CN114502671A - Clear coating composition - Google Patents
Clear coating composition Download PDFInfo
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- CN114502671A CN114502671A CN202080070132.5A CN202080070132A CN114502671A CN 114502671 A CN114502671 A CN 114502671A CN 202080070132 A CN202080070132 A CN 202080070132A CN 114502671 A CN114502671 A CN 114502671A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to a clear coating composition comprising a silane-modified acrylic resin, a first polyester polyol resin, a second polyester polyol resin, a melamine resin and a urethane resin, wherein the number average molecular weight of the first polyester polyol resin is greater than the number average molecular weight of the second polyester polyol resin.
Description
Technical Field
The present invention relates to a clear coating composition capable of producing a coating film having excellent appearance characteristics, chipping resistance (scratch resistance), and scratch resistance.
Background
In order to provide an appearance and protect the surface thereof from the external environment, the vehicle body is generally subjected to various coating processes such as electrodeposition coating, intercoat coating, top coat coating, clear coating, and the like. Specifically, a common automotive painting process is to apply and cure an intercoat coating after electrodeposition coating on a vehicle body, apply a topcoat coating and a clear coating on the intercoat coating in succession, and then dry and cure them. Such an automobile coating process is generally performed by a 3-coat 2-bake (3C2B) coating method in which a primary curing is performed after a middle-coat coating and a secondary curing is performed after a clear coat coating.
As a clear coating for automobiles, thermosetting coating compositions containing an acrylic resin or an amino resin having a hydroxyl group are widely used. For example, a conventional composition generally used for a clear coating contains an acrylic resin and a melamine resin, and the melamine resin reacts with a hydroxyl group contained in the acrylic resin to form a chemical bond and form a coating film. However, the conventional compositions for clear coatings as described above have a limitation in that the scratch resistance of the coating film prepared therefrom is significantly insufficient due to the lack of mechanical physical properties, particularly surface tension and flexibility, of the prepared coating layer.
As an alternative to overcoming the limitations of such conventional clear coating materials, korean patent registration No.1,115,869 (patent document 1) discloses a 1K clear coating composition for automobiles for improving scratch resistance, which includes an acrylic resin, a melamine resin, a silane-modified blocked isocyanate resin, and a resin for adjusting flow characteristics. However, with the clear coating composition of patent document 1, the appearance characteristics of the coating film prepared therefrom are deteriorated, and thus there is a limitation in its application as an automobile body coating material.
Therefore, there is a need to research and develop a clear coating composition capable of producing a coating film having excellent appearance characteristics and mechanical physical properties, particularly excellent scratch resistance, flexibility and hardness.
Disclosure of Invention
[ problem ] to
The present invention provides a clear coating composition capable of preparing a coating film having excellent scratch resistance and chipping resistance by enhancing the surface tension and flexibility of the prepared coating layer.
[ solution ]
The present invention provides a clear coating composition comprising a silane-modified acrylic resin, a first polyester polyol resin, a second polyester polyol resin, a melamine resin, and a urethane resin (urethane resin), wherein the number average molecular weight of the first polyester polyol resin is greater than the number average molecular weight of the second polyester polyol resin.
[ advantageous effects ]
The clear coating composition according to the present invention uses an organic resin and an inorganic resin in combination to enhance the surface tension and flexibility of a coating film prepared therefrom, and thus the coating film prepared therefrom has excellent scratch resistance. Further, the clear coating composition comprises a low molecular weight polyester resin, and thus a coating film prepared therefrom has excellent flexibility and resilience, and the clear coating composition further comprises two polyester resins, and thus a coating film prepared therefrom has excellent appearance characteristics, flexibility, chipping resistance, and scratch resistance.
Best mode for carrying out the invention
Hereinafter, the present invention will be described in detail.
As used herein, "weight average molecular weight" and "number average molecular weight" are measured by conventional methods known in the art, and can be measured by, for example, a Gel Permeation Chromatography (GPC) method. Further, the "glass transition temperature" is measured by conventional methods known in the art, and can be measured, for example, by Differential Scanning Calorimetry (DSC). Further, functional group values such as "acid value" and "hydroxyl value" can be measured by methods well known in the art, and can represent values measured by, for example, a titration method.
Further, the term "(meth) acrylate" in the present specification means acrylate and/or methacrylate.
The clear coating composition according to the present invention includes a silane-modified acrylic resin, a first polyester polyol resin, a second polyester polyol resin, a melamine resin, and a urethane resin.
Silane-modified acrylic resins
The silane-modified acrylic resin is used to improve physical properties of the coating film, such as hardness, acid resistance, and scratch resistance.
The silane-modified acrylic resin may be directly synthesized according to a known method, or may be a commercially available product. At this time, the silane-modified acrylic resin may be, for example, one prepared by modifying an acrylic resin by using a silane monomer, the acrylic resin being prepared by polymerization of at least one selected from a vinyl monomer and a (meth) acrylate monomer.
The type of the vinyl monomer is not particularly limited, but may be, for example, at least one selected from the following: styrene, methylstyrene, dimethylstyrene, fluorostyrene, ethoxystyrene, methoxystyrene, phenylene vinyl ketone, vinyl tert-butylbenzoate, vinyl cyclohexanoate, vinyl acetate, vinylpyrrolidone, vinyl chloride, vinyl alcohol, acetoxystyrene, tert-butylstyrene, vinyltoluene, chlorostyrene, and cyclohexyl vinyl ether.
Further, the (meth) acrylate monomer may be, for example, at least one selected from the group consisting of: 2-hydroxypropyl methacrylate, propyl methacrylate, t-butylaminoethyl methacrylate, dicyclopentenylethoxy methacrylate, acrylic acid dimer, hexanediol diacrylate, butyl acrylate, triisopropylsilyl acrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, ethyl methacrylate, isobutyl methacrylate, hydroxyisopropyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, triisopropylsilyl methacrylate, isobornyl acrylate, t-butylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, methyl methacrylate, acrylic acid, t-butyl methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and butyl methacrylate, Isobornyl methacrylate, methacrylonitrile, methacrylic acid, acrylamide and methacrylamide.
The silane monomer may be an alkoxy-containing silane monomer. For example, the silane monomer may include gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, gamma-acetoacetoxypropyltrimethoxysilane, gamma-acetoacetoxypropyltriethoxysilane, beta-cyanoacetyltrimethoxysilane, beta-cyanoacetyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyl-alkoxysilane, gamma-glycidoxypropyl-hydroxysilane, gamma-hydroxysilane, beta-hydroxysilane, beta-hydroxysilane, beta-hydroxysilane, beta-, Acetoxyacetyltrimethoxysilane, and the like.
The silane-modified acrylic resin may have a glass transition temperature of 30 to 50 ℃, 35 to 48 ℃, or 40 to 45 ℃, a weight average molecular weight (Mw) of 5,500 to 8,500g/mol, 6,000 to 8,000g/mol, or 6,500 to 7,500g/mol, and a viscosity of 500 to 2,500cps, 700 to 2,000cps, or 900 to 1,800cps at 25 ℃. If the glass transition temperature of the silane-modified acrylic resin is within the above range, appropriate physical properties of the coating layer can be secured while having good storage stability. If the weight average molecular weight is within the above range, long-term physical properties such as durability and weather resistance of the coating film produced are improved. If the viscosity at 25 ℃ is within the above range, there is an effect that the processability of the composition is easy.
Further, the silane-modified acrylic resin may have a hydroxyl value (OHV) of 80 to 90mgKOH/g, or 82 to 88mgKOH/g, and an acid value (Av) of 5mgKOH/g or less, 4mgKOH/g or less, or 1 to 3 mgKOH/g. If the hydroxyl value of the silane-modified acrylic resin is within the above range, the hardenability of the composition is improved, thereby ensuring impact resistance, water resistance, adhesion, and cold chip resistance (cold cracking resistance). If the acid value is within the above range, the reactivity of the composition is adjusted, thereby improving the appearance characteristics of the coating film.
The silane-modified acrylic resin may be included in a content of 1 to 20 parts by weight, 5 to 15 parts by weight, or 7 to 13 parts by weight, based on 1 to 20 parts by weight of the first polyester polyol resin. If the content of the silane-modified acrylic resin is within the above range, it is possible to prevent the problem of deterioration in gloss of a coating film prepared from a coating composition containing the silane-modified acrylic resin, and the problem of deterioration in appearance characteristics and hardening density of the coating film.
A first polyester polyol resin
The first polyester polyol resin is used to improve the appearance characteristics and flexibility of the prepared coating film.
The first polyester polyol resin may be a product directly synthesized according to a known method or a commercially available product. For example, the first polyester polyol resin may be prepared by reacting a carboxylic acid with a polyol.
In this case, the carboxylic acid may be at least one selected from the group consisting of: isononanoic acid, Adipic Acid (AA), isophthalic acid (IPA), trimellitic anhydride (TMA), alicyclic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, fumaric acid, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (HHPA), and derivatives thereof. Further, the polyol may be at least one selected from the group consisting of: methoxypolyethylene glycol, 1, 6-hexanediol (1,6-HD), neopentyl glycol (NPG), Trimethylolpropane (TMP), ethylene glycol, propylene glycol, diethylene glycol, butanediol, 1, 4-hexanediol, and 3-methylpentanediol.
The first polyester polyol resin may have a hydroxyl value (OHv) of 100 to 180mgKOH/g, 120 to 150mgKOH/g, or 130 to 145mgKOH/g, and an acid value (Av) of 10 to 50mgKOH/g, 15 to 35mgKOH/g, or 20 to 25 mgKOH/g. If the hydroxyl value of the first polyester polyol resin is within the above range, the composition has good water dispersibility, and a coating layer formed therefrom has good physical properties. If the acid value is within the above range, there is an effect of improving storage stability and crosslink density, and therefore cold-cracking resistance is good.
Further, the number average molecular weight (Mn) of the first polyester polyol resin is greater than that of the second polyester polyol resin. For example, the first polyester polyol resin may have a number average molecular weight (Mn) of 1,300 to 2,500g/mol, 1,400 to 2,300g/mol, or 1,500 to 2,000 g/mol.
The first polyester polyol resin may have a lower hydroxyl value (OHv) than the second polyester polyol resin. That is, the first polyester polyol resin may have a larger number average molecular weight and a lower hydroxyl value than the second polyester polyol resin.
Further, the viscosity of the first polyester polyol resin at 25 ℃ may be 1,000 to 3,500cps, 1,500 to 3,000cps, or 1,800 to 2,700 cps. If the viscosity of the first polyester polyol resin at 25 ℃ is within the above range, there is an effect that the workability is easy.
The first polyester polyol resin may be included in a content of 1 to 20 parts by weight, 5 to 15 parts by weight, or 7 to 13 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin. If the content of the first polyester polyol resin is within the above range, there is an effect that the appearance, impact resistance and cold-cracking resistance of the prepared coating film are good.
Second polyester polyol resin
The second polyester polyol resin plays a role in improving chipping resistance and scratch resistance by increasing the solid content and reactivity of the composition, and improving flexibility and resilience of the prepared coating film.
In this case, the second polyester polyol resin may be a product directly synthesized according to a known method or a commercially available product. For example, the second polyester polyol resin may be prepared by reacting caprolactone and a polyol. In this case, the polyol may be Cyclohexanedimethanol (CHDM) or the like, but is not limited thereto.
Further, the second polyester polyol resin may have a hydroxyl value (OHv) of 200 to 400mgKOH/g, 230 to 350mgKOH/g, or 250 to 300 mgKOH/g. If the hydroxyl value of the second polyester polyol resin is within the above range, there is an effect of increasing the crosslink density with the curing agent, thereby improving the durability of the coating film produced.
The number average molecular weight (Mn) of the second polyester polyol resin is smaller than the number average molecular weight (Mn) of the first polyester polyol resin. For example, the second polyester polyol resin can have a number average molecular weight of 500 to 1,000g/mol, 550 to 900g/mol, or 600 to 800 g/mol.
Further, the second polyester polyol resin may have a viscosity of 700 to 2,500cps, 800 to 2,400cps, or 850 to 2,300cps at 25 ℃. If the viscosity of the second polyester polyol resin at 25 ℃ is within the above range, there is an effect that workability is easy and appearance is excellent.
The second polyester polyol resin may be included in a content of 1 to 20 parts by weight, 5 to 15 parts by weight, or 7 to 13 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin. If the content of the second polyester polyol resin is within the above range, there is an effect that the prepared coating film has good impact resistance and cold chip resistance.
The clear coating composition may include the first polyester polyol resin and the second polyester polyol resin in a weight ratio of 1:0.1 to 1:5, a weight ratio of 1:0.2 to 1:3, or a weight ratio of 1:0.5 to 1: 2. If the mixing weight ratio of the first polyester polyol resin and the second polyester polyol resin is within the above range, the durability, cold chip resistance and appearance of the prepared coating film can be improved.
Melamine resin
The melamine resin as the curing agent plays a role in curing the composition by crosslinking with each component of the clear coating composition.
The melamine resin may be a product directly synthesized according to a known method or a commercially available product. For example, the melamine resin may be at least one selected from the group consisting of: methoxymethylmelamine, methylmelamine, butylmelamine, isobutyloxymelamine, butoxymelamine, hexamethylolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, hexamethoxybutoxymethylmelamine and iminomethoxymethylmelamine.
Further, the melamine resin can have a weight average molecular weight (Mw) of 100 to 5,000g/mol, 500 to 4,500g/mol, or 1,000 to 4,000g/mol, and a viscosity of 400 to 1,200cps, 500 to 1,100cps, or 600 to 1,000cps at 25 ℃. If the weight average molecular weight of the melamine resin is within the above range, there is an effect of improving the adhesion and hardness of the prepared coating film by increasing the crosslinking density. When the viscosity at 25 ℃ is within the above range, the gloss and appearance are excellent.
The melamine resin may be included in an amount of 15 to 35 parts by weight, 16 to 30 parts by weight, or 17 to 27 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin. If the content of the melamine resin is within the above range, there is an effect of improving the adhesion and hardness of the prepared coating film by increasing the crosslinking density.
Urethane resin
The urethane resin plays a role in improving the workability of the clear coating composition and improving the appearance characteristics of the coating film prepared from the composition.
The urethane resin may be a product directly synthesized according to a known method, or may be a commercially available product. For example, the urethane resin may be prepared by reacting an alcohol with a diisocyanate.
In this case, the alcohol may be at least one selected from the group consisting of: cyclohexanol, ethylhexanol, butanol, 1, 6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, trimethylolpropane, butanediol, 1, 4-hexanediol and 3-methylpentanediol.
In addition, the diisocyanate may be, for example, at least one selected from the group consisting of: isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene diisocyanate, 2, 3-dimethylethylene diisocyanate, 1-methyltrimethylene diisocyanate, 1, 3-cyclopentene diisocyanate, 1, 4-cyclopentene diisocyanate, 1, 2-cyclopentene diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4-diphenylpropane diisocyanate, xylene diisocyanate, and 1,1,6, 6-tetramethylhexamethylene diisocyanate.
The urethane resin may not contain unreacted NCO groups. If a urethane resin containing no unreacted NCO group is used, there is an effect that the appearance of the resulting coating film is excellent.
Further, the urethane resin can have a weight average molecular weight (Mw) of 8,000 to 13,000g/mol, 9,000 to 12,500g/mol, or 10,000 to 12,000g/mol, and a solids content of 60 to 80 wt.%, 65 to 75 wt.%, or 67 to 73 wt.%. When the weight average molecular weight of the urethane resin is within the above range, the gloss and appearance characteristics of the coating film are excellent. If the solid content is within the above range, there is an effect that the workability of the composition is excellent.
The urethane resin may be included in an amount of 1 to 10 parts by weight, 2 to 9 parts by weight, or 3 to 8 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin. If the content of the urethane resin is within the above range, there is an effect that the prepared coating film has excellent flexibility and appearance characteristics.
Solvent(s)
The clear coating composition may further comprise a solvent. In this case, the solvent controls the viscosity of the clear coating composition and plays a role in controlling the quick-drying characteristics of the composition, and may be a conventional solvent for the clear coating composition.
The solvent may comprise, for example, at least one selected from the group consisting of: acetate-based solvents, alkylbenzene-based solvents, ketone-based solvents, and carbonate-based solvents. As another example, the solvent may be: non-polar solvents such as n-heptane, toluene, xylene, petroleum compounds and n-hexane; polar solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dibasic esters, 3-methoxybutyl acetate, amyl acetate, butyl ethylene glycol acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, diisobutyl ketone, isophorone and cyclohexanone; and a mixture of a non-polar solvent and a polar solvent, etc., and may be appropriately selected and used according to the characteristics or volatilization rate of the resin contained in the composition.
In addition, the solvent may be included in an amount of 5 to 30 parts by weight, 10 to 25 parts by weight, or 12 to 23 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin. If the content of the solvent is within the above range, problems such as defects in the coating film, such as the occurrence of pinholes and the occurrence of stains in the coating film, can be prevented.
Additive agent
The clear coating composition may further comprise an additive selected from at least one of the following: dispersing agent, moisture absorbent, leveling agent (leveling agent), anti-sagging agent and UV absorbent.
The additive may be included in an amount of 20 to 40 parts by weight, 23 to 37 parts by weight, or 25 to 35 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin. If the content of the additive is outside the above range, the appearance characteristics of the prepared coating film may be deteriorated.
The dispersant plays a role in improving the storage stability of the composition. Further, the dispersant may be used without any particular limitation as long as it can be used in the coating composition, and may be, for example, phenylpropionic acid. In addition, the dispersant may be included in an amount of 0.1 to 3 parts by weight, 0.2 to 2 parts by weight, or 0.3 to 1 part by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin.
The moisture absorbent plays a role in improving the anti-fouling property of the prepared coating film. The moisture absorbent may be used without any particular limitation as long as it can be used in the coating composition, and may be, for example, an orthoester-based compound. The orthoester-based moisture absorbent may be, for example, formamidine acetate, 2-methoxy-1, 3-dioxolane, 1,3, 3-tetramethoxypropane, triethyl orthoacetate, triethyl orthoformate, triethyl orthopropionate, triisopropyl orthoformate, trimethyl orthoacetate, trimethyl orthoformate, or the like. Further, the moisture absorbent may be included in a content of 1 to 10 parts by weight, 2 to 9 parts by weight, or 3 to 8 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin.
The leveling agent plays a role in imparting leveling property and wetting property to the prepared coating film. Further, the leveling agent may be used without any particular limitation as long as it can be used in the coating composition, and may be, for example, based on polyether-modified polysiloxane. In addition, the leveling agent may be included in an amount of 0.1 to 2 parts by weight, 0.2 to 1.5 parts by weight, or 0.5 to 1 part by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin.
Anti-sagging agents play a role in improving the processability of the composition by controlling sagging of the composition. Further, the anti-sagging agent may be used without any particular limitation as long as it can be used for the coating composition, and may be, for example, a polyester resin having a diurea group. Further, the anti-sagging agent may be included in an amount of 10 to 30 parts by weight, 15 to 25 parts by weight, or 17 to 23 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin.
The UV absorber plays a role in blocking UV rays reaching the prepared coating film and improving weather resistance of the final coating film. The UV absorber may be a benzotriazole-based UV absorber. Further, the UV absorber may be included in an amount of 1 to 5 parts by weight, 1 to 4 parts by weight, or 1 to 3 parts by weight, based on 1 to 20 parts by weight of the silane-modified acrylic resin.
As described above, the clear coating composition according to the present invention uses an organic resin and an inorganic resin in combination to enhance the surface tension and flexibility of a coating film prepared therefrom, and thus the coating film prepared therefrom has excellent scratch resistance. Further, the clear coating composition comprises a low molecular weight polyester, and thus the resulting coating film has excellent flexibility and resilience, and the clear coating composition further comprises two polyester resins, and thus the resulting coating film has excellent appearance characteristics, flexibility, chipping resistance, and scratch resistance.
Detailed Description
Hereinafter, the present invention will be described in more detail by examples.
However, these examples are only for assisting understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
Examples 1 to 9 and comparative examples 1 to 4 preparation of clear coating compositions
Silane-modified acrylic resin, first polyester polyol resin, second polyester polyol resin, melamine resin, urethane resin, solvent and additives were mixed according to the contents of tables 1 and 2 to prepare clear coating compositions.
Table 1:
table 2:
the components and brand names of the respective components used in the following examples and comparative examples are shown in table 3.
Table 3:
experimental example: evaluation of Properties of the coating film thus prepared
On the electrodeposition-coated test specimens, a primer coat (primer coat) composition (manufacturer: KCC, trade name: FU2270 oil-based) bell was applied (bell-padded) to a dry thickness of 35 μm and first cured at 140 ℃ for 25 minutes. Thereafter, a base coat (base coat) composition (manufacturer: KCC, brand name: TT663, water base) bell was applied to a dry thickness of 15 μm, and the remaining water in the coating was evaporated (dried) in a drying oven at 80 ℃ for 3 minutes. Thereafter, after cooling to room temperature for 2 minutes, the clear coating compositions (oil-based) bell from examples and comparative examples were applied to a dry thickness of 40 μm, followed by secondary curing at 140 ℃ for 25 minutes to form a final coating film. Appearance characteristics and physical properties of the final coating film were measured in the following manner, and the results are shown in Table 4.
(1) Appearance of coating film
For the final coating, the CF value was measured using an automobile appearance measuring instrument wave scan doi (byk gardner), and it was determined that the higher the CF value, the better the appearance characteristics of the coating film. Specifically, if the CF value is 70 or more, the evaluation is excellent (. circleincircle.), if the CF value is 65 or more and less than 70, the evaluation is good (. largecircle.), if the CF value is 60 or more and less than 65, the evaluation is normal (. DELTA.), and if the CF value is less than 60, the evaluation is bad (. largecircle.).
(2) Hardness of
The hardness of the clear coating film was measured by the pencil hardness method. Specifically, 3B, 2B, HB, F, H, 2H, and 3H pencils (3B, 2B, HB, F, H, 2H, 3H: inferior)
Excellent) the maximum hardness without damaging the clear coating film was measured.
(3) Adhesion Property
After the sample was heat-treated and left at room temperature for 24 hours, the adhesion was evaluated by the cross-cut adhesion test method.
Specifically, in the cross-hatch adhesion test method, 100 squares of 2mm width and 2mm length were prepared on the surface of a clear coating film with a knife, and then the squares were removed using an adhesive tape to measure adhesion. At this time, if 100 squares remain 100% intact, the measured adhesion is represented as M-1 (excellent), and if the remaining squares are 70% or more and less than 100%, it is represented as M-2 (excellent), and if the remaining squares are 50% or more and less than 70%, it is represented as M-3 (normal), and if the remaining squares are 30% or more and less than 50%, it is represented as M-4 (poor), and the remaining squares are less than 30%, it is represented as M-5 (very poor).
Further, the heat treatment was repeated at 150 ℃ for 20 minutes and then left at room temperature for 20 minutes as one cycle, and a total of 3 cycles were repeated.
(4) Water resistance
After the test piece was immersed in a constant-temperature water bath at 40 ℃ for 240 hours and left at room temperature for 1 hour, a peel test was performed in the same manner as the cross-hatch adhesion test method of item (3), and the same evaluation criteria were also applied.
(5) Acid resistance
After 0.2ml of 0.1N sulfuric acid was added dropwise to the surface of the coating film of the sample, it was treated in an oven preheated to 30 ℃ or more for 150 minutes. At this time, the occurrence of etching, staining, or swelling of the portion where sulfuric acid was dropped on the specimen was visually observed, and the highest temperature at which no damage occurred in the specimen was determined as the acid-resistant temperature.
(6) Scratch resistance
The 20 ° gloss of the test piece was measured (measurement of initial gloss), and after the surface of the test piece was reciprocated 10 times using an automobile wash resistance tester (product from Amtec Kistler corporation), the 20 ° gloss was measured. Thereafter, the gloss retention ratio was calculated from the initial gloss and the gloss after surface treatment using the following equation 1.
[ equation 1]
Gloss retention ═ gloss after surface treatment/initial gloss × 100
(7) Solvent resistance
After placing a cotton cloth moistened with xylene on the coating film of the sample, it was scratched 4 times every 1 minute with a force of 2kg to record the time when the surface of the underlying coating film appeared.
Table 4:
as shown in table 4, the coating films prepared from the clear coating compositions of examples 1 to 9 were excellent in appearance characteristics, hardness, adhesion, acid resistance, solvent resistance and scratch resistance.
On the other hand, the physical properties such as appearance characteristics and adhesion, water resistance, acid resistance, scratch resistance and solvent resistance of the coating films prepared from the compositions of comparative examples 1 to 4 were insufficient.
In particular, comparative example 1 containing no silane-modified acrylic resin and comparative example 3 containing no second polyester polyol resin were significantly insufficient in coating film appearance, water resistance and solvent resistance. Further, comparative example 2 not containing the first polyester polyol resin and comparative example 4 not containing the urethane resin are significantly insufficient in hardness and adhesion.
Claims (6)
1. A clear coating composition comprising a silane-modified acrylic resin, a first polyester polyol resin, a second polyester polyol resin, a melamine resin, and a urethane resin, wherein the first polyester polyol resin has a number average molecular weight greater than that of the second polyester polyol resin.
2. The clear coating composition according to claim 1, wherein the silane-modified acrylic resin has a glass transition temperature of 30 to 50 ℃, a hydroxyl value of 80 to 90mg KOH/g, and an acid value of 5mg KOH/g or less.
3. The clear coating composition according to claim 1, wherein the first polyester polyol resin has a hydroxyl value of 100 to 180mgKOH/g, an acid value of 10 to 50mgKOH/g, and a number average molecular weight of 1,300 to 2,500 g/mol.
4. The clear coating composition according to claim 1, wherein the second polyester polyol resin has a hydroxyl value of 200 to 400mgKOH/g, and a number average molecular weight of 500 to 1,000 g/mol.
5. The clear coating composition according to claim 1, wherein the mixing ratio of the first polyester polyol resin and the second polyester polyol resin is 1:0.1 to 1:5 by weight.
6. The clear coating composition according to claim 1, wherein the composition contains 1 to 20 parts by weight of the silane-modified acrylic resin, 1 to 20 parts by weight of the first polyester polyol resin, 1 to 20 parts by weight of the second polyester polyol resin, 15 to 35 parts by weight of the melamine resin, and 1 to 10 parts by weight of the urethane resin.
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| KR1020190122572A KR102340545B1 (en) | 2019-10-02 | 2019-10-02 | Composition for clear coat |
| KR10-2019-0122572 | 2019-10-02 | ||
| PCT/KR2020/013177 WO2021066440A2 (en) | 2019-10-02 | 2020-09-28 | Clear paint composition |
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