CN114426796A - High-weather-resistance coil coating composition and application thereof - Google Patents

High-weather-resistance coil coating composition and application thereof Download PDF

Info

Publication number
CN114426796A
CN114426796A CN202011177320.6A CN202011177320A CN114426796A CN 114426796 A CN114426796 A CN 114426796A CN 202011177320 A CN202011177320 A CN 202011177320A CN 114426796 A CN114426796 A CN 114426796A
Authority
CN
China
Prior art keywords
coating composition
coil coating
polyester resin
agent
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011177320.6A
Other languages
Chinese (zh)
Inventor
李玉玲
林宏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paint Industrial Coatings Shanghai Co ltd
Original Assignee
Nippon Paint Industrial Coatings Shanghai Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Paint Industrial Coatings Shanghai Co ltd filed Critical Nippon Paint Industrial Coatings Shanghai Co ltd
Priority to CN202011177320.6A priority Critical patent/CN114426796A/en
Publication of CN114426796A publication Critical patent/CN114426796A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00Metallic substrate
    • B05D2202/10Metallic substrate based on Fe
    • B05D2202/15Stainless steel
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides a high-weather-resistance coil coating composition, which comprises the following components in percentage by mass: 30-80% of polyester resin; 2-15% of amino resin; 4-10% of a curing agent; 1-3% of an adhesion promoter; 1-5% of an auxiliary agent; and, the balance of solvent; the polyester resin is saturated polyester resin, the number average molecular weight Mn is 3000-20000, the hydroxyl value is 30-70mg KOH/g, the acid value is not more than 10mg KOH/g, and a molecular chain of the polyester resin contains a neopentyl structure. The high-weather-resistance coil coating composition can be directly coated on a metal substrate such as stainless steel without pretreatment, has excellent processability and adhesion, has excellent weather resistance, stain resistance, MEK resistance, corrosion resistance and wear resistance after being cured, and is mainly applied to external coating of metal coils such as stainless steel.

Description

High-weather-resistance coil coating composition and application thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a weather-resistant coating for a stainless steel plate, a preparation method and application.
Background
The stainless steel has the excellent characteristics of unique mirror surface brightness, higher wear resistance, excellent corrosion resistance and the like, is widely applied to the industries of life medical treatment, home appliance decoration and landscape finishing, and gives people a gorgeous and noble feeling.
With the improvement of the requirements of people on the high-grade and diversified decoration of materials, the application development prospect of the stainless steel plate is wider and wider. However, the application development of stainless steel depends greatly on its surface treatment technology, and the surface of stainless steel is required to have excellent antifouling, protecting, polishing and antifouling effects, and the daily cleaning and maintenance of users are simple and convenient.
In the prior art, a common 304 stainless steel plate is subjected to surface treatment, so that the stainless steel plate has antifouling and stain-resistant characteristics and can keep mirror brightness in an indoor environment. However, in the outdoors, the smooth surface is corroded by sunlight and rain, and the luster is easily removed, so that the beauty of the stainless steel plate is influenced. The key to solving this problem is to improve the weatherability of stainless steel. The existing outdoor stainless steel is added with elements such as nickel, cobalt and the like on the basis of common stainless steel, so that the weather resistance is improved, but the process is complex, the production cost is higher, and the environmental pollution is serious.
Patent CN101215438B discloses a stain-resistant and aging-resistant stainless steel coating and a preparation method thereof, wherein silicon dioxide and fluorine-containing resin are used to modify acrylic acid, but the addition amount of fluorine-containing resin needs to be strictly controlled, which hinders the wide application of the coating.
Patent CN105462460B discloses an anti-fouling and fingerprint-resistant stainless steel plate water-based paint and a preparation method thereof, which mainly comprises modified water-based polyester resin and silica sol, but the corrosion resistance of the paint is less than 360h, and the paint cannot be applied to outdoor high-corrosion-resistance environment.
Therefore, it is required to provide a stainless steel surface treatment coating with high weather resistance, which has a simple coating process and can meet different conditions and the use requirements of specific environments such as indoor household appliances to outdoor solarization and the like.
Disclosure of Invention
The first purpose of the invention is to provide a single-component coating composition, which combines the primer and the topcoat in the traditional sense into a whole, so that the coating formed by curing the single-component coating composition has high interlayer bonding force and high adhesive force with a base material, has the decoration of the topcoat and can meet the requirements of diversified decoration.
A second object of the present invention is to provide the use of the above one-component coating composition, which can be directly coated on a general stainless steel substrate without performing a surface chemical treatment of the substrate. The roll coating process is a coiled roll coating process, is quick in baking, does not need pretreatment, and is simple to operate, high in production efficiency, energy-saving and efficient in process.
In order to achieve the above object, according to one aspect of the present invention, there is provided a highly weather-resistant coil coating composition comprising, in mass percent: 30-80% of polyester resin, 2-15% of amino resin, 4-10% of curing agent and 1-3% of adhesion promoter; 1-5% of an auxiliary agent; and, the balance solvent; the polyester resin is saturated polyester resin, the number average molecular weight Mn is 3000-20000, the hydroxyl value is 30-70mg KOH/g, the acid value is not more than 10mg KOH/g, and a molecular chain of the polyester resin contains a neopentyl structure.
In some embodiments, the polyester resin is polymerized from a polyol and a polyacid. Preferably, the polyester resin is polymerized from a diol and a diacid. More preferably, the polyester resin is polymerized from neopentyl glycol and a dibasic acid in the presence of an organotin catalyst.
In some embodiments, the polyester resin is prepared by polymerizing neopentyl glycol, adipic acid, isophthalic acid, terephthalic acid, and trimellitic anhydride in the presence of an organotin catalyst, followed by dilution with a solvent. Therefore, the molecular chain of the synthesized polyester resin has a neopentyl structure, so that the polyester resin has shield-shaped protection.
Further, in the polyester resin obtained by the polymerization reaction, the thermal stability and the weather resistance of a coating layer cured by the high weather resistance coil coating composition are greatly improved by the steric hindrance effect provided by the molecular side groups such as isophthalic acid, terephthalic acid and trimellitic anhydride.
Further, the polyester resin obtained by the above polymerization reaction has a highly branched dendritic structure, contains a plurality of terminal functional groups, not only provides a high hydroxyl value and high processing flexibility to the polyester resin, but also allows the polyester resin to react with an adhesion promoter-based polymer, thereby providing excellent film-forming properties to the high weather-resistant coil coating composition. Therefore, the high-weatherability coil coating composition provided by the invention can form stable chemical interaction with a substrate (especially a metal substrate) directly through the bridging link of the adhesion promoter after curing.
Further, the polyester resin obtained by the polymerization reaction has high density of a network structure, and can greatly improve the characteristics of stain resistance, fingerprint resistance, MEK resistance, abrasion resistance, corrosion resistance and the like of a coating formed by curing the high-weather-resistant coil coating composition.
Further, the polyester resin obtained by the above polymerization reaction can also help the wetting and dispersion of toner, so that the coating layer formed by curing the high weather resistance coil coating composition also has high gloss, thereby ensuring the effects of light retention and coloring of the coating layer.
In some embodiments, the amino resin is at least one of a methylated melamine resin, a butylated urea formaldehyde resin, a butylated melamine resin, and a benzoguanamine formaldehyde resin.
In some embodiments, the curing agent is an isocyanate resin. Preferably, the curing agent is a blocked isocyanate resin.
In some embodiments, the solvent is at least one of cyclohexanone, propylene glycol methyl ether acetate, ethylene glycol butyl ether, xylene, S-100 mineral spirits, S-150 mineral spirits, trimethylbenzene mineral spirits, and a mixture of dibasic esters.
In some embodiments, the adhesion promoter is an epoxy, silanol, phosphate modified polymer.
In some embodiments, the highly weatherable coil coating composition further includes an auxiliary agent that is at least one of a catalyst, a leveling agent, a defoamer, a dispersant, a pigment and a matting agent.
In some embodiments, the catalyst is a blocked sulfonic acid catalyst, the leveling agent is a non-silicon leveling agent, the defoaming agent is a non-silicon defoaming agent, and the particle size of the matting powder is less than or equal to 3 μm; and, preferably, the catalyst is at least one of dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, dodecylbenzene sulfonic acid, and p-toluenesulfonic acid.
According to another aspect of the present invention, there is also provided a method of preparing the high weather-resistant coil coating composition as described above, comprising:
(1) adding saturated polyester resin, amino resin and curing agent into a reaction vessel in sequence, mixing and stirring uniformly;
(2) then adding the auxiliary agent under the stirring state, and adding the solvent after uniformly stirring;
(3) adjusting the viscosity to obtain the high-weather-resistance coil coating composition.
The rotating speed in the stirring process in the step (1) and the step (2) is 600-800RPM, and the stirring time is 10 minutes.
According to a further aspect of the invention, the invention also provides the use of the above-described highly weather-resistant coil coating composition in painting.
In some embodiments, in the application, the high weather resistance coil coating composition is directly coated on a substrate and cured and formed by high temperature baking.
The invention has the following beneficial effects:
the invention solves the problems of easy pulverization, reduced gloss and poor durability of the common stainless steel coating outdoors, and simultaneously endows the surface of the stainless steel with fingerprint resistance, so that the stainless steel can keep the exquisite appearance for a long time in the using process. Meanwhile, the coating formula is suitable for a roller coating process, so that the production efficiency is effectively improved, and the energy and the cost are saved.
Compared with the prior art, the invention has the advantages and positive effects that:
1) tests show that the ultraviolet light aging resistance, chalking resistance, stain resistance and paint film durability of a coating formed by curing the high-weather-resistance coil coating composition are far higher than those of common fingerprint-resistant coatings, and the coating has more excellent weather resistance;
2) tests show that the interlayer adhesion between a coating formed by curing the high-weather-resistance coil coating composition and a substrate is strong, and the high-weather-resistance coil coating composition has good processing and forming performance, excellent MEK wiping resistance effect, excellent wear resistance and durability in use;
3) the high-weather-resistance coil coating composition is a single-component coating, and is different from the existing double-component coating in that the high-weather-resistance coil coating composition can be coated in a coil form by adopting a roller coating process and quickly baked, and the coating process is simple and efficient;
4) the high-weather-resistance coil coating composition combines the traditional primer and the traditional top coat into a whole, can realize various decorations, and enables the appearance of a workpiece product to be more changed.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The invention provides a high-weather-resistance coil coating composition, which comprises the following components: polyester resin, amino resin, a curing agent, an adhesion promoter, an auxiliary agent and a solvent.
<Polyester resin>
The polyester resin is present in an amount of not less than 30% by weight, preferably not less than 40% by weight, based on the weight of the highly weatherable coil coating composition. And the polyester resin is contained in an amount of not more than 80% by mass, preferably not more than 70% by mass, more preferably not more than 60% by mass, based on the weight of the highly weather-resistant coil coating composition.
The polyester resin is a saturated polyester resin. The acid value of the polyester resin is 3-5mg KOH/g, the hydroxyl value is 60mg KOH/g, the solid content is 60 wt%, and the number average molecular weight Mn is 3700-14000.
The polyester resin is polymerized from polyhydric alcohol and polybasic acid. Preferably, the polyester resin is polymerized from a diol and a diacid. More preferably, the polyester resin is polymerized from neopentyl glycol and a dibasic acid in the presence of an organotin catalyst. Particularly, the polyester resin is prepared by carrying out polymerization reaction on neopentyl glycol, adipic acid, isophthalic acid, terephthalic acid and trimellitic anhydride under the action of an organic tin catalyst, and then diluting the obtained product by a solvent. Therefore, the molecular chain of the synthesized polyester resin has a neopentyl structure, so that the polyester resin has shield-shaped protection.
The polyester resin may be any commercially available saturated polyester resin satisfying the above description, such as, but not limited to, saturated polyester resins produced by Toyobo, Evonik, Arkema, Changxing, Kolida, SK, and the like, with specific models such as, but not limited to, SKYBON ES 420, ETERKYD 50566-R-60, VIALKYD AN 950/70X, and the like.
<Amino resin>
The amino resin is present in an amount of not less than 2% by weight, preferably not less than 3% by weight, based on the weight of the highly weather resistant coil coating composition. And the amino resin is contained in an amount of not more than 15% by mass, preferably not more than 10% by mass, based on the weight of the highly weather-resistant coil coating composition.
The amino resin is at least one of methylated melamine resin, butylated urea formaldehyde resin, butylated melamine resin and benzoguanamine formaldehyde resin. Preferably, the amino resin is one or a mixture of methylated melamine resin and butylated melamine resin. More preferably, the amino resin is methylated melamine resin, so that the cured film of the high-weather-resistance coil coating composition has high flexibility, excellent formula stability, and excellent scratch resistance and interlayer adhesion.
The amino resin may be any commercially available amino resin satisfying the above description, such as, but not limited to, cyanotex (r) manufactured amino resins, specific types such as, but not limited to, CYMEL303, CYMEL688, CYMEL 325.
<Curing agent>
The curing agent is present in an amount of not less than 4% by weight, preferably not less than 5% by weight, based on the weight of the highly weatherable coil coating composition. And the curing agent is contained in an amount of not more than 10% by mass, preferably not more than 8% by mass, based on the weight of the highly weather-resistant coil coating composition.
The curing agent is closed isocyanate resin. And (3) condensing the unblocked isocyanic acid and the alcohol to form the polyurethane resin. Exemplary isocyanate resins include, but are not limited to, polyisocyanates, such as the cyclic trimer, the cocyclic trimer of hexamethylene diisocyanate or methylene diphenyl diisocyanate, or mixtures of these polyisocyanates.
The curing agent may be any commercially available blocked isocyanate resin satisfying the above description, such as but not limited to bayer BL3175, Evonik B1358.
<Adhesion promoter>
The weight of the high-weather-resistance coil coating composition is taken as a calculation unit, and the mass percentage content of the adhesion promoter is not less than 1.0%. And the mass percentage content of the adhesion promoter is not higher than 3 percent by weight of the high-weather-resistance coil coating composition.
The adhesion promoter is epoxy, silanol and phosphate modified polymer. Preferably, the adhesion promoter is a phosphate modified polymer.
The adhesion promoter may be any commercially available adhesion promoter that meets the above description, such as, but not limited to, SN-7063, TZ8805, ADP, PAE206, Lubrizol-2063.
<Auxiliary agent>
The auxiliary agent is at least one of a catalyst, a flatting agent, a defoaming agent, a dispersing agent, a pigment and a matting agent. These adjuvants may optionally be added to the composition to aid in the flow, wetting and appearance of the coating.
If used, the coagent is present in an amount of no less than 0.01 percent by weight, preferably no less than 0.1 percent by weight, based on the weight of resin solids. And the mass percentage of the auxiliary agent is not higher than 5% based on the weight of the resin solid.
The catalyst is a blocked sulfonic acid catalyst, preferably, the catalyst is at least one of dinonylnaphthalene disulfonic acid (DNNDSA), dinonylnaphthalene sulfonic acid (DNNSA), dodecylbenzene sulfonic acid (DDBSA) and P-toluenesulfonic acid (P-TSA). The catalyst may be any commercially available blocked sulfonic acid type acid catalyst satisfying the above description, such as, but not limited to, BYK 110, BYK 115, BYK P-104, SOLSPERSE 2000. If used, the catalyst is present in an amount of no less than 0.1% by weight, based on the weight of the highly weatherable coil coating composition. And the mass percentage of the catalyst is not higher than 2 percent by weight of the high weather resistance coil coating composition.
The leveling agent is a non-silicon leveling agent. The leveling agent may be any commercially available non-silicon leveling agent that meets the above description, such as, but not limited to BYK-392, BYK-054, BYK-355, BYK-358N, AFCONA-3773 of Pico chemistry.
The defoaming agent is a non-silicon defoaming agent. The defoamer can be any commercially available non-silicon defoamer that meets the above description, such as, but not limited to, BYK-352, BYK-354, AFCONA 2720.
The dispersant is a commercially available dispersant such as, but not limited to, a DA1040 type dispersant and BYK170 dispersant, BYK180 dispersant.
The pigments are commercially available pigments such as, but not limited to, COLOUR BLACK FW200 carbon BLACK pigment and phthalocyanine blue P.B.15:2 pigment.
The matting powder is commercially available matting powder with the particle size less than or equal to 3 mu m, such as but not limited to Tosoh E-1011 matting powder and SYLOID ED-2 matting powder.
<Solvent(s)>
The solvent is at least one selected from cyclohexanone, propylene glycol methyl ether acetate, ethylene glycol butyl ether, xylene, S-100 solvent oil, S-150 solvent oil, trimethylbenzene solvent oil and dibasic ester mixture.
In the invention, the high-weatherability coil coating composition is directly coated on a substrate and is baked and cured at high temperature to form a coating on the substrate (especially a stainless steel substrate). And the resulting coating was tested.
Unless stated otherwise, the test is carried out according to the national standard GB/T13448-2006 in the following examples, and the result meets the requirements of the national standard GB/T13448-2006.
The MEK wiping resistance test requires sample preparation, test environment and test procedures as specified in GB/T13448-2006 of 10.2. The coated surface was wiped with a cotton gauze by hand, dipped in butanone solution, rubbed 100 times with an arm force of about 10N, and then compared to the non-wiped area, the area wiped with organic solution butanone (MEK) should have no visible color difference and coating breakage. The specific test method can refer to the Haier group enterprise standard Q/HR 0502008-2009.
The contamination resistance test requires sample preparation, test environment and test procedures as specified in GB/T13448-2006 of 10.2. The test piece is coated by the marker pen (red, blue and black), and after being placed for 24 hours, the surface of the test piece is not discolored after being wiped by the neutral lotion.
The weather-resistant QUVB test requires that an artificial aging resistance test is carried out by adopting UV-b aging resistance equipment of Q-Lab company according to the TB/T1527-2011 standard. The wavelength of a light source is 313nm, the irradiance is 0.71W/m2, the illumination and condensation period is 4h, the cycle is continuous, and the gloss, the color difference and the appearance change of the coating film are tested at intervals.
Example 1
The highly weatherable coil coating composition according to the present invention was prepared according to the following formulation of table 1:
table 1 example 1 highly weatherable coil coating composition
Components Name (R) Amount (wt%)
Polyester resin NP 5055 65%
Amino resin Cymel 303 6%
Curing agent DESMODUR BL3175A 4%
Catalyst and process for preparing same AAC2500 1.0%
Adhesion promoter SN7063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
Adding saturated polyester resin, amino resin and a curing agent into a container in sequence, mixing and stirring uniformly, then adding a catalyst, an adhesion promoter, a flatting agent and a defoaming agent under stirring, stirring uniformly, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a coating-4 cup, filtering and packaging to obtain the high-weather-resistance coil coating composition.
Coating and plate making: the obtained high weather resistance coil coating composition was roll coated on a stainless steel plate with a wire bar, baked in an oven at 320 ℃ for 30s, and the sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
Example 2
The highly weatherable coil coating composition according to the present invention was prepared according to the following formulation of table 2:
table 2 example 2 high weather resistance coil coating composition
Components Name (R) Amount (wt%)
Polyester resin NP 5055 54%
Amino resin Cymel 325 4%
Curing agent DESMODUR BL3175A 4%
Catalyst and process for preparing same Nacure 1051 0.4%
Adhesion promoter SN7063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
Adding saturated polyester resin, amino resin and a curing agent into a container in sequence, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a flatting agent and a defoaming agent under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the high-weather-resistance coil coating composition.
Coating and plate making: the obtained high weather resistance coil coating composition was roll coated on a stainless steel plate with a wire bar, baked in an oven at 320 ℃ for 30s, and the sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
Example 3
The highly weatherable coil coating composition according to the present invention was prepared according to the following formulation of table 3:
table 3 example 3 high weather resistance coil coating composition
Components Name (R) Amount (wt%)
Polyester resin NP 5055 60%
Amino resin Cymel 688 4%
Curing agent DESMODUR BL3175A 6%
Catalyst and process for preparing same Nacure 1051 0.6%
Adhesion promoter SN-7063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
Adding saturated polyester resin, amino resin and a curing agent into a container in sequence, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a flatting agent and a defoaming agent under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the high-weather-resistance coil coating composition.
Coating and plate making: the obtained high weather resistance coil coating composition was roll coated on a stainless steel plate with a wire bar, baked in an oven at 320 ℃ for 30s, and the sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
Example 4
The highly weatherable coil coating composition of the present invention was prepared according to the following formulation of table 4:
table 4 example 4 high weather resistance coil coating composition
Components Name (R) Amount (wt%)
Polyester resin NP 5055 65%
Amino resin Cymel 303 6%
Curing agent DESMODUR BL3175A 8%
Catalyst and process for preparing same AAC2500 0.8%
Adhesion promoter Lubrizol2063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
Adding saturated polyester resin, amino resin and a curing agent into a container in sequence, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a flatting agent and a defoaming agent under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the high-weather-resistance coil coating composition.
Coating and plate making: the obtained high weather resistance coil coating composition was roll coated on a stainless steel plate with a wire bar, baked in an oven at 320 ℃ for 30s, and the sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
Example 5
The highly weatherable coil coating composition of the present invention was prepared according to the following formulation of table 5:
table 5 example 5 highly weatherable coil coating composition
Components Name (R) Amount (wt%)
Polyester resin NP 5055 65%
Amino resin Cymel 303 6%
Curing agent DESMODUR BL3175A 6%
Catalyst and process for preparing same Nacure 1051 0.5%
Adhesion promoter Lubrizol2063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
Adding saturated polyester resin, amino resin and a curing agent into a container in sequence, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a flatting agent and a defoaming agent under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the high-weather-resistance coil coating composition.
Coating and plate making: the obtained high weather resistance coil coating composition was roll coated on a stainless steel plate with a wire bar, baked in an oven at 320 ℃ for 30s, and the sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
Example 6
The highly weatherable coil coating composition of the present invention was prepared according to the following formulation of table 6:
TABLE 6 EXAMPLE 6 highly weatherable coil coating composition
Components Name (R) Amount (wt%)
Polyester resin NP 5055 65%
Dispersing agent DA 1040 0.5
Pigment (I) COLOUR BLACK FW200 0.34
Amino resin Cymel 303 6%
Curing agent DESMODUR BL3175A 6%
Catalyst and process for preparing same AAC2500 0.8%
Adhesion promoter Lubrizol2063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Matting powder E-1011 1.0%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
Adding saturated polyester resin, S100 solvent and DA1040 into a container in sequence, mixing and stirring uniformly, then adding pigment COLOUR BLACK FW200 under stirring, stirring for 3 minutes, then grinding by using a grinder until the fineness is not more than 10 micrometers, then adding amino resin, curing agent, adhesion promoter, acid catalyst, defoaming and leveling agent and the like under stirring, stirring uniformly, adjusting color, gloss and viscosity as required, adding residual solvent, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a coating-4 cup, filtering and packaging to obtain the high-weather-resistance coil coating composition.
Coating and plate making: the obtained high weather resistance coil coating composition was roll coated on a stainless steel plate with a wire bar, baked in an oven at 320 ℃ for 30s, and the sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
Example 7
The highly weatherable coil coating composition of the present invention was prepared according to the following formulation of table 7:
table 7 example 7 high weather resistance coil coating composition
Components Name (R) Amount (wt%)
Polyester resin NP 5055 65%
Dispersing agent BYK 170 0.5
Pigment (I) Phthalocyanine blue P.B.15:2 1.6
Amino resin Cymel 303 6%
Curing agent DESMODUR BL3175A 8%
Catalyst and process for preparing same Nacure 1051 0.5%
Adhesion promoter Lubrizol2063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Matting powder E-1011 1.0%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
Adding saturated polyester resin, S100 solvent and BYK170 into a container in sequence, mixing and uniformly stirring, then adding pigment phthalocyanine blue P.B.15:2 under stirring, stirring for 3 minutes, then grinding by using a grinding machine until the fineness is not more than 10 micrometers, then adding amino resin, curing agent, adhesion promoter, acid catalyst, defoaming and leveling agent, matting powder and the like under stirring, uniformly stirring, adjusting color, gloss and viscosity as required, finally adding residual solvent, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the high-weather-resistance coil coating composition.
Coating and plate making: the obtained high weather resistance coil coating composition was roll coated on a stainless steel plate with a wire bar, baked in an oven at 320 ℃ for 30s, and the sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
Comparative example 1
The coating composition of comparative example 1 was prepared according to the formulation of table 8 below:
TABLE 8 coating composition of comparative example 1
Figure BDA0002749046280000131
Figure BDA0002749046280000141
Adding saturated polyester resin, amino resin and a curing agent into a container in sequence, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a flatting agent and a defoaming agent under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the coating composition with the proportion of 1.
Coating and plate making: the coating composition of the ratio 1 obtained was roll coated on a stainless steel plate with a wire bar, baked in an oven at 320 ℃ for 30s, sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
It should be noted that: the polyester resin used in comparative example 1 was a 3011A type polyester resin supplied by NOROO. The hydroxyl value of the polyester resin is 20 to 30 (excluding 30) mg KOH/g, and is not within the range of the hydroxyl value of the polyester resin described in the present invention, and therefore, is not a polyester resin to which the present invention is applied. Thus, this comparative example 1 is only a comparative example.
Comparative example 2
The coating composition of comparative example 2 was prepared according to the formulation of table 9 below:
TABLE 9 coating composition of comparative example 2
Components Name (R) Amount (wt%)
Polyester resin YL-301(Yili) 60%
Amino resin Cymel 303 6%
Curing agent DESMODUR BL3175A 6%
Catalyst and process for preparing same AAC2500 1.0%
Adhesion promoter SN7063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
And (2) sequentially adding saturated polyester resin, amino resin and a curing agent into a container, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a leveling agent and a defoaming agent under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the coating composition of the comparative example 2.
Coating and plate making: the resulting coating composition of comparative example 2 was wire bar roll coated on a stainless steel plate, baked in an oven at 320 ℃ for 30s, sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
It should be noted that: the polyester resin used in this comparative example 2 was a polyester resin supplied by Yillie corporation as YL-301 type. The number average molecular weight Mn of the polyester resin is 2000 to 3000 (not including 3000), and is not within the range of the number average molecular weight of the polyester resin described in the present invention, and therefore is not a polyester resin to which the present invention is applied. Therefore, this comparative example 2 is merely a comparative example.
Comparative example 3
The coating composition of comparative example 3 was prepared according to the formulation of table 10 below:
TABLE 10 coating composition of comparative example 3
Components Name (R) Amount (wt%)
Polyester resin NP 5055 60%
Amino resin Cymel 303 8%
Curing agent DESMODUR BL3175A 4%
Catalyst and process for preparing same AAC2500 1.0%
Adhesion promoter K-FLEX188 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
And (2) sequentially adding saturated polyester resin, amino resin and a curing agent into a container, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a leveling agent and a defoaming agent under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the coating composition of the comparative example 3.
Coating and plate making: the resulting coating composition of comparative example 3 was wire bar roll coated on a stainless steel plate, baked in an oven at 320 ℃ for 30s, sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
It should be noted that: the adhesion promoter used in this comparative example 3 was K-FLEX188, available from KING corporation. The adhesion promoter improves adhesion by improving curing reactivity, rather than improving adhesion through 'bridging links' as described in the present invention, and is not an adhesion promoter suitable for use in the present invention. Therefore, this comparative example 3 is merely a comparative example.
Comparative example 4
A coating composition of comparative example 4 was prepared according to the formulation of table 11 below:
TABLE 11 coating composition of comparative example 4
Components Name (R) Amount (wt%)
Polyester resin NP 5055 25%
Amino resin Cymel 303 6%
Curing agent DESMODUR BL3175A 6%
Catalyst and process for preparing same Nacure 1051 0.4%
Adhesion promoter K-FLEX188 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
And (2) sequentially adding saturated polyester resin, amino resin and a curing agent into a container, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a leveling agent and a defoaming agent under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the coating composition of the comparative example 4.
Coating and plate making: the resulting coating composition of comparative example 4 was wire bar roll coated on a stainless steel plate, baked in an oven at 320 ℃ for 30s, sheet metal temperature PMT: 216 to 224 ℃ to give a paint film having a thickness of 8 μm.
It should be noted that: first, the comparative example 4 used a polyester resin of 25% by mass, which is not within the range of the polyester resin of the present invention. Second, the adhesion promoter used in this comparative example 4 was KING providing a K-FLEX188 adhesion promoter. The adhesion promoter improves adhesion by improving curing reactivity, rather than improving adhesion through 'bridging links' as described in the present invention, and is not an adhesion promoter suitable for use in the present invention. Therefore, combining the above two points, this comparative example 4 is merely a comparative example.
Comparative example 5
A coating composition of comparative example 5 was prepared according to the formulation of table 12 below:
TABLE 12 coating composition of comparative example 5
Components Name (R) Amount (wt%)
Polyester resin NP 5055 60%
Amino resin Cymel 303 6%
Curing agent DESMODUR BL3175A 8%
Catalyst and process for preparing same Nacure 1051 0.4%
Adhesion promoter Lubrizol2063 1.5%
Defoaming agent L-T 0.5%
Leveling agent L-C 1%
Matting powder SYLOID C809 0.5%
Solvent(s) S-100 4%
Solvent(s) Propylene glycol methyl ether acetate 10%
Solvent(s) DBE 6%
And (2) sequentially adding saturated polyester resin, amino resin and a curing agent into a container, mixing and uniformly stirring, then adding an acid catalyst, an adhesion promoter, a flatting agent, a defoaming agent and matting powder under stirring, uniformly stirring, finally adding a solvent, adjusting the gloss and the viscosity as required, adjusting the viscosity of the mixture to be 100-140 seconds, measuring by using a paint-4 cup, filtering and packaging to obtain the coating composition of the comparative example 5.
Coating and plate making: the resulting coating composition of comparative example 5 was wire bar roll coated on a stainless steel plate, baked in an oven at 320 ℃ for 30s, sheet metal temperature PMT: 224 ℃ to give a paint film having a thickness of 8 μm.
It is to be noted that the matting agent used in this comparative example 5 was a matting agent supplied by Grace under the name SYLOID C809. The matting powder has an average particle size of 8.0 μm and a particle size of more than 3 μm, and is not suitable for the matting powder of the present invention. Therefore, this comparative example 5 is only a comparative example.
The applicant carries out tests with national standard GB/T13448-2006 and obtains the test results of the properties of the coatings formed by curing the high weather resistance coil coating compositions of the invention of examples 1-7 shown in Table 13.
TABLE 13 results of testing the properties of the coatings prepared in examples 1-7 above
Figure BDA0002749046280000181
The applicant carried out tests in national standard GB/T13448-2006 to obtain the test results of the properties of the coatings formed by curing the coating compositions of comparative examples 1-5 shown in Table 14.
TABLE 14 results of the performance test of the coatings prepared in comparative examples 1 to 5
Figure BDA0002749046280000182
Figure BDA0002749046280000191
The test results show that the high-weather-resistance coil coating composition can be firmly combined with a stainless steel substrate, the interlayer adhesion is good, a workpiece product is easy to process and form, the formed coating has excellent fingerprint resistance, MEK resistance and weather resistance, the provided coil coating has high transparency and diversified colors, the antifouling, protecting, polishing and antifouling effects of metal products such as stainless steel and the like are enhanced after coating, and the actual requirements of further processing and decoration can be completely met.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. A highly weatherable coil coating composition characterized in that it comprises, in mass percent:
Figure FDA0002749046270000011
the polyester resin is saturated polyester resin, the number average molecular weight Mn is 3000-20000, the hydroxyl value is 30-70mg KOH/g, the acid value is not more than 10mg KOH/g, and a molecular chain of the polyester resin contains a neopentyl structure.
2. The highly weatherable coil coating composition according to claim 1, wherein said polyester resin is polymerized from a polyhydric alcohol and a polybasic acid; preferably, the polyester resin is polymerized from a diol and a diacid.
3. The highly weatherable coil coating composition according to claim 1, wherein said amino resin is at least one of methylated melamine resin, butylated urea formaldehyde resin, butylated melamine resin, and benzoguanamine formaldehyde resin.
4. The highly weatherable coil coating composition according to claim 1, wherein said curing agent is an isocyanate resin; preferably, the curing agent is a blocked isocyanate resin.
5. The highly weather resistant coil coating composition as claimed in claim 1, wherein the solvent is at least one of cyclohexanone, propylene glycol methyl ether acetate, ethylene glycol butyl ether, xylene, S-100 # solvent oil, S-150 # solvent oil, trimethylbenzene solvent oil, and a dibasic ester mixture.
6. The highly weather resistant coil coating composition as claimed in claim 1, wherein the adhesion promoter is an epoxy, silanol, phosphate modified polymer.
7. The highly weatherable coil coating composition according to claim 1, further comprising an auxiliary agent, wherein the auxiliary agent is at least one of a catalyst, a leveling agent, a defoaming agent, a dispersing agent, a pigment and a matting agent.
8. The highly weather-resistant coil coating composition according to claim 7, wherein the catalyst is a blocked sulfonic acid-based catalyst, the leveling agent is a non-silicon leveling agent, the defoaming agent is a non-silicon defoaming agent, and the particle size of the matting powder is less than or equal to 3 μm; and, preferably, the catalyst is at least one of dinonylnaphthalene disulfonic acid, dinonylnaphthalene sulfonic acid, dodecylbenzene sulfonic acid, and p-toluenesulfonic acid.
9. Use of the highly weather-resistant coil coating composition according to any one of claims 1 to 8 in painting.
10. The use according to claim 9, wherein the high weather resistance coil coating composition is directly coated on a substrate and cured and formed by high temperature baking.
CN202011177320.6A 2020-10-29 2020-10-29 High-weather-resistance coil coating composition and application thereof Pending CN114426796A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011177320.6A CN114426796A (en) 2020-10-29 2020-10-29 High-weather-resistance coil coating composition and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011177320.6A CN114426796A (en) 2020-10-29 2020-10-29 High-weather-resistance coil coating composition and application thereof

Publications (1)

Publication Number Publication Date
CN114426796A true CN114426796A (en) 2022-05-03

Family

ID=81309382

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011177320.6A Pending CN114426796A (en) 2020-10-29 2020-10-29 High-weather-resistance coil coating composition and application thereof

Country Status (1)

Country Link
CN (1) CN114426796A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114773967A (en) * 2022-05-11 2022-07-22 上海一田涂料有限公司 Super-weather-resistant coating composition for decorating aluminum veneer and preparation method thereof
CN115160904A (en) * 2022-07-28 2022-10-11 上海佑戈金属科技有限公司 Metal base band polymer coating for automobile and building field and preparation method thereof
CN115160905A (en) * 2022-07-28 2022-10-11 上海佑戈金属科技有限公司 Metal base band black precoating coating and preparation method thereof
CN115677989A (en) * 2022-10-26 2023-02-03 上海昱彩包装材料有限公司 Synthetic polyester resin, polyester resin coating for home appliances and preparation method of polyester resin coating
CN115785785A (en) * 2022-12-07 2023-03-14 雨中情防水技术集团股份有限公司 Water-curing bi-component polyurethane waterproof coating and preparation method thereof
CN116102949A (en) * 2022-12-27 2023-05-12 江苏金土木精工制造有限公司 High-performance protective paint and paint spraying process thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114773967A (en) * 2022-05-11 2022-07-22 上海一田涂料有限公司 Super-weather-resistant coating composition for decorating aluminum veneer and preparation method thereof
CN115160904A (en) * 2022-07-28 2022-10-11 上海佑戈金属科技有限公司 Metal base band polymer coating for automobile and building field and preparation method thereof
CN115160905A (en) * 2022-07-28 2022-10-11 上海佑戈金属科技有限公司 Metal base band black precoating coating and preparation method thereof
CN115677989A (en) * 2022-10-26 2023-02-03 上海昱彩包装材料有限公司 Synthetic polyester resin, polyester resin coating for home appliances and preparation method of polyester resin coating
CN115785785A (en) * 2022-12-07 2023-03-14 雨中情防水技术集团股份有限公司 Water-curing bi-component polyurethane waterproof coating and preparation method thereof
CN116102949A (en) * 2022-12-27 2023-05-12 江苏金土木精工制造有限公司 High-performance protective paint and paint spraying process thereof
CN116102949B (en) * 2022-12-27 2024-02-20 江苏金土木精工制造有限公司 High-performance protective paint and paint spraying process thereof

Similar Documents

Publication Publication Date Title
CN114426796A (en) High-weather-resistance coil coating composition and application thereof
EP0086085B1 (en) A high solids coating composition of an acrylic polymer, a polyester polyol and an alkylated melamine crosslinking agent
AU2008208419B2 (en) Coating composition
WO1996034063A1 (en) Coating composition, process for preparing the composition, and process for preparing dispersion of inorganic oxide sol
JP5814929B2 (en) Anti-stain coating composition with excellent durability
WO2012002095A1 (en) Contamination resistant coating composition with excellent durability
JP3937739B2 (en) Top coating composition, coating finishing method and coated article
TWI654220B (en) Polyester resin having excellent heat resistance and solvent solubility and coating composition containing the same
CN112852273B (en) Water-based matte scratch-resistant paint and application thereof
US20160297987A1 (en) Silicone-modified polyester coating
CN113248999A (en) Recyclable water-based double-component white finish suitable for mechanical spraying and preparation method thereof
JP5840132B2 (en) Anti-stain coating composition with excellent durability
US4388445A (en) Heat-curable coating composition
CN110804383A (en) Primer composition for high-film-thickness coating, primer and application thereof
CN111995940B (en) Super-matte PU odor-free clear finishing coat and preparation method thereof
DK2150590T3 (en) Composition covering antibrodannelsesmiddel
CN114736604B (en) High-solid-content DTM polyurethane coating and preparation method thereof
US11407919B2 (en) Curable film-forming compositions demonstrating increased wet-edge time
CN116285607A (en) High-processability coiled material coating composition and preparation method and application thereof
US10822518B2 (en) Curable coating compositions using succinic acid
CN110982396B (en) High-corrosion-resistance color plate coil coating
CN111234192B (en) Preparation method of organic silicon modified saturated polyester resin with high weather resistance
CN111019497B (en) High-adhesion water-based polyurea colored paint and preparation method thereof
KR101029489B1 (en) One component type polyurethane paint composition forming thickness film
KR100240600B1 (en) Resin composition for pre-coated metal coating paint having improved contamination resistance

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination