 to 30%, more preferably 10 to 25%, of the weight of the vinyl copolymer.
The above-mentioned ethylenically unsaturated monomer containing a phosphoric acid group may be selected from at least one of ethylene glycol methacrylate phosphate, polyethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, polypropylene glycol methacrylate phosphate, butylene glycol methacrylate phosphate, polybutylene glycol methacrylate phosphate, and the like, but the kind of ethylenically unsaturated monomer containing a phosphoric acid group is not limited thereto. In some preferred embodiments, the weight of the phosphorus acid group containing ethylenically unsaturated monomer is from 0.05 to 20%, more preferably from 5 to 18%, of the weight of the vinyl copolymer.
In some preferred embodiments, the structure of the ethylenically unsaturated monomer containing phosphoric acid group in the vinyl copolymer is shown in formula (1),
wherein m is 1 or 2,m + n =3.
Optionally, the ethylenically unsaturated monomer may further comprise an acrylate-based monomer.
As used herein, the term "acrylate monomer" refers to acrylates and derivatives thereof. It is preferred to use acrylate monomers of low polarity, i.e. having an acid number between 0.1 and 2mg KOH/g. The low polarity acrylate monomer may be selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-phenoxyethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, cyclic trimethylolpropane formal acrylate, isooctyl methacrylate, isodecyl acrylate, 2-ethylhexyl acrylate, ethoxylated 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, ethoxylated dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, 2-methyl-1, 3-propanediol diacrylate, ethoxylated 2-methyl-1, 3-propanediol diacrylateEsters, 2-butyl-2-ethyl-1, 3-propanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tris (2-hydroxyethyl) isocyanurate acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tripropylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated glycerol tri (meth) acrylate, triethylene glycol dimethacrylate or trimethylolpropane tri (meth) acrylate; it can also be selected from other commercially available products, such as those of Changxing materials industry (Guangdong) Co., ltd
Or
Etc.; and may be selected from two or more of the above acrylate monomers. In some embodiments of the present invention, alkyl (meth) acrylates are used as acrylate monomers, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl acrylate, isooctyl (meth) acrylate, or any combination thereof. In some preferred embodiments, the weight of the acrylate monomer is 30 to 80%, more preferably 35 to 60%, and even more preferably 40 to 55% of the weight of the vinyl copolymer.
Optionally, the ethylenically unsaturated monomer may further comprise a styrenic monomer (styrene-based monomer).
Optionally, the ethylenically unsaturated monomer may further comprise a styrenic monomer and an acrylate monomer.
As used herein, the term "styrenic monomer" refers to styrene and its derivatives. The styrene monomer may be selected from the group consisting of styrene, 4-chloro- α -methylstyrene (4-chloro- α -methylstyrene), α -methylstyrene, 4-methylstyrene, α -ethylstyrene, 4-ethylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, divinylbenzene, 3-methoxy- α -nitrostyrene (3-methoxy- α -nitrostyrene), nitrostyrene, fluorostyrene, bromostyrene, chlorostyrene, chloromethylstyrene, aminostyrene (aminostyrene), 4-methoxystyrene, 4-ethoxystyrene, acetoxystyrene (acetoxystyrene), 1-vinylnaphthalene (1-vinylnaphthalene), 2-vinylnaphthalene (2-vinylnaphthalene), 4-dodecylstyrene, 2-ethyl-4-styrene, 4- (phenyl) styrene, and combinations thereof. It is preferable to use a low-polarity styrenic monomer, examples of which include: styrene, alpha-methylstyrene, 4-methylstyrene, alpha-ethylstyrene, 4-ethylstyrene, 3-methylstyrene, 4-propylstyrene, 4-dodecylstyrene, 4-methoxystyrene, 4-ethoxystyrene or a combination of any two or more thereof. According to one embodiment of the present invention, styrene is used as the styrenic monomer. In some preferred embodiments, the styrenic monomer is present in an amount of 1 to 20%, more preferably 3 to 15%, and even more preferably 5 to 10% by weight of the vinyl copolymer.
The vinyl copolymer of the present invention can be prepared by any known vinyl polymerization method in the art to which the present invention pertains.
2. Coating composition
The coating composition of the present invention comprises the above-mentioned vinyl copolymer and amino resin, but does not contain isocyanates, acrylic copolymers having an alkoxysilyl group, silicon, particulate components, and the like. Therefore, the coating composition of the invention can realize the function of a matting coating without containing a conventional matting powder component.
Preferably, the weight ratio of the vinyl copolymer to the amino resin is in the range of 1.
The amino resin is a condensate of an amino compound such as melamine, urea, or benzoguanamine and an aldehyde compound such as formaldehyde or acetaldehyde, which is modified with a lower alcohol such as methanol, ethanol, propanol, or butanol. Specific examples of such amino resins include one or two or more kinds of fully alkyl methyl/butyl mixed etherified melamine resins, methylol methyl/butyl mixed etherified melamine resins, imino methyl/butyl mixed etherified melamine resins, fully alkyl methylated melamine resins, and imino methylated melamine resins. Preferably, the amino resin is the above melamine resin containing mixed etherified melamine, for example: a fully alkyl methyl/butyl mixed etherified melamine resin, a methylol methyl/butyl mixed etherified melamine resin or an imino methyl/butyl mixed etherified melamine resin. More preferred is a fully alkyl methyl/butyl mixed etherified melamine resin (e.g., ETERMINO 9611-98 manufactured by Changxing materials industries, guangdong, ltd.).
The amino resin of the curing agent is a condensation product of an amine or amide and an aldehyde. Examples of suitable amines or amides are melamine, benzoguanamine, urea and similar compounds. Typically, the aldehyde used is formaldehyde, but may also be selected from other aldehydes such as acetaldehyde and furfural. The condensation product contains methylol or similar hydroxyalkyl groups depending on the particular aldehyde used. Typically, the methylol group is etherified by reaction with an alcohol such as a monohydric alcohol containing one of 1 to 4 carbon atoms (e.g., methanol, ethanol, isopropanol, and n-butanol). Amino resins are available under the trademark CYMEL from American Cyanamid and RESIMENE from Monsanto Chemical. The melamine-based compound (melamine) may be a commercially available product such as Cymel 202, cymel 203, cymel 254, cymel 303, cymel 325, cymel 327, cymel 328, cymel 370, cymel 380, cymel 385, cymel 1116, cymel 1130, cymel 1133, cymel 1141, cymel 1161, cymel 1168 or Cymel 3020 manufactured by Cymite corporation; ETERMINO 9210 series, ETERMINO 9211 series, ETERMINO 9212 series, ETERMINO 9216 series, ETERMINO 9223 series, ETERMINO 9226 series, ETERMINO 9228 series, ETERMINO 9229 series, ETERMINO 9411 series (e.g. ETERMINO 9411-75), ETERMINO 9412 series (e.g. ETERMINO 9412-70), ETERMINO 9603 series (e.g. ETERMINO 9603-80), ETERMINO 9610 series (e.g. ETERMINO 9610-100), ETERMINO 9611 series (e.g. ETERMINO 9611-98), or a combination of two or more thereof, manufactured by Changxing materials industries (Guangdong) Limited.
The coating composition typically also comprises a solvent. In general, the weight fraction of the vinyl copolymer in the coating composition is 20 to 60%, for example, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, etc.; the weight fraction of amino resin is 20 to 60%, such as 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, etc.; the weight fraction of the solvent is 10 to 50%, for example, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, etc.
The solvent may be selected from at least one of hydrocarbon, alcohol, ketone, ether, alcohol ether, nitrile, sulfoxide, amide, but is not limited thereto. Wherein, the hydrocarbon can be selected from one or more of n-hexane, cyclohexane, gasoline, kerosene, pine oil, etc., but the selection is not limited to the above; the alcohol can be selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, etc., but the selection is not limited thereto; the ether is selected from diethyl ether, but is not limited thereto; the alcohol ether can be selected from one or more of ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, etc., but the selection is not limited to the above; the nitrile can be selected from one or more of acetonitrile, phenylacetonitrile and the like, but the selection is not limited to the above; the sulfoxide can be selected from one or more of dimethyl sulfoxide, etc., but the selection is not limited to the above; the amide may be selected from one or more of N, N-dimethylformamide, dimethylacetamide, and the like, but the selection is not limited thereto.
According to a preferred embodiment of the present invention, the solvent is selected from at least two of hydrocarbons, alcohols, ketones, ethers, alcohol ethers, nitriles, sulfoxides, amides, and more preferably from at least two of alcohols, ethers, alcohol ethers. More preferably at least two of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, methyl ether, diethyl ether, n-butyl ether, isobutyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol butyl ether.
3. Use of coating compositions
The coating composition can be used for preparing a delustering coating film. Preferably, the matte coating film is prepared by means of anodic electrophoretic coating.
[ electrodeposition coating method ]
The electrodeposition coating obtained by the present invention is diluted with deionized water or deionized water containing a part of a hydrophilic solvent as necessary, and used for a matte or glossy type electrodeposition coating. When the electrodeposition coating is performed, the solid content concentration of the coating bath is preferably 4 to 20% by weight. If it is less than 4% by weight, it takes a long time to obtain the desired coating thickness, and if it exceeds 20% by weight, the state of the bath becomes unstable, and it is also a problem to be able to control the amount of coating taken out from the coating system.
As for the coating method, electrodeposition is performed using the object to be coated as an anode. The coating voltage is 30 to 350 volts, preferably 50 to 300V; the energization time is 0.5 to 7 minutes, preferably 1 to 1.5 minutes. The higher the voltage, the shorter the energization time, whereas the lower the voltage, the longer the energization time. The coating voltage may be a method of applying the set voltage while applying the current, or a method of gradually increasing the set voltage. The electrodeposition object to be coated is washed with water if necessary, and then heated at 150 to 200 ℃ for 15 to 60 minutes to obtain a final coating film. The coating film thickness is preferably 5 to 30 μm. The material of the object to be coated by the electrodeposition coating method of the present invention is not particularly limited as long as it has conductivity, but a material of aluminum or an aluminum alloy is preferably used. In addition, the obtained coating film has excellent appearance such as smoothness and uniformity, and also has excellent properties such as mechanical properties, solvent resistance, chemical resistance and weather resistance.
Synthesis examples 1 to 3
Synthesis examples 1 to 3 each provide a method for preparing a resin, which specifically comprises: preparing a reaction apparatus having a stirrer, a thermometer, a monomer dropping device and a reflux cooling device, weighing each raw material according to tables 1 and 2, uniformly mixing (A1) - (A8) and (E1) in advance, adding (C) into the reaction apparatus, raising the reflux temperature to 90 ℃ under stirring, dropping the mixture of (A1) - (A8) and (E1) at 90 ℃ for 3.5 hours, adding (E2) from the end of dropping, continuing the reaction at 120 ℃ for 2 hours, and finally adding (B) and (D), to prepare a transparent viscous resin liquid having a solid content of 60% and an acid value of 36 mgKOH/g.
TABLE 1
TABLE 2
| (Code) | Synthesis example 1 | Synthesis example 2 | Synthesis example 3 |
| A1 | 2 parts by weight of | 2 parts by weight of | 2 parts by weight of |
| A2 | 2 parts by weight of | 4 parts by weight of | 1 part by |
| A3 | |||
| 4 parts by weight of | 6 parts by weight | 12 parts by weight | |
| A4 | 6 parts by weight of | 8 parts by weight of | 5 parts by weight of |
| A5 | 8 parts by weight | 10 parts by weight | 8 parts by weight of |
| |
4 parts by weight of | 4 parts by weight of | 4 parts by weight of |
| |
4 parts by weight of | 4 parts by weight of | 4 parts by weight of |
| A8 | 6 parts by weight | 0 part by weight | 0 part by weight of |
| B | 30 parts by weight of | 30 parts by weight of | 30 parts by weight of |
| C | 10 parts by weight | 10 parts by weight | 10 parts by weight |
| D | 24 parts by weight | 24 parts by weight | 24 parts by weight |
| E1 | 0.7 parts by weight | 0.7 parts by weight | 0.7 parts by weight |
| E2 | 0.2 part by weight | 0.2 part by weight | 0.2 part by weight |
| A/D value | 1.5 | 1.58 | 1.5 |
In table 2, the a/D value is the weight ratio of the vinyl copolymer to the amino resin, i.e., a/D = (A1 + A2+ A3+ A4+ A5+ A6+ A7+ A8)/D.
Example 1
176.2 parts by weight of the resin solution obtained in synthesis example 1 was taken, heated to 80 ℃ and then 7.2 parts by weight of triethylamine was added thereto, followed by stirring for 30 minutes, 160.0 parts by weight of deionized water was added thereto, and the mixture was stirred for 2 hours to obtain a uniform electrodeposition coating liquid. Placing the coating liquid in an electrolytic bath, placing a required coating test piece on an anode, electroplating for 2 minutes under the voltage of 120V and the current of 800A, then placing the test piece for air drying, baking for 30 minutes at 180 ℃, cooling for one day, measuring the physical properties of a paint film, wherein the test results are shown in Table 3, and part of the test item methods are as follows:
film thickness: the Japanese KETT LH-373 eddy current film thickness meter is specially used for measuring the thickness of an insulating film on a nonmagnetic metal material such as aluminum alloy, magnesium alloy, zinc alloy, stainless steel, copper and the like. Meets the specifications JIS K5600-1-7, JIS H8680-2, JIS H8501, ISO 2808, ISO 2360, ISO 2064, ISO 19840, BS 3900-C5, ASTM D7091-5 and ASTM E376.
Initial gloss of the coating film (60 °): the gloss was observed in the film at a light intensity of 60 ℃ as measured by UGV-5K (manufactured by Suga Test Instruments Co., ltd.).
Boiling water resistance test: preparing a sealed groove, sealing the edge of the test piece by using an adhesive tape, putting the sealed groove into the groove, covering the test piece with water, starting heating, controlling the temperature to be 98 ℃, and maintaining for 12 hours;
and (3) testing acid resistance: preparing a sealSealing the edge of the test piece with adhesive tape, placing into a groove, and adding 5wt% (H) 2 SO 4 ) Covering the test piece with the solution, and maintaining for 24 hours;
alkali resistance test: preparing a closed groove, sealing the edge of the test piece by using an adhesive tape, putting the sealed groove into the test piece, covering the test piece with 10wt% (NaOH) solution, and maintaining for 24 hours;
impact resistance: 50cm,1/4inch, load of 1kg, ASTM D2794;
MEK resistance: the paint film was wiped back and forth using a wiper with a load of 1kg, ASTM D2486;
pencil hardness: the coating hardness test pencil made by Mitsubishi Japan was used on the paint film, the load was 1kg, ASTM D3363-00;
adhesion: the film was tested using a crosscut method (Cross-cut) with 1mmX1mm per compartment and then using a 3M #600 hundred compartments adhesive tape, ASTM D3359.
Comparative example 1
The same procedures as in example 1 were conducted except that the resin solution obtained in Synthesis example 1 was replaced with the resin solution obtained in Synthesis example 2, and the test results are shown in Table 3.
Comparative example 2
The same procedures as in example 1 were conducted except that the resin solution obtained in Synthesis example 1 was replaced with the resin solution obtained in Synthesis example 3, and the test results are shown in Table 3.
Example 2
Taking 176.2 parts by weight of the resin solution obtained in synthesis example 1, heating to 80 ℃, adding 7.2 parts by weight of triethylamine, stirring for 30 minutes, adding 20 parts by weight of aqueous black color paste, finally adding 160.0 parts by weight of deionized water, and stirring for 2 hours to obtain the uniform electrodeposition coating liquid. The coating liquid is placed in an electrolytic bath, a required 6063S alloy plate test piece is placed on an anode, electroplating is carried out for 2 minutes under the voltage of 120V and the current of 800A, then the test piece is placed for air drying, the test piece is cooled for one day after being baked for 30 minutes at 180 ℃, the gloss of a paint film is measured, the gloss (60 ℃) is 9, and the test result is shown in the lower part of a picture 2.
TABLE 3
The comparative test piece appearance and gloss results of example 1 compared to comparative example 1 can be illustrated by fig. 1 and table 3.
The appearance and gloss results of the example 2 coating composition applied to a matte black coating film compared to the original untreated substrate coupon are illustrated in FIG. 2.
Compared with the comparative examples 1-2, the vinyl copolymer is subjected to phosphating treatment, and the obtained paint film has better flatting property, flatness and coating hardness, is excellent in acid resistance, alkali resistance, solvent resistance and impact resistance, and is suitable for application of the anodic electrophoretic paint.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. An anode electrophoretic coating composition, which is characterized by comprising a vinyl copolymer and an amino resin, wherein the vinyl copolymer is a vinyl copolymer of ethylenically unsaturated monomers, and the ethylenically unsaturated monomers comprise ethylenically unsaturated carboxylic acid monomers, hydroxyl-containing ethylenically unsaturated monomers, acrylate monomers, styrene monomers and phosphoric acid group-containing ethylenically unsaturated monomers; meanwhile, the coating composition does not contain isocyanate, acrylic copolymer with alkoxy silane group and silicon particle components, and realizes the function of the extinction coating under the condition of not containing extinction powder components;
the weight of the ethylenic unsaturated carboxylic acid monomer is 1-20% of the weight of the vinyl copolymer, the weight of the hydroxyl-containing ethylenic unsaturated monomer is 5-30% of the weight of the vinyl copolymer, the weight of the acrylic ester monomer is 30-80% of the weight of the vinyl copolymer, the weight of the styrene monomer is 1-20% of the weight of the vinyl copolymer, and the weight of the phosphoric acid group-containing ethylenic unsaturated monomer is 5-18% of the weight of the vinyl copolymer.
2. The coating composition of claim 1, wherein the ethylenically unsaturated monomer containing a phosphoric acid group has the structure of formula (1),
wherein m is 1 or 2,m + n=3.
3. The coating composition according to claim 1, wherein the weight ratio of the vinyl copolymer to the amino resin is 1.
4. The coating composition according to any one of claims 1 to 3, further comprising a solvent; in the coating composition, the weight fraction of the vinyl copolymer is 20-60%, the weight fraction of the amino resin is 20-60%, and the weight fraction of the solvent is 10-50%.
5. The coating composition of claim 4, wherein the solvent is at least one of a hydrocarbon, an alcohol, a ketone, an ether, an alcohol ether, a nitrile, a sulfoxide, an amide; the amino resin is at least one selected from complete alkyl methyl/butyl mixed etherified melamine resin, hydroxymethyl methyl/butyl mixed etherified melamine resin, imino methyl/butyl mixed etherified melamine resin, complete alkyl methylated melamine resin and imino methylated melamine resin.
6. The coating composition of claim 5, wherein the solvent is at least two of a hydrocarbon, an alcohol, a ketone, an ether, an alcohol ether, a nitrile, a sulfoxide, and an amide.
7. Use of a coating composition according to any one of claims 1 to 6 for anodic electrocoating to produce a matte coating film.
8. A matte coating film obtained from the coating composition according to any one of claims 1 to 6.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5967396A (en) * | 1982-10-08 | 1984-04-17 | Kansai Paint Co Ltd | Dull finish coating method by electrodeposition |
| JP2002363503A (en) * | 2001-06-11 | 2002-12-18 | Shinto Paint Co Ltd | High weatherability color electrodeposition coating material and its electrodeposition coating method |
| CN109320652A (en) * | 2018-09-29 | 2019-02-12 | 佛山市三水协佳化工有限公司 | A kind of synthetic method from delustring water-based acrylic resin |
| CN112771127A (en) * | 2018-06-27 | 2021-05-07 | Prc-迪索托国际公司 | Electrodepositable coating compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11199803A (en) * | 1998-01-14 | 1999-07-27 | Toray Ind Inc | Matte electrocoating material composition and its production |
| JP6821399B2 (en) * | 2016-11-10 | 2021-01-27 | 関西ペイント株式会社 | Matte clear paint composition for aluminum parts |
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- 2021-11-11 CN CN202111337561.7A patent/CN114149719B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5967396A (en) * | 1982-10-08 | 1984-04-17 | Kansai Paint Co Ltd | Dull finish coating method by electrodeposition |
| JP2002363503A (en) * | 2001-06-11 | 2002-12-18 | Shinto Paint Co Ltd | High weatherability color electrodeposition coating material and its electrodeposition coating method |
| CN112771127A (en) * | 2018-06-27 | 2021-05-07 | Prc-迪索托国际公司 | Electrodepositable coating compositions |
| CN109320652A (en) * | 2018-09-29 | 2019-02-12 | 佛山市三水协佳化工有限公司 | A kind of synthetic method from delustring water-based acrylic resin |
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