CN110016272B - Coating composition - Google Patents
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- CN110016272B CN110016272B CN201811549710.4A CN201811549710A CN110016272B CN 110016272 B CN110016272 B CN 110016272B CN 201811549710 A CN201811549710 A CN 201811549710A CN 110016272 B CN110016272 B CN 110016272B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/63—Additives non-macromolecular organic
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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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention relates to a coating composition comprising a polyester-acrylic hybrid polyol resin, a curing agent, an acid catalyst and a solvent.
Description
Technical Field
The present invention relates to a clear coating composition for PCM (Pre-Coated Metal) which can exhibit excellent workability, high hardness, and excellent appearance and Distinctness of Image (DOI).
Background
Recently, as the interior decoration of home electric appliances is emphasized, demands for home electric appliances having beautiful appearances such as various textures and beautiful colors are increasing. The printed (print) products for home appliances are mainly coated by PCM gravure offset printing, and it is necessary to ensure distinctness of image and high gloss at a high gloss level. Therefore, a coating material having excellent processability and hardness, and having high distinctness of image and scratch resistance, which are basic physical properties required for PCM household electrical appliances, has been developed.
Conventionally, a varnish for printing products for home electric appliances uses a polyester resin having a number average molecular weight of 1,000 to 10,000 in order to ensure excellent processability. When such a polyester resin is used, a coating film having excellent processability can be obtained, but there is a limit that the polyester resin alone cannot exhibit excellent appearance and high distinctness of image.
[ Prior art documents ]
[ patent document ]
Korean laid-open patent No. 2011-0064816
Disclosure of Invention
Technical problem
The present invention provides a clear coating composition for PCM having excellent distinctness of image, processability and high hardness.
Means for solving the problems
The present invention provides a coating composition comprising a polyester-acrylic hybrid polyol resin, a curing agent, an acid catalyst, and a solvent.
The present invention also provides a PCM steel sheet comprising a steel sheet and a coating film formed from the coating composition.
Effects of the invention
The coating composition of the present invention exhibits excellent appearance characteristics and distinctness of image while exhibiting excellent processability and high hardness.
Detailed Description
The present invention will be described in detail below, but the present invention is not limited to the following, and various modifications and alternative combinations of the respective components may be made as necessary. Therefore, the present invention should be construed as including all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention.
< coating composition >
The coating composition of the present invention comprises a polyester-acrylic hybrid polyol resin (polyester-acrylic hybrid polyol resin), a curing agent, an acid catalyst and a solvent. If necessary, usual additives in the PCM field may be further included.
The composition of the coating composition is specifically examined below, as follows.
Polyester-acrylic hybrid polyol resins
In the coating composition of the present invention, a polyester-acrylic hybrid polyol resin is used as a main (main) resin. In the present specification, "polyol" or its modification means a substance having an average value of 2 or more hydroxyl groups per molecule. The main resin reacts with a curing agent to form a coating film, and thus, the coating film has high gloss and high distinctness of image, and has the functions of ensuring basic properties of the coating film, excellent processability, high hardness, chemical resistance, hardness, adhesion, and the like.
The polyester-acrylic hybrid polyol resin can have a number average molecular weight (Mn) of 1,500 to 5,500g/mol, for example 2,000 to 4,500 g/mol. If the number average molecular weight is less than 1,500, the processability is lowered, and if it exceeds 5,500, the appearance (distinctness of image) is lowered. The polyester-acrylic hybrid polyol resin may have a hydroxyl value (OH value, based on solids) of 20 to 70mgKOH/g, for example 20 to 50 mgKOH/g. If the hydroxyl value is less than 20, the solvent resistance (MEK, methyl ethyl ketone rubbing property) and chemical resistance are reduced, and if it exceeds 70, the processability is reduced. The polyester-acrylic hybrid polyol resin may have an Acid value (based on solid parts) of 5 to 30mgKOH/g, for example, 7 to 25 mgKOH/g. If the acid value is less than 5, the modification ratio of acrylic acid and polyester is low, and the hardness, processability and appearance (distinctness of image) of the coating film are lowered, while if it exceeds 30, the coating film is yellowed due to unreacted double bonds. The glass transition temperature (Tg) of the polyester-acrylic hybrid polyol resin may be 20 to 50 ℃, for example 25 to 45 ℃. If the glass transition temperature is less than 20 ℃, the hardness of the coating film is lowered, and if it exceeds 50 ℃, the processability is lowered.
The polyester-acrylic hybrid polyol resin of the present invention can be prepared as follows using at least one acid monomer containing a carboxylic acid functional group, at least one polyfunctional alcohol monomer, a metal catalyst, an acid anhydride, and the like. However, the present invention is not limited to the following production method, and the steps of the respective processes may be modified or selectively performed in combination as necessary.
The preparation method of the polyester-acrylic hybrid polyol resin may include: polymerizing a mixture of at least one acid monomer containing a carboxylic acid functional group and at least one polyfunctional alcohol monomer, adding an anhydride with an unsaturated group, carrying out a ring-opening reaction at the tail end of a polyester main chain to prepare a polyester polyol prepolymer (pre-polymer) containing the unsaturated group, and then polymerizing the polyester polyol prepolymer containing the unsaturated group, an acrylic monomer and an ethylenic unsaturated monomer to prepare the polyester-acrylic hybrid polyol resin.
The preparation process is described separately in the following steps.
i) Preparation of polyester polyol prepolymer containing unsaturated group
A mixture of at least one acid monomer containing a carboxylic acid functional group and at least one polyfunctional alcohol monomer is polymerized in the presence of a metal catalyst, and then an acid anhydride having an unsaturated group is added to perform a ring-opening reaction at the end of a polyester main chain.
As the acid monomer, carboxylic acid and its derivative compounds that are generally used in the art and have a carboxylic acid functional group may be used without limitation. Examples of the functional group include an aromatic carboxylic acid, an aliphatic carboxylic acid, an alicyclic carboxylic acid, a fatty acid, a dimer acid, an acid anhydride (acid anhydride), a mixture thereof, and the like.
As non-limiting examples of acid monomers that can be used, there are isophthalic acid, terephthalic acid, dimethyl terephthalate, dimethyl isophthalate, trimellitic anhydride, adipic acid, azelaic acid, sebacic acid, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 12-hydroxystearic acid, stearic acid, benzoic acid, isononanoic acid, dodecanedioic acid, dimer fatty acid (dimer fatty acid), hydrogenated dimer acid, fumaric acid, maleic anhydride, and the like. The aforementioned components may be used alone, or 2 or more of the aforementioned components may be used in combination.
The acid monomer of the present invention may contain two or more functional alicyclic carboxylic acids and aliphatic carboxylic acids. As an example, the acid monomer may be a mixture containing 70 to 95 equivalent% of two or more functional alicyclic carboxylic acids and 5 to 30 equivalent% of aliphatic carboxylic acids, based on 100 equivalent% of the total acid monomers.
When the amount of the two or more functional alicyclic carboxylic acids is less than 70 equivalent%, visual clarity is lowered, pencil hardness is lowered, and when it exceeds 95 equivalent%, workability is lowered. When the amount of the aliphatic carboxylic acid used exceeds 30 equivalent%, the glass transition temperature of the coating film is lowered, and the pencil hardness is seriously lowered, and when the amount is less than 5 equivalent%, the workability is lowered.
As the polyfunctional alcohol monomer, there may be used, without limitation, an alcohol in the art and a derivative compound thereof, which have two or more functional alcohol groups. As an example, there are aliphatic alcohol, alicyclic alcohol, aromatic alcohol, or a mixture thereof.
As one example of the polyfunctional alcohol monomer which can be used, there is an alcohol having 2 to 16 carbon atoms, and as a non-limiting example thereof, there are ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-butyl-2-ethyl-1, 3-propanediol, cyclohexanedimethanol, diethylene glycol, glycerol, 2-methyl-1, 3-propanediol, neopentyl glycol, pentaerythritol, trishydroxyethyl isocyanurate, trimethylolethane, trimethylolpropane, ditrimethylolpropane and the like. The aforementioned components may be used alone or in combination of 2 or more.
The polyfunctional alcohol monomer of the present invention may include two functional aliphatic alcohols, alicyclic alcohols, and polyfunctional alcohols having three or more functions. In this case, as the polyfunctional alcohol monomer having three or more functions, there can be used, without limitation, a general alcohol having three or more functions known in the art. As non-limiting examples of the three or more functional alcohol monomers that can be used, trimethylolpropane, pentaerythritol, trimethylolpropane, and the like are given.
As an example, the polyfunctional alcohol monomer may be a mixture containing 40 to 80 equivalent% of two functional aliphatic alcohols, 20 to 60 equivalent% of alicyclic alcohols, and 0 to 5 equivalent% of polyfunctional alcohols having three or more functions, based on 100 equivalent% of the total alcohol monomers.
If the amount of the two functional aliphatic alcohol monomers is less than 40 equivalent%, the processability of a coating film using the polyester-acrylic hybrid polyol resin is poor, and if it exceeds 80 equivalent%, the pencil hardness is poor. When the amount of the alicyclic alcohol monomer used is less than 20 equivalent%, pencil hardness is low, and when it exceeds 60 equivalent%, workability is low. Further, if the amount of the three or more functional alcohol monomers used exceeds 5 equivalent%, the processability is lowered, and the uniformity is lowered when an unsaturated group is added.
As an example, the mixture of the acid monomer and the polyfunctional alcohol monomer and the reaction catalyst are charged into a reactor equipped with a reactor, a thermometer, a packed column, an H-type separation tube, a condenser, and a nitrogen injection tube, heated to 220 to 250 ℃ while injecting an inert gas, and cooled if the acid value reaches a specific range (for example, 15 to 30mgKOH/g) in the case of removing condensation water, a solvent (for example, xylene) is charged, azeotropic distillation is performed at 210 to 250 ℃, and if the acid value reaches a specific range (for example, 5 or less), cooled to 150 ℃ or less, and then an acid anhydride (acid anhydride) containing an unsaturated group is charged to perform a ring-opening reaction.
As the reaction catalyst, a general metal catalyst used in the preparation of the polyester polyol resin can be used, and as an example, a tin catalyst can be used. Such metal catalysts may be used in the range of 0.01 to 0.1% by weight based on the total solid parts of the polyester polyol prepolymer.
As the acid anhydride, a general acid anhydride having at least one unsaturated group in a molecule, for example, an ethylenically unsaturated group, which is known in the art, can be used without limitation. For example, at least one of maleic anhydride (maleic anhydride) represented by the following chemical formula 1 and tetrahydrophthalic anhydride (tetrahydrophthalic anhydride) represented by the following chemical formula 2 may be used.
[ chemical formula 1]
[ chemical formula 2]
The acid monomer having a carboxylic acid functional group and the polyfunctional alcohol monomer may be added in such a manner that an equivalent ratio of alcohol/carboxylic acid is 1.05 to 1.50.
The acid anhydride may be used in a range of 10 to 110 mol% based on the number of moles (mol) of the polyester produced. When the amount of the acid anhydride used is less than 10 mol%, unsaturated groups are relatively small and the amount of the polyester polyol prepolymer which does not participate in the reaction after the preparation of the polyester-acrylic hybrid polyol resin is increased, and the pencil hardness of the coating film may be decreased. However, when the amount of the acid anhydride used exceeds 110 mol%, processability is reduced, and the polyester-acrylic hybrid polyol resin is gelled when prepared.
As described above, a polyester polyol prepolymer having an unsaturated group is prepared by a ring-opening reaction according to an acid anhydride having an unsaturated group. The polyester polyol prepolymer having an unsaturated group may have a number average molecular weight (Mn) of 500 to 3,000g/mol, a hydroxyl value (OH value) of 25 to 120mgKOH/g, an acid value of 10 to 50mgKOH/g, and a glass transition temperature (Tg) of-10 to 50 ℃. If the number average molecular weight is less than 500, the processability is lowered, and if it exceeds 3,000, the appearance (distinctness of image) is lowered, whereas if the hydroxyl value is less than 40mgKOH/g based on the solid portion, the appearance (distinctness of image) is lowered, and if it exceeds 120mgKOH/g, the processability is lowered. When the acid value is less than 10mgKOH/g, the modification ratio of the acrylic-polyester is lowered, and the appearance, processability and hardness are lowered, and when it exceeds 50mgKOH/g, the transparent coating film is finally yellowed due to unreacted unsaturated groups. Further, if the glass transition temperature of the polyester polyol prepolymer is less than-10 ℃, the hardness is lowered, and if it exceeds 50 ℃, the processability is lowered.
ii) preparation of polyester-acrylic hybrid polyol resin
Polymerizing the mixture of the polyester polyol prepolymer having an unsaturated group, the acrylic monomer and the ethylenically unsaturated monomer prepared in the reaction to prepare a polyester-acrylic hybrid polyol resin. In the polymerization reaction, a radical polymerization initiator and an organic solvent may be used.
As the acrylic monomer, acrylic monomers known in the art may be used without limitation, and for example, at least one of a non-functional acrylic monomer and a hydroxyl group-containing acrylic monomer may be included.
The non-functional acrylic monomer is not particularly limited as long as it does not adversely affect the formation of the acrylic polyol resin. Non-limiting examples of the non-functional acrylic monomer that may be used, if listed, may be at least one selected from the group consisting of alkyl (meth) acrylates, cycloalkyl (meth) acrylates, and bicycloalkyl (meth) acrylates. For example, there are methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, cyclohexyl acrylate, or mixtures thereof, and the like.
As non-limiting examples of the hydroxyl-containing acrylic monomer, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polyalphaolefin acrylate (cardura acrylate), polyalphaolefin methacrylate (cardura methacrylate), caprolactone acrylate, 2, 3-dihydroxypropyl methacrylate, polypropylene-modified acrylate, polypropylene-modified methacrylate, 4-hydroxymethylcyclohexyl-methyl acrylate, 4-hydroxymethylcyclohexyl-methyl methacrylate, a monomer derived from an ethylenically unsaturated acid such as monocarboxylic acid (e.g., (meth) acrylic acid) and an epoxy compound unrelated to radical polymerization (e.g., glycidyl ethers and esters) functional monomers, and the like.
As the ethylenically unsaturated monomer, unsaturated monomers known in the art may be used without limitation. As one example, there are styrene and its derivatives, butadiene, alkyl acrylic acid or methacrylic acid ester having a carbon number of 1 to 12, a mixture thereof, and the like.
The unsaturated group-containing polyester polyol prepolymer and the mixture of the acrylic monomer and the ethylenically unsaturated monomer may be used in a ratio of 20:80 to 80:20 by weight, for example, 30:70 to 70:30 by weight. When the content of the mixture in which the acrylic monomer and the ethylenically unsaturated monomer are added together is less than 20% by weight, hardness and distinctness of image are reduced, and when it exceeds 80% by weight, processability is reduced.
As the polymerization initiator, a general initiator known in the art may be used without limitation. As non-limiting examples of initiators that can be used, there are 2,2 '-azobis (2-methylbutyronitrile), 2' -azobisisobutyronitrile, dibenzoyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyacetate, t-amyl peroxy-2-ethylhexanoate, di-t-amyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, or mixtures thereof, and the like. The content of the initiator may be 0.5 to 10% by weight based on the entire weight of the reaction mixture for preparing the polyester-acrylic hybrid polyol resin. When the content of the initiator corresponds to the above range, the molecular weight of the resin can be prevented from being lowered, and the uncured phenomenon of the coating composition can be prevented.
The solvent is not particularly limited as long as it does not adversely affect the polymerization reaction of the acrylic polyol resin, and any known solvent in the art may be used. As non-limiting examples of the solvent that can be used, there are aromatic hydrocarbon solvents such as toluene, xylene, Kocosol-100, Kocosol-150, ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, ethyl ethoxypropionate, etc., alcohol solvents such as n-butanol, propanol, 1-methoxy-2-propanol, etc. The aforementioned components may be used alone or in combination of 2 or more of them.
As an example, the polyester-acrylic hybrid polyol resin can be obtained by mixing the polyester polyol prepolymer having an unsaturated group with a solvent, heating the mixture to a predetermined temperature (for example, 145 ℃) while injecting an inert gas into the reactor, holding the mixture for a predetermined time, and then adding a mixture of an acrylic monomer and an ethylenically unsaturated monomer to perform an acrylic polymerization reaction. The polyester-acrylic hybrid polyol resin exhibits high distinctness of image, high hardness, and excellent processability.
The polyester-acrylic hybrid polyol resin may have a number average molecular weight (Mn) of 1,500 to 5,500g/mol, a hydroxyl value (OH value) of 20 to 70mgKOH/g, an acid value of 5 to 30mgKOH/g, and a glass transition temperature (Tg) of 20 to 50 ℃ based on solid parts.
In the coating composition of the present invention, the content of the polyester-acrylic hybrid polyol resin may be 50 to 75% by weight based on the total weight (100% by weight) of the coating composition. When the content of the polyester-acrylic hybrid polyol resin is less than 50% by weight, the derived corrosion resistance, processability and curability are low, and when it exceeds 75% by weight, the appearance is low and the workability is poor. The content of the polyester-acrylic hybrid polyol resin may be 35 to 50% by weight based on the total weight of the solid parts.
Curing agent
In the coating composition of the present invention, the curing agent functions to cure the polyester-acrylic hybrid polyol resin to form a stable coating film.
As the curing agent, a curing agent generally used in a resin having a hydroxyl group can be used without limitation, and as one example, a melamine resin or the like can be used. Melamine resin as a substance obtained by polymerizing an alcohol with formaldehyde, for example, a methoxy melamine resin can be obtained by polymerizing methanol with formaldehyde, and a methoxy/butoxy mixed type melamine resin can be obtained by polymerizing a mixture of methanol and isobutanol or n-butanol with formaldehyde. As non-limiting examples of melamine resins that can be used in the present invention, there are hexamethylolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, mixtures thereof, and the like. The melamine resin may have a molecular weight ranging from 300 to 1,000.
The curing agent may be present in an amount of 5 to 15 wt%, based on the total weight of the coating composition (100 wt%). When the content of the curing agent is less than 5% by weight, the hardness, the curability, the solvent resistance, the stain resistance, the chemical resistance, the weather resistance, and the like of the coating film are lowered, and when it exceeds 15% by weight, the flexibility, the impact resistance, and the acid resistance of the coating film are lowered.
Acid catalyst
In the coating composition of the present invention, the acid catalyst promotes the curing of the polyester-acrylic hybrid polyol resin and the curing agent (melamine resin), thereby functioning as a curing accelerator for improving the compactness of the coating film.
As the acid catalyst which can be used, there are sulfonic acid-based compounds, and as non-limiting examples thereof, there are amine-or epoxy-blocked p-toluenesulfonic acid (p-TSA, para-toluene sulfonic acid), dinonylnaphthalene sulfonic acid (DNNSA, dinonylnaphthalene sulfonic acid), dinonylnaphthalene disulfonic acid, dodecylbenzenesulfonic acid (DDBSA, dodecylbenzene sulfonic acid), and the like. They may be used alone or in combination of 2 or more.
The acid catalyst may be present in an amount of 0.1 to 3 wt% based on the total weight of the coating composition (100 wt%). If the content of the acid catalyst is less than 0.1% by weight, the hardness, chemical resistance, degree of curing and weather resistance of the coating film will be low because the coating film is not cured, and if it exceeds 3% by weight, the chemical resistance, appearance and the like of the coating film will be low because of the large amount of the acid catalyst remaining in the coating film.
Solvent(s)
As the solvent of the coating composition of the present invention, a general organic solvent known in the art can be used without limitation. The organic solvent may be an aromatic hydrocarbon, an ester solvent, an ether solvent, an alcohol solvent, or a mixture thereof.
As non-limiting examples of the organic solvent that can be used, Kocosol #100(K-100, SK energy Severe Co., Ltd.), Kocosol #150(K-150, SK energy Severe Co., Ltd.), cyclohexanone, xylene, toluene, cellosolve acetate, methyl ethyl ketone, dibasic ester, propylene glycol methyl ether acetate, n-butyl acetate, propylene glycol monomethyl acetate, 3-methoxybutyl acetate, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, ethanol, isopropanol, n-butanol, pentanol, or a mixed solvent thereof, and the like can be given.
The organic solvent may be contained in an amount such that the balance is satisfied with the total weight (100 wt%) of the coating composition, for example, may be 30 to 50 wt% based on the total weight of the coating composition. When the solvent is in the above range, workability is improved and excellent physical properties of the coating film are exhibited.
Additive agent
The coating composition of the present invention may further include additives commonly used in the field of PCM coating compositions within a range that does not hinder the effects of the present invention.
As non-limiting examples of the additives that can be used, there are dispersing agents, leveling agents, adhesion improving agents, curing retarders, surface conditioning agents, antifoaming agents, surfactants, softening agents, thickeners, weather-resistant additives, drying agents, appearance adjusting agents, moisture absorbing agents, matting agents, coupling agents, pigments, or a mixture of 2 or more thereof, and the like. The aforementioned additives may be added in amounts known in the art, and the content thereof is not particularly limited. As an example, the content of each additive may be 0.1 to 10 wt%, for example, 0.5 to 5 wt%, based on the total weight (100 wt%) of the coating composition.
The dispersant serves to disperse the respective materials constituting the coating composition and to prevent re-aggregation by maintaining a distance, so that uniform physical properties of the coating film are expressed. As the dispersant, a usual one known in the art can be used, and as an example, there is a block copolymer type dispersant having a high molecular weight.
The leveling agent is used to level the coating composition for flat, smooth coating, thereby improving the appearance characteristics of the coating film while increasing the adhesion within the composition. As the leveling agent, a general one known in the art can be used without limitation, and as one example, there are acrylic, silicone, polyester, amine leveling agents, and the like.
The adhesion improving agent is added to improve the adhesion between the coating film and the material. Examples of the adhesion improving agent that can be used include silane-based adhesion improving agents, polyester-based adhesion improving agents, and mixtures thereof.
The defoaming agent serves as a mixture of the oleophilic material and the polysiloxane, and serves to suppress air bubbles generated during coating and improve the appearance of the coating film. As the defoaming agent, a general defoaming agent known in the art can be used without limitation. As an example, a silicone type defoaming agent may be used.
The matting agent is added to scatter light on the surface of the coating film to reduce the gloss. As non-limiting examples of matting agents that can be used, there are synthetic silica matting agents, polypropylene matting agents, polyethylene matting agents, or mixtures thereof, and the like. The matting agent can be adjusted to have a certain particle size, and can increase the surface area of the undercoat film to improve the adhesion to the topcoat.
The curing retarder may be used for the purpose of adjusting the curing speed of the surface of the coating film, thereby improving the smoothness of the cured coating film and suppressing the swelling phenomenon, and as an example, triethylamine, dimethylethanolamine, and the like are given.
The coating composition of the present invention can be prepared according to a general method known in the art, and as an example, can be prepared by mixing the polyester-acrylic hybrid polyol resin of the aforementioned composition, a curing agent, a curing catalyst, an additive, and a solvent in a specific ratio.
< PCM Steel plate >
The present invention provides a PCM steel sheet having a coating film formed by using the coating composition.
The PCM steel plate comprises a steel plate and more than 1 coating film layer formed on the surface of the steel plate, wherein at least one of the more than 1 coating film layer comprises a coating film (for example, a PCM transparent coating film) formed by the coating composition containing the polyester-acrylic hybrid polyol resin. The PCM clear coating film can simultaneously ensure high hardness, high distinctness of image and excellent processability.
The 1 or more coating layers may include a coating film (e.g., a clear layer) formed from the coating composition of the present invention, and may further include a primer layer and/or an overcoat layer. In such a base coat and a top coat, a base coat or a top coat, respectively, which are common in the art, may be applied without limitation.
As the steel sheet, a metal sheet used as an interior and exterior material of a building in the art may be used without limitation, and as one example, there are cold rolled steel (CR), hot dip galvanized steel (GI), electrogalvanized steel (EGI), alloy steel sheet (GA), aluminized zinc steel (Galvalume), stainless steel (SUS), tin or copper plated steel, hot dip galvanized steel sheet, galvannealed steel sheet, electrogalvanized steel sheet, hot dip aluminum zinc alloy steel sheet, aluminum sheet, and the like.
The thickness of the coating film layer formed on the metal plate is not particularly limited, and as an example, the dry coating film thickness may be 3 to 30 μm.
The PCM steel sheet of the present invention may be prepared according to a method generally used in the art, and may be composed of a step of coating the aforementioned coating composition on a metal sheet as a Substrate (Substrate) and then drying it, as one example. As the coating method, a general coating method known in the art may be applied, and curtain coating, roll coating, dip coating, bar coating, spray coating, and the like may be used as an example.
The drying condition may be appropriately changed according to the atmospheric condition to be dried by the width and thickness of the dried metal plate and the line speed, and as an example, may be performed for 30 to 40 seconds under the condition that PMT (peak metal temperature) is 190 to 230 ℃.
The PCM steel sheet prepared as described above may be pretreated with chromate, phosphate, or the like before coating. The PCM steel sheet of the present invention can be usefully used for printed products for home appliances, and can also be suitably used for interior and exterior materials for buildings. However, the use is not limited to the above.
The present invention will be described more specifically with reference to examples. However, the following examples are only for the purpose of aiding the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
Synthesis example 1 preparation of polyester-acrylic hybrid polyol (A) resin
1-1.Preparation of unsaturated group-containing polyester polyol prepolymer
In a four-neck flask for synthesis equipped with a thermometer, a stirrer, a packed column, an H separation tube, a condenser and a heating device, 130g of neopentyl glycol, 180g of 1, 4-cyclohexanedimethanol, 335g of hexahydrophthalic anhydride and 0.06g of Fascat 4101(pmc organometallix Co.) were charged, and the reaction was carried out by removing the condensation water under an inert gas atmosphere and raising the temperature to 240 ℃. 24g of xylene was charged under cooling at an acid value of 25, azeotropic distillation was carried out at 230 ℃ to give an acid value of 4, cooling was carried out, 35g of maleic anhydride was charged at 160 ℃ or lower, the reaction was maintained at 160 ℃ to give an acid value of 30 to 40, cooling was carried out, and the mixture was diluted with Kocosol-10068 g, Kocosol-15027 g and cyclohexanone 41g to give an unsaturated group-containing polyester polyol prepolymer having a number average molecular weight (Mn) of 2,100g/mol, a solid content of 80%, a hydroxyl value of 26mgKOH/g, an acid value of 35mgKOH/g and a glass transition temperature (Tg) of 19 ℃.
1-2.Preparation of polyester-acrylic hybrid polyol resin
And (3) carrying out acrylic polymerization by using the unsaturated group-containing polyester polyol prepolymer. 377g of the unsaturated group-containing polyester polyol prepolymer prepared in the above 1-1 and Kocosol-100145 g were put into a four-necked flask for synthesis equipped with a thermometer, a stirrer, a condenser and a heating device, and mixed uniformly, and heated to 145 ℃ under nitrogen injection and held. The preparation method comprises the steps of uniformly mixing 90g of styrene monomer, 13g of 2-hydroxyethyl acrylate, 56g of n-butyl methacrylate, 6g of ethylhexyl methacrylate, 17g of isobornyl acrylate and 10g of cyclohexyl methacrylate, uniformly mixing 3g of tert-butyl peroxy-2-ethylhexanoate and Kocosol-10029 g, uniformly separating and dripping for 240 minutes, and keeping the constant temperature for 120 minutes. After completion of the holding, the reaction mixture was cooled while diluting with 45g of butyl acetate, to obtain a polyester-acrylic hybrid polyol resin having a solid content of 60%, a Gardner viscosity of Z, a hydroxyl value of 30mgKOH/g on the solid weight basis, an acid value of 20mgKOH/g, a number average molecular weight (Mn) of 3,300mol/g, a weight average molecular weight (Mw) of 8,000g/mol, and a glass transition temperature (Tg) of 35 ℃.
Synthesis example 2 preparation of polyester-acrylic hybrid polyol (B) resin
2-1.Preparation of unsaturated group-containing polyester polyol prepolymer
In a four-necked flask for synthesis equipped with a thermometer, a stirrer, a packed column, an H separation tube, a condenser and a heating device, 167g of neopentyl glycol, 232g of 1, 4-cyclohexanedimethanol, 430g of hexahydrophthalic anhydride and 0.08g of Fascat 4101(pmc organometallix Co.) were put, and the reaction was carried out by removing the condensation water under an inert gas atmosphere and raising the temperature to 240 ℃. The reaction was carried out by cooling at an acid value of 25, adding 31g of xylene, carrying out azeotropic distillation at 230 ℃ to give an acid value of 4, cooling, adding 21g of maleic anhydride at 160 ℃ or lower, maintaining the reaction at 160 ℃ to give an acid value of 15, cooling, and diluting with Kocosol-10084 g, Kocosol-15034 g, and 51g of cyclohexanone to give an unsaturated group-containing polyester polyol prepolymer having a number average molecular weight (Mn) of 2,000g/mol, a solid content of 80%, a hydroxyl value of 44mgKOH/g, an acid value of 16mgKOH/g, and a glass transition temperature (Tg) of 17 ℃.
2-2.Preparation of polyester-acrylic hybrid polyol resin
And (3) carrying out acrylic polymerization by using the unsaturated group-containing polyester polyol prepolymer. 377g of the unsaturated group-containing polyester polyol prepolymer prepared in the above 2-1 and Kocosol-100145 g were put into a four-necked flask for synthesis equipped with a thermometer, a stirrer, a condenser and a heating device, and mixed uniformly, and heated to 145 ℃ under nitrogen injection and held. The preparation method comprises the steps of uniformly mixing 90g of styrene monomer, 13g of 2-hydroxyethyl acrylate, 56g of n-butyl methacrylate, 6g of ethylhexyl methacrylate, 17g of isobornyl acrylate and 10g of cyclohexyl methacrylate, uniformly mixing 3g of tert-butyl peroxy-2-ethylhexanoate and Kocosol-10029 g, uniformly separating and dripping for 240 minutes, and keeping the constant temperature for 120 minutes. After completion of the holding, the reaction mixture was cooled while diluting with 45g of butyl acetate, to obtain a polyester-acrylic hybrid polyol resin having a solid content of 60%, a Gardner viscosity of Z-, a hydroxyl value of 40mgKOH/g on a solid weight basis, an acid value of 10mgKOH/g, a number average molecular weight (Mn) of 3,200mol/g, a weight average molecular weight (Mw) of 8,000g/mol, and a glass transition temperature (Tg) of 32 ℃.
Synthesis example 3 preparation of polyester polyol (C) resin
98g of neopentyl glycol, 56g of trimethylolpropane, 39g of ethylene glycol, 135g of 1, 4-cyclohexanedimethanol, 116g of phthalic anhydride, 114g of adipic acid, 43g of terephthalic acid, 130g of isophthalic acid, and 0.3g of Fascat 4101(pmc organometallix Co.) were put into a four-neck flask for synthesis equipped with a thermometer, a stirrer, a packed column, an H separation tube, a condenser, and a heating device, and the polycondensation water was removed under an inert gas atmosphere and the temperature was raised to 220 ℃ to carry out a reaction. After cooling at an acid value of 15 to 20, 32g of xylene was charged, and azeotropic distillation was carried out at 210 ℃ to reduce the acid value to 5 or less, the resulting product was cooled and diluted with 317g of Kocosol-100(SK chemical Co.) to obtain a polyester polyol resin having a solid content of 65%, a Gardner viscosity of Z2, an acid value of 3.7mgKOH/g, a hydroxyl value of 90mgKOH/g based on the weight of the solid content, and a weight average molecular weight (Mw) of 2,000 g/mol.
Synthesis example 4 preparation of polyurethane-modified polyester-acrylic hybrid resin (D)
4-1.Preparation of polyester polyol prepolymer
In a four-necked flask for synthesis equipped with a thermometer, a stirrer, a packed column, an H separation tube, a condenser and a heating device, 137g of neopentyl glycol, 190g of cyclohexanedimethanol, 354g of hexahydrophthalic anhydride and 0.06g of Fascat 4101(pmc organometallix) were placed, and the reaction was carried out by removing the condensed water under an inert gas atmosphere and raising the temperature to 240 ℃. After cooling at an acid value of 25, 24g of xylene was charged, and azeotropic distillation was carried out at 230 ℃ to reduce the acid value to 5 or less, the mixture was cooled and diluted with 67g of Kocosol-100(SK chemical Co.), 27g of Kocosol-150(SK chemical Co.), and 40g of cyclohexanone to obtain a polyester polyol prepolymer having a number average molecular weight (Mn) of 1,950g/mol, a solid content of 80%, an acid value of 3.8mgKOH/g, and a glass transition temperature (Tg) of 16 ℃.
4-2.Preparation of acrylic prepolymer
In a four-necked flask for synthesis equipped with a thermometer, a stirrer, a condenser and a heating device, Kocosol-100140g was charged and mixed uniformly, and the mixture was heated to a constant temperature (145 ℃) under nitrogen injection. After keeping stable at constant temperature, 196g of methyl methacrylate, 42g of 2-hydroxyethyl acrylate, 70g of n-butyl acrylate and 252g of isobornyl acrylate were uniformly mixed, 14g of di-tert-butyl peroxide and Kocosol-10067 g were uniformly mixed, and after uniform separation and dropwise addition over 240 minutes, the mixture was kept at constant temperature for 120 minutes. After the completion of the holding, the reaction mixture was cooled while diluting with 13g of butyl acetate, thereby obtaining an acrylic prepolymer resin having a solid content of 70%, a hydroxyl value of 32mgKOH/g on a solid weight basis, a Gardner viscosity of Y, a number average molecular weight (Mn) of 2,400g/mol, a weight average molecular weight (Mw) of 4,800g/mol, and a glass transition temperature (Tg) of 30 ℃.
4-3.Preparation of polyurethane modified polyester-acrylic hybrid resin
In a four-necked flask for synthesis equipped with a thermometer, a stirrer, an H separation tube, a condenser and a heating device, 151g of the polyester polyol prepolymer obtained in the above 4-1 and 402g of the acrylic prepolymer obtained in the above 4-2 were charged, uniformly mixed, heated to 50 ℃ and then charged with 17.8g of hexamethylene diisocyanate, and the mixture was heated to 60 ℃ under an inert gas atmosphere to carry out a maintenance reaction. When the residual NCO% was measured and became 0.02% or less, the maintenance reaction was terminated, and the reaction solution was diluted with Kocosol 29g and cooled to obtain a polyurethane-modified polyester-acrylic hybrid resin having a solid content of 65%, a hydroxyl value of 30mgKOH/g based on the solid content, a Gardner viscosity Z3, a number average molecular weight (Mn) of 4,700g/mol, a weight average molecular weight (Mw) of 35,000g/mol, and a glass transition temperature (Tg) of 20 ℃.
Synthesis example 5 preparation of polyester-acrylic acid blend polyol (E)
153g of the polyester polyol prepolymer prepared in Synthesis example 4-1, 175g of the acrylic prepolymer prepared in Synthesis example 4-2, and Kocosol-10022 g were uniformly mixed in a flask equipped with a stirrer to obtain a polyester-acrylic acid blend polyol resin having a number average molecular weight (Mn) of 3,400g/mol, a solid content of 70%, a hydroxyl value of 60mgKOH/g on a solid weight basis, and a glass transition temperature (Tg) of 23 ℃.
[ examples 1-2]
Coating compositions of examples 1-2 were prepared according to the compositions of table 1 below.
Comparative examples 1 to 3
Coating compositions of comparative examples 1 to 3 were prepared according to the compositions of the table 1.
[ TABLE 1]
[ Experimental example and evaluation of physical Properties ]
Physical properties of the clear coating compositions for PCM prepared in examples 1 to 2 and comparative examples 1 to 3 were evaluated as follows.
After applying a 5 μm and 20 μm thick coating of a lower coating (KCC company, FP1817) and an upper coating (KCC company, FJ2604) to a PCM material for a GI (Galvanized Iron) material, the clear coatings of examples 1-2 and comparative examples 1-3 were applied to the PCM material for a 20 μm thickness to prepare test pieces. Then, the physical properties of each test piece were measured in the following manner, and the results are shown in table 2.
(1) Hardness of pencil
Hardness of each pencil without damaging the coating film was measured using Mitsubishi pencil (3B, 2B, HB, F, H, 2H, 3H).
(2) Processability (T bonding)
The test piece was bent (bending) in accordance with ASTM D4145, and the level of cracking of the coating film at the bent portion and the peeling of the coating film (Peel-off) after Taping and tearing (Taping) were evaluated.
(3) Gloss of
The 60 degree gloss was measured using a BYK gloss meter (gloss meter).
(4) Degree of curing
After the MEK (Methylketone) solution was sufficiently soaked in the gauze, the gauze was rubbed (rubbed) by a length of 10cm for a predetermined number of times at a speed of 100 cycles per minute with a load of about 1 to 1.5kg applied by the index finger, and after the test was completed, the test piece was observed and evaluated.
(5) Appearance (distinctness of image)
CF (combined factor) values were measured using WAVESCAN, BYK. The higher the CF value, the more excellent the distinctness of image.
(6) Yellow stain
After the transparent coating film was applied on the white upper coat, whether the transparent coating film was yellowed or not was judged by visual observation.
[ TABLE 2]
As shown in table 2 above, it was confirmed that the coating materials of examples 1 and 2, which comprise the polyester-acrylic hybrid polyol resins (a) and (B) of the present invention, exhibit excellent physical properties in all of gloss, processability, hardness, appearance, and degree of curing. On the other hand, the coating materials of comparative examples 1 to 3, which did not contain the polyester-acrylic hybrid polyol resin, exhibited poor physical properties of at least one of processability, hardness and gloss.
From the above results, it is understood that the coating composition comprising the polyester-acrylic hybrid polyol resin of the present invention satisfies high processability while exhibiting high appearance (distinctness of image) and high hardness.
Claims (5)
1. A coating composition comprising a polyester-acrylic hybrid polyol resin, a curing agent, an acid catalyst, and a solvent,
the polyester-acrylic hybrid polyol resin has a number average molecular weight of 1,500 to 5,500g/mol, a hydroxyl value of 20 to 70mgKOH/g, an acid value of 5 to 30mgKOH/g, a glass transition temperature of 20 to 50 ℃ on the basis of solid parts,
the polyester-acrylic hybrid polyol resin comprises a polymerization reaction product,
the product of the polymerization reaction is that,
a polyester polyol prepolymer having a number average molecular weight of 500 to 3,000g/mol, a hydroxyl value of 25 to 120mgKOH/g, an acid value of 10 to 50mgKOH/g, and a glass transition temperature of-10 to 50 ℃ on a solid basis, and a polyester polyol having an unsaturated group,
Acrylic acid monomer, and
a polymerization reaction product of an ethylenically unsaturated monomer,
the unsaturated group-containing polyester polyol prepolymer is a polycondensate comprising a mixture of at least one acid monomer containing a carboxylic acid functional group, at least one polyfunctional alcohol monomer, and an anhydride having an unsaturated group, the double bond of the anhydride being located at the end of the main chain,
the acid monomer is a mixture containing 70 to 95 equivalent% of two or more functional alicyclic carboxylic acids and 5 to 30 equivalent% of aliphatic carboxylic acids based on 100 equivalent% of the total acid monomer,
the polyfunctional alcohol monomer is a mixture containing 40 to 80 equivalent% of two functional aliphatic alcohols, 20 to 60 equivalent% of alicyclic alcohols, and 0 to 5 equivalent% of three or more functional polyfunctional alcohols, based on 100 equivalent% of the total alcohol monomers.
2. The coating composition of claim 1,
the unsaturated group-containing polyester polyol prepolymer is used in a ratio of 20:80 to 80:20 by weight with respect to a mixture of an acrylic monomer and an ethylenically unsaturated monomer.
3. The coating composition of claim 1,
the acid monomer having a carboxylic acid functional group and the polyfunctional alcohol monomer are used in a ratio of an alcohol/carboxylic acid equivalent ratio of 1.05 to 1.50.
4. The coating composition of claim 1,
the content of the acid anhydride is in the range of 10 to 110 mol% based on the number of moles of the polyester in the unsaturated group-containing polyester polyol prepolymer.
5. The coating composition of claim 1,
comprising 50 to 75% by weight of a polyester-acrylic hybrid polyol resin, 5 to 15% by weight of a curing agent, 0.1 to 3% by weight of an acid catalyst, and the balance of a solvent satisfying 100% by weight of the whole composition.
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