CN112831242B - Amino resin alkyd extinction paint - Google Patents
Amino resin alkyd extinction paint Download PDFInfo
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- CN112831242B CN112831242B CN202110018232.XA CN202110018232A CN112831242B CN 112831242 B CN112831242 B CN 112831242B CN 202110018232 A CN202110018232 A CN 202110018232A CN 112831242 B CN112831242 B CN 112831242B
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- etherified
- alkyd
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- acrylate
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
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- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides amino resin alkyd extinction paint which comprises the following raw materials in percentage by mass: 30-50% of acrylate polymerized monomer, 15-30% of etherified alkyl benzene melamine resin, 4-12% of hydrogenated castor oil and 4-10% of poly-hydroxyalkyl aliphatic carboxylic acid. The amino resin formed by the condensation polymerization of etherified alkyl benzoguanamine formed by grafting the triazine ring of the etherified melamine on the benzene ring has good extinction property and hardness, and on the other hand, the etherified alkyl benzoguanamine resin has lower polarity and good miscibility with various alkyd resins. According to the invention, etherified alkylbenzene melamine resin is used as an amino resin component and is matched with alkyd resin, so that the amino resin alkyd flatting paint compounded by the amino resin alkyd flatting paint has good flatting property and rapid drying, and a formed paint film has good flatting property, higher hardness and excellent weather resistance, is not easy to yellow and is suitable for outdoor use.
Description
Technical Field
The invention belongs to the field of chemical coatings, and particularly relates to amino resin alkyd extinction paint.
Background
The automobile interior material mainly comprises parts such as an instrument panel, a door panel, a stand column, a seat, a ceiling, a sun shield, a side wall and the like. With the enhancement of environmental awareness of people, the requirements on the internal quality of automotive interior materials, such as environmental recycling, smell, haze, high and low temperature resistance, aging resistance, weather resistance and the like, are more and more strict. These parts have a common appearance, and the surface has decorative patterns, and the brightness tends to be dull.
At present, in order to create an extinction effect on the surface of a base material, a certain extinction agent is generally added into gloss oil, the gloss oil containing the extinction agent is coated on the surface of the base material, and the extinction agent can be distributed on the surface of a paint film formed by the gloss oil after curing and shrinking, so that the reflection of incident light rays is reduced to achieve the extinction effect. However, the extinction effect of the paint film is related to the solid content of the paint, the solid content of the solvent-based ink is low, the shrinkage degree of the paint film is high, the extinction surface is easier to form, the solid content of the UV gloss oil is high, the paint film hardly shrinks, and the paint film with the extinction effect is difficult to form. If an ultra-matte paint film with low glossiness needs to be formed, a high proportion of a flatting agent needs to be added into the UV gloss oil, so that the curing speed of the UV gloss oil is easily reduced, and meanwhile, in the production process, the glossiness of the paint film is easily unstable due to uneven distribution of the flatting agent or uneven thickness of the paint film, so that an even flatting paint film cannot be obtained. In addition, the hardness and the wear resistance of the surface of the paint film are easily reduced due to the excessively high content of the flatting agent in the coating, and the touch of the paint film is not obvious, so that the requirements of customers on the paint film with deep flatting, high wear resistance, scratch resistance, chemical resistance, weather resistance and UV resistance cannot be met.
Disclosure of Invention
The invention aims to provide an amino resin alkyd extinction paint, which is used for forming a matte film with good extinction effect on the surface of a base material.
According to one aspect of the invention, an amino resin alkyd flatting paint is provided, which comprises the following raw materials in percentage by mass: 30-50% of acrylate polymerized monomer, 15-30% of etherified alkyl benzene melamine resin, 4-12% of hydrogenated castor oil and 4-10% of poly-hydroxyalkyl aliphatic carboxylic acid. The amino resin formed by the condensation polymerization of etherified alkyl benzoguanamine formed by grafting the triazine ring of the etherified melamine on the benzene ring has good extinction property and hardness, and on the other hand, the etherified alkyl benzoguanamine resin has lower polarity and good miscibility with various alkyd resins. According to the invention, etherified alkyl benzene melamine resin is used as an amino resin component, and is matched with alkyd resin, so that the amino resin alkyd extinction paint compounded by the amino resin alkyd resin extinction paint has good extinction property and rapid drying, and a paint film formed by the amino resin alkyd extinction paint has good extinction property, higher hardness and excellent weather resistance, is not easy to yellow and is suitable for outdoor use.
Preferably, the polycondensation monomer of the etherified alkylbenzene melamine resin is etherified alkylbenzene melamine, and the number of carbon atoms included in a main carbon chain of etherified alkyl groups on the etherified alkylbenzene melamine is not less than 10. Therefore, the network structure with etherified alkyl benzoguanamine as the crosslinking center is relatively concentrated, and the matting paint containing the network structure can form a compact paint film.
Preferably, the number of carbon atoms included in the main carbon chain of the etherified alkyl group on the etherified alkylphenyl melamine is 4-10. The length of the etherified alkyl group is within the above range, and the steric effect on the polysubstituted triazine ring is alleviated, so that the polymerization reaction can be smoothly carried out. On the other hand, the triazine ring and the benzene ring in the etherified alkyl benzene substituted melamine belong to hard segments, the etherified alkyl belongs to soft segments, and the ratio of the soft segments in the etherified alkyl benzene substituted melamine is increased by increasing the chain length of the etherified alkyl, so that the construction property of the paint vehicle is improved.
Preferably, the polyhydroxyalkyl aliphatic carboxylic acid is dimethylolbutyric acid.
Preferably, the acrylate polymerized monomer includes at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
Preferably, the acrylate polymerization monomer comprises 10-20 parts by weight of butyl methacrylate and 15-25 parts by weight of ethyl acrylate.
Preferably, the raw materials further comprise 5-10% of hydroxyl acrylate by mass percent. The hydroxy acrylate has double functional groups of C ═ C double bond and COOR ester group, can participate in various polymerization reactions, and improves the crosslinking degree of the film-forming material.
Preferably, the amino resin alkyd flatting paint is prepared according to the following method: s1, catalyzing etherified alkyl benzene substituted melamine resin, hydrogenated castor oil and polyhydroxyalkyl aliphatic carboxylic acid to perform cross-linking polymerization in an aromatic hydrocarbon solvent by using organic tin under the nitrogen atmosphere to generate a prepolymer; s2, adding hydroxyl acrylate into the prepolymer, and copolymerizing the hydroxyl acrylate and the prepolymer to generate unsaturated polyester with the end group of C-C; s3, initiating unsaturated polyester and acrylic acid polymerization monomer to carry out polymerization reaction by utilizing persulfate to generate cross-linked polyester; s4, adding a polymerization inhibitor dropwise into the cross-linked polyester to block further cross-linking polymerization of the cross-linked polyester; and S5, adding a drier and a flatting agent into the slurry prepared in the S4, uniformly mixing, and sieving.
Preferably, in the raw materials of the amino resin alkyd flatting paint, the organic tin accounts for 0.2-0.5 percent, the persulfate accounts for 0.2-0.8 percent, the aromatic hydrocarbon solvent accounts for 10-20 percent, the drier accounts for 0.02-0.1 percent, and the flatting agent accounts for 1.5-2.5 percent by mass percent.
Preferably, the aromatic hydrocarbon solvent is xylene.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example 1
The embodiment is a preparation embodiment of etherified alkyl benzene substituted melamine resin, and the raw material formula of the etherified alkyl benzene substituted melamine resin related in the embodiments 2 to 4 is shown in table 1, and the production process is as follows:
the etherified alkyl benzoguanamine resin prepared in this example has the following formulation as shown in table 1, and is produced as follows:
s1, preparing materials according to the table 1;
s2, putting formaldehyde and fatty alcohol into a reaction kettle, and adding magnesium carbonate and benzoguanamine under stirring;
s3, heating after uniformly stirring, and refluxing for 3 hours;
s4, adding phthalic anhydride, adjusting the pH value to 4.4-4.5, and refluxing for 2 hours;
s5, adding dimethylbenzene, uniformly stirring, standing, and separating out a water layer;
s6, refluxing and discharging water under normal pressure, wherein the tolerance of the resin to the No. 200 paint solvent oil is 1:4 when the temperature is over 104 ℃;
s7, evaporating excessive fatty alcohol, adjusting viscosity, cooling and filtering.
TABLE 1 raw material formulation (parts by mass) of etherified alkylphenyl melamine resin
The etherified alkyl benzene substituted melamine resin prepared by adopting different kinds of fatty alcohol according to the method has the following corresponding polymerized monomer structure: (resin type, corresponding polymerized monomer)
The methyl etherified benzene substituted melamine resin is prepared by reacting methyl etherified benzene substituted melamine resin,
the ethyl etherified benzene substituted melamine resin,
propyl ether is used for etherifying benzene-substituted melamine resin,
butyl etherified benzoguanamine resin,
example 2
1. Preparation of amino resin alkyd paints
Urea-formaldehyde resin, melamine resin and the butyl-etherified benzoguanamine resin prepared in example 1 were respectively used as amino resins shown in table 2, the raw material formulations shown in table 2 were prepared, and three kinds of amino resin alkyd paints using different kinds of amino resins as raw materials were respectively prepared according to the following steps:
s1, adding amino resin, hydrogenated castor oil, dimethylolbutyric acid and dibutyltin dilaurate into dimethylbenzene in a nitrogen atmosphere, reacting for 2 hours at 80 ℃, and polymerizing the amino resin, the hydrogenated castor oil and the dimethylolbutyric acid under the catalysis of dibutyltin dilaurate to generate a prepolymer;
s2, adding hydroxyethyl acrylate into the prepolymer, keeping the temperature for 2 hours, and copolymerizing the hydroxyethyl acrylate and the prepolymer to generate unsaturated polyester with the end group of C-C;
s3, stirring the reaction liquid containing the unsaturated polyester, adding butyl methacrylate and ethyl acrylate into the reaction liquid, then adding potassium persulfate into the reaction liquid to initiate polymerization reaction of the unsaturated polyester, the butyl methacrylate and the ethyl acrylate, and continuing to keep the temperature for 1.5 hours to generate crosslinked polyester;
s4, introducing air into the cross-linked polyester, dropwise adding hydroquinone, blocking further cross-linked polymerization of the cross-linked polyester, and naturally cooling;
and S5, adding a drier and a flatting agent into the slurry prepared in the S4, uniformly mixing, and sieving.
TABLE 2 raw material formulation for amino resin alkyd paints
2. Preparation of coating film and coating film performance test
The 3 kinds of amino resin alkyd paints prepared in the example are respectively diluted until the viscosity reaches 80000mPa · s, and then the 3 kinds of amino resin alkyd flatting paints are respectively adopted to prepare a film coating sample according to the national standard GB/T1727 general paint film preparation method. And then, using the coating template to carry out a gloss test, wherein the gloss test standard is GB/T9754-88, and a 60-degree angle is selected for measurement. The test results are shown in table 3, the three amino resin alkyd paints have better quick drying property and application property, compared with the amino resin alkyd paints which respectively adopt urea-formaldehyde resin and melamine resin as amino components, the amino resin alkyd paint which is prepared by adopting butyl etherified benzoguanamine resin as the amino resin component has excellent extinction property, and the glossiness of the formed paint film is lower than 10 degrees.
TABLE 3 paintability of amino alkyd paints
Example 3
1. Preparation of amino resin alkyd extinction paint
The 4 kinds of etherified benzoguanamine resins prepared in example 1 were used as amino resin components, prepared according to the raw material formula shown in table 2 in example 2, and prepared according to the steps of amino resin alkyd paint provided in example 2, and the prepared paint is amino resin alkyd flatting paint.
2. Preparation of coating film and coating film performance test
The 4 amino resin alkyd flatting paints prepared in the example are respectively diluted until the viscosity reaches 80000mPa · s, and then the 4 amino resin alkyd flatting paints are respectively adopted to prepare a film coating sample according to the national standard GB/T1727 general paint film preparation method. The paint template was then used to perform a correlation test, the correlation test criteria being as follows: pencil hardness, QZTB J000 00013A-2016; flexibility, GB/T1731-79; adhesion, GB/T1720-79; abrasion resistance, GB/T15102-94; the glossiness GB/T9754-88 is measured by selecting a 60-degree angle.
The test results are shown in table 4, the amino resin alkyd flatting paint prepared in the embodiment 4 has a good coating effect, and as the length of the main carbon chain of the etherified alkyl group in the polymerized monomer for etherifying the benzoguanamine resin is increased, the mechanical properties such as hardness, flexibility, adhesion and wear resistance of the paint film formed by the amino resin alkyd flatting paint are optimized.
TABLE 4 Performance testing of amino resin alkyd matting paints
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the true spirit and scope of the present invention.
Claims (7)
1. The amino resin alkyd extinction paint is characterized by comprising the following raw materials in percentage by mass: 30-50% of acrylate polymerized monomer, 15-30% of etherified alkyl benzene melamine resin, 4-12% of hydrogenated castor oil, 4-10% of polyhydroxyalkyl aliphatic carboxylic acid, 5-10% of hydroxyl acrylate, 0.2-0.5% of organic tin, 0.2-0.8% of persulfate, 10-20% of aromatic hydrocarbon solvent, 0.02-0.1% of drier and 1.5-2.5% of flatting agent;
the amino resin alkyd extinction paint is prepared according to the following method:
s1, under the nitrogen atmosphere, organic tin is used for catalyzing the etherified alkyl benzene substituted melamine resin, the hydrogenated castor oil and the polyhydroxyalkyl aliphatic carboxylic acid to be cross-linked and polymerized in an aromatic hydrocarbon solvent to generate a prepolymer;
s2, adding the hydroxyl acrylate into the prepolymer, and copolymerizing the hydroxyl acrylate and the prepolymer to generate unsaturated polyester with the end group of C = C;
s3, initiating the unsaturated polyester and the acrylic acid polymerization monomer to perform polymerization reaction by utilizing persulfate to generate cross-linked polyester;
s4, adding a polymerization inhibitor dropwise into the cross-linked polyester to block further cross-linking polymerization of the cross-linked polyester;
and S5, adding a drier and a flatting agent into the slurry prepared in the S4, uniformly mixing, and sieving.
2. An amino resin alkyd matting paint according to claim 1 characterised in that: the polymeric monomer of the etherified alkylbenzene melamine resin is etherified alkylbenzene melamine, and the number of carbon atoms included in a main carbon chain of etherified alkyl on the etherified alkylbenzene melamine is not less than 10.
3. An amino resin alkyd matting paint according to claim 2 characterised in that: the number of carbon atoms included in a main carbon chain of the etherified alkyl group on the etherified alkylbenzene melamine is 4-10.
4. An amino resin alkyd matting paint according to claim 1 characterised in that: the polyhydroxyalkyl aliphatic carboxylic acid is dimethylolbutyric acid.
5. An amino resin alkyd matting paint according to claim 1 characterised in that: the acrylate polymerized monomer comprises at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.
6. The amino alkyd resin of claim 5, wherein: the acrylate polymerization monomer comprises, by mass, 10-20 parts of butyl methacrylate and 15-25 parts of ethyl acrylate.
7. An amino resin alkyd matting paint according to claim 1 characterised in that: the aromatic hydrocarbon solvent is xylene.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110018232.XA CN112831242B (en) | 2021-01-07 | 2021-01-07 | Amino resin alkyd extinction paint |
| AU2022201104A AU2022201104B2 (en) | 2021-01-07 | 2022-01-06 | Amino resin alkyd matting paint |
| PCT/CN2022/070523 WO2022148399A1 (en) | 2021-01-07 | 2022-01-06 | Amino resin alkyd matting paint |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110018232.XA CN112831242B (en) | 2021-01-07 | 2021-01-07 | Amino resin alkyd extinction paint |
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| CN112831242A CN112831242A (en) | 2021-05-25 |
| CN112831242B true CN112831242B (en) | 2022-06-10 |
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| CN (1) | CN112831242B (en) |
| AU (1) | AU2022201104B2 (en) |
| WO (1) | WO2022148399A1 (en) |
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| CN112831242B (en) * | 2021-01-07 | 2022-06-10 | 广东美涂士建材股份有限公司 | Amino resin alkyd extinction paint |
| CN115926085A (en) * | 2022-12-26 | 2023-04-07 | 佛山市华立龙科技有限公司 | Water-based phenylamine resin and preparation method and application thereof |
| CN115873464A (en) * | 2023-01-06 | 2023-03-31 | 东莞大宝化工制品有限公司 | Yellow-phase transparent extinction coating for copper blackening material and preparation method and application thereof |
| CN116284636B (en) * | 2023-04-12 | 2025-07-11 | 安徽省海徽化工有限公司 | A kind of methyl etherified amino resin and its synthesis method |
| CN117106167A (en) * | 2023-08-02 | 2023-11-24 | 江苏斯德瑞克化工有限公司 | Macromolecular polyether polyol and preparation method thereof |
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| CN103725145A (en) * | 2013-12-13 | 2014-04-16 | 武汉工程大学 | Aqueous alkide resin-acrylic acid resin hybrid coating and preparation method thereof |
| CN105153387A (en) * | 2015-09-28 | 2015-12-16 | 华南理工大学 | Polyurethane-amino resin modified waterborne alkyd resin and preparation and application thereof |
| CN111763307A (en) * | 2020-07-06 | 2020-10-13 | 华伦纳路新材料有限公司 | Fatty acid modified waterborne alkyd resin and preparation method thereof |
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| GB957367A (en) * | 1961-06-29 | 1964-05-06 | Allied Chem | Improvements relating to synthetic resin coating compositions |
| US4273690A (en) * | 1979-10-09 | 1981-06-16 | E. I. Du Pont De Nemours And Company | Coating compositions of an alkyd-acrylic graft copolymer |
| JPS60221471A (en) * | 1984-04-18 | 1985-11-06 | Nissan Motor Co Ltd | Matte coating material composition |
| JPH08165408A (en) * | 1994-10-12 | 1996-06-25 | Mitsui Toatsu Chem Inc | Aqueous resin composition |
| WO2011159909A2 (en) * | 2010-06-16 | 2011-12-22 | Ndsu Research Foundation | Monomer-grafted alkyd ester resins |
| RU2689567C1 (en) * | 2018-12-21 | 2019-05-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Composition for coating rolled and sheet metal intended for production of preserves |
| CN112831242B (en) * | 2021-01-07 | 2022-06-10 | 广东美涂士建材股份有限公司 | Amino resin alkyd extinction paint |
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- 2021-01-07 CN CN202110018232.XA patent/CN112831242B/en active Active
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- 2022-01-06 AU AU2022201104A patent/AU2022201104B2/en active Active
- 2022-01-06 WO PCT/CN2022/070523 patent/WO2022148399A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101503563A (en) * | 2009-03-17 | 2009-08-12 | 佛山市鲸鲨化工有限公司 | Water soluble alkyd resin solution and water-soluble alcohol acid amino baking varnish |
| CN103725145A (en) * | 2013-12-13 | 2014-04-16 | 武汉工程大学 | Aqueous alkide resin-acrylic acid resin hybrid coating and preparation method thereof |
| CN105153387A (en) * | 2015-09-28 | 2015-12-16 | 华南理工大学 | Polyurethane-amino resin modified waterborne alkyd resin and preparation and application thereof |
| CN111763307A (en) * | 2020-07-06 | 2020-10-13 | 华伦纳路新材料有限公司 | Fatty acid modified waterborne alkyd resin and preparation method thereof |
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| CN112831242A (en) | 2021-05-25 |
| WO2022148399A1 (en) | 2022-07-14 |
| AU2022201104B2 (en) | 2024-03-21 |
| AU2022201104A1 (en) | 2022-07-21 |
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