CN111630120A - Clear paint composition - Google Patents
Clear paint composition Download PDFInfo
- Publication number
- CN111630120A CN111630120A CN201880087383.7A CN201880087383A CN111630120A CN 111630120 A CN111630120 A CN 111630120A CN 201880087383 A CN201880087383 A CN 201880087383A CN 111630120 A CN111630120 A CN 111630120A
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- CN
- China
- Prior art keywords
- acrylic polyol
- clear paint
- paint composition
- resin
- polyol resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
Abstract
The present invention relates to a one-component clear paint composition comprising: one or more types of acrylic polyol resins; a modified acrylic polyol resin produced by the reaction of a glycidyl ester with an acrylic resin containing carboxyl groups and hydroxyl groups; and a hardening agent.
Description
Technical Field
The present invention relates to clear paint compositions.
Background
Depending on the nature, automotive coating systems can be divided into midcoat, which determines the basic mechanical properties, topbase coat, which is highly important for color and appearance, and topclear coat, which can impart final gloss and clarity to the automobile as well as complement the mechanical properties.
Conventionally, as a top clear coating composition applied to a vehicle body, a one-component clear coating composed of a hydroxyl group-containing acrylic resin, a melamine resin, and a blocked isocyanate resin is widely used, and additives including a leveling agent, a slip agent, a UV absorber, an antioxidant, and the like, and an acid catalyst are further added thereto. However, conventional clear paints produced using hydroxyl group-containing acrylic resins exhibit poor recoat adhesion when applied to water-soluble base paint lacquers and have poor chemical resistance to acid rain and the like. As a solution to this, in korean registered patent No. 0576447 focused on developing a system capable of improving acid resistance while maintaining conventional acrylic polyol resin, melamine resin, blocked isocyanate and conventional paint curing system, acrylic polyol resin was synthesized and selected to minimize the content of melamine, maximize the content of characteristic blocked isocyanate and employ epoxy resin, and thus an automotive solvent-based one-component transparent top paint composition was developed, which exhibits excellent acid resistance and recoat adhesion, exhibits excellent scratch resistance and water resistance, is capable of minimizing yellowing caused by impurities and the like, and forms a film having excellent acid resistance and excellent appearance quality. However, one-component clear coating systems employing epoxy functional groups have the following basic problems: has poor storage stability due to poor stability of the acid-epoxy resin itself, and gradually forms a gel if not used immediately after production. In addition, when applied over water-soluble top substrate coatings, the one-component clear coat system may react with amines applied to the water-soluble top substrate coating, resulting in yellowing.
In order to solve the problem of the one-component clear top paint, in korean laid-open patent application No. 2006-0119012, a two-component automotive paint composition was developed, which is composed of a main material component including a hydroxyl group-containing acrylic polyol main resin, a biurea group-containing acrylic polyol auxiliary resin, and a solvent, and a hardener component including a hexamethylene diisocyanate trimer, an isophorone diisocyanate trimer, and a solvent. Such compositions can impart excellent appearance qualities, excellent mechanical properties, compatibility with water-soluble top matrix coatings, layering, clarity, and the like. However, two-component clear paints are hazardous to health due to the use of isocyanates, and when exposed to moisture, may have undesirable side reactions due to moisture, and have a short shelf life.
Therefore, a great deal of technical development is underway to improve the appearance quality and mechanical properties of the top clear coat layer.
[ related Art document ]
Korean registered patent publication No. 0576447
Korean laid-open patent application No. 2006 + 0119012
Korean laid-open patent application No. 2006-
BRIEF SUMMARY OF THE PRESENT DISCLOSURE
Technical problem
The present invention relates to providing clear paint compositions.
Technical scheme
The present invention provides a one-part clear paint composition comprising one or more acrylic polyol resins, a modified acrylic polyol resin produced by the reaction of an acrylic resin containing carboxyl and hydroxyl groups with a glycidyl ester, and a hardener component.
Advantageous effects
The clear paint composition of the present invention has excellent weather resistance and chipping resistance, imparts excellent image clarity to a high-gloss coating, and has excellent scratch resistance, compared to conventional one-component paint compositions.
Best mode
Hereinafter, the present invention will be described in detail.
The present invention provides clear paint compositions.
The one-component clear paint composition of the present invention comprises: one or more acrylic polyol resins; a modified acrylic polyol resin produced by the reaction of an acrylic resin containing carboxyl groups and hydroxyl groups with a glycidyl ester; and a hardener component.
Hereinafter, each of the above components will be described in detail.
< acrylic polyol resin >
The clear paint composition of the present invention comprises one or more acrylic polyol resins.
The acrylic polyol resin used in the present invention can be used to improve the appearance quality and mechanical properties of the coating.
The acrylic polyol resin may be polymerized using a hydroxyl group-containing acrylic monomer. For example, the hydroxyl group-containing acrylic monomer may be monohydroxyalkyl (meth) acrylate, dihydroxyalkyl (meth) acrylate, lactone (meth) acrylate, a hydroxy alicyclic (meth) acrylate, or the like. For example, the hydroxyl group-containing acrylic monomer may be 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropanediol (meth) acrylate, cardura methacrylate, caprolactone acrylate, caprolactone methacrylate, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxyethyl (meth) acrylate, 2, 4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 4-hydroxymethylcyclohexylmethyl acrylate, 1, 6-hexanediol di (meth) acrylate, and the like.
The hydroxyl group-containing acrylic monomer may be copolymerized with a monomer such as styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, or a mixture thereof.
The acrylic polyol resin may be included in an amount of 30 to 70 wt%, 30 to 60 wt%, or 30 to 50 wt% with respect to the total weight of the clear paint composition. When the content of the acrylic polyol resin is less than 30 wt%, appearance quality cannot be effectively improved due to a decrease in chemical properties such as chemical resistance, and when the content of the acrylic polyol resin is more than 70 wt%, chipping resistance may be reduced due to the coating film becoming too hard.
Glass transition temperature (T) of acrylic polyol resing) May be 10 ℃ to 50 ℃. When the glass transition temperature is less than 10 ℃, the drying ability of the coating film may be deteriorated, and when the glass transition temperature is more than 50 ℃, the impact resistance may be lowered due to the increase in hardness of the coating film.
The acrylic polyol resin of the present invention may include two or more acrylic polyol resins having different viscosities, and the two or more acrylic polyol resins may be a first acrylic polyol resin having a viscosity of 950cP to 2,400cP at 25 ℃ and a second acrylic polyol resin having a viscosity of 20cP to 55cP at 25 ℃.
The first acrylic polyol resin may serve as a main resin in the clear paint composition, and may have an acid value of 5 to 15mgKOH/g, a hydroxyl value of 120 to 170mgKOH/g, a glass transition temperature of 10 to 20 ℃, and a weight average molecular weight of 10,000 to 30,000g/mol, but the present invention is not limited thereto. Further, the first acrylic polyol resin may have a solid content of 55 wt% to 70 wt% or 58 wt% to 61 wt%.
The first acrylic polyol resin may be included in an amount of 20 to 69.9 wt%, 20 to 69 wt%, or 25 to 69 wt% with respect to the total weight of the clear paint composition. When the content of the first acrylic polyol resin is less than 20 wt%, chemical properties such as chemical resistance may be reduced, and when the content of the first acrylic polyol resin is more than 69.9 wt%, chipping resistance may be reduced since the coating film becomes too hard.
The second acrylic polyol resin may function as a leveling agent in the clear paint composition, and may have an acid value and a hydroxyl value of 0mgKOH/g, a glass transition temperature of 10 ℃ to 50 ℃, a weight average molecular weight of 3,000g/mol to 15,000g/mol, and a solid content of 40 wt% to 60 wt% or 49 wt% to 51 wt%.
The second acrylic polyol resin may be included in an amount of 0.1 to 30 wt%, 1 to 10 wt%, or 1 to 5 wt% with respect to the total weight of the clear paint composition. When the content of the second acryl polyol resin is less than 0.1 wt%, appearance quality may be reduced since the surface of the paint is not leveled, and when the content of the second acryl polyol resin is more than 30 wt%, the properties of the coating film may be reduced.
< modified acrylic polyol resin >
The clear paint composition of the present invention comprises a modified acrylic polyol resin.
The modified acrylic polyol resin is added to the clear paint composition as a secondary resin in addition to one or more acrylic polyol primary resins, and may be used to improve the gloss, distinctness of image (DOI), and scratch resistance of the resulting coating film.
The modified acrylic polyol resin can be produced by the reaction of an acrylic resin containing carboxyl groups and hydroxyl groups with a glycidyl ester.
The carboxyl-and hydroxyl-containing acrylic resin may be prepared by polymerizing an ethylenically unsaturated monomer, a non-functional acrylic monomer, a carboxyl-containing acrylic monomer, and a hydroxyl-containing acrylic monomer.
The ethylenically unsaturated monomer may be styrene, methyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, or the like. The ethylenically unsaturated monomer may be included in an amount of 10 to 16 wt% or 11 to 12 wt% with respect to the total amount of monomers used to prepare the acrylic resin. When the content of the ethylenically unsaturated monomer is less than 10 wt%, appearance quality may be reduced due to influence on gloss, and when the content of the ethylenically unsaturated monomer is more than 16 wt%, long-term weather resistance may be reduced when the composition is applied to paint.
The non-functional acrylic monomer is not particularly limited as long as it does not have an adverse effect on the acrylic polyol resin, and may be one or more selected from the group consisting of alkyl (meth) acrylates, cycloalkyl (meth) acrylates, and dicycloalkyl (meth) acrylates. For example, as the non-functional acrylic monomer, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isobornyl acrylate, cyclohexyl acrylate, and the like may be used, but the present invention is not limited thereto. The non-functional acrylic monomer may be included in an amount of 55 to 62 wt% or 59 to 62 wt% with respect to the total amount of monomers used to prepare the acrylic resin. When the content of the non-functional acrylic monomer is less than 55 wt%, weather resistance may be reduced due to the increase in the amount of the functional acrylic monomer, and when the content of the non-functional acrylic monomer is more than 62 wt%, weather resistance and scratch resistance of the paint may be deteriorated due to the reduction in the hydroxyl value of the resulting modified acrylic polyol resin.
As the carboxyl group-containing monomer, benzoic acid, cyclohexanecarboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, natural or synthetic fatty acid, acrylic acid, methacrylic acid, dimeric acrylic acid, crotonic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, and the like can be used, but the present invention is not limited thereto. The carboxyl group-containing monomer may be included in an amount of 4 to 7 wt% or 5 to 6.2 wt% with respect to the total amount of monomers used to prepare the acrylic resin. When the content of the carboxyl group-containing monomer is less than 4 wt%, scratch resistance may be negatively affected due to a decrease in viscosity, and when the content of the carboxyl group-containing monomer is more than 7 wt%, viscosity may increase due to an increase in hydrogen bonds in or between the acrylic resins.
The hydroxyl group-containing monomer may be 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, cardura methacrylate, caprolactone acrylate, caprolactone methacrylate, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, 4-hydroxymethylcyclohexylmethyl acrylate, etc., but the present invention is not limited thereto. The hydroxyl group-containing monomer may be included in an amount of 15 to 22 wt% or 18 to 22 wt% with respect to the total amount of monomers used to prepare the acrylic resin. When the content of the hydroxyl group-containing monomer is less than 15 wt%, the properties of the paint may be reduced due to a decrease in the crosslinking density of the coating film, and when the content of the hydroxyl group-containing monomer is more than 22 wt%, the properties of the coating film are improved due to an increase in the crosslinking density, but the spreadability of the coating film is reduced due to an increase in surface tension, and the appearance quality of the coating film may be deteriorated due to a decrease in compatibility with other components.
In the preparation of the acrylic resin, an organic solvent or an initiator may also be used.
The type of the organic solvent is not particularly limited. For example, the organic solvent may be: hydrocarbon-based solvents such as toluene or xylene; ketone-based solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, or ethyl propyl ketone; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, ethyl ethoxypropionate, or t-butyl peroxyacetate; alcohol-based solvents such as n-butanol, propanol, butanol or 1-methoxy-2-propanol; and the like.
The initiator may be a radical polymerization initiator, and the type of the initiator is not particularly limited. For example, the initiator may be 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, cumyl hydroperoxide, dicumyl peroxide, and the like. The initiator may be included in an amount of 1 to 7 wt%, 5 to 7 wt%, or 6 to 7 wt% with respect to the total amount of monomers used to prepare the acrylic resin. When the content of the initiator is less than 1 wt%, properties may be reduced due to low polymerization degree, and when the content of the initiator is more than 7 wt%, appearance quality of the coating film may be deteriorated due to excessive hardening of the coating composition.
The glycidyl ester may have a chemical structure of the following chemical formula 1.
[ chemical formula 1]
(Here, R is a C1 to C30 alkyl group.)
R may be represented by the structure
And R1 and R2 may each independently be a C1 to C10 alkyl group. Dot
Represents a site in which a substituent is bonded to the main chain.
The alkyl group may be straight-chain or branched, and may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethylpropyl, 1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but the invention is not limited thereto.
The glycidyl ester may be included in an amount of 6 to 12 wt% or 10 to 12 wt% with respect to the total amount of monomers used to prepare the acrylic resin. When the content of the glycidyl ester is less than 6 wt%, scratch resistance and weather resistance of the paint may be negatively affected due to insufficient reaction of the acrylic resin with the glycidyl ester, and when the content of the glycidyl ester is more than 12 wt%, excessive hardening may occur due to the presence of an excessive amount of hydroxyl groups, and thus appearance quality of the coating film may be negatively affected.
The glycidyl ester may react with an acrylic resin containing a carboxyl group and a hydroxyl group, thereby causing a ring-opening polymerization reaction of an epoxy group including the glycidyl group. When a modified acrylic polyol resin in which the carboxyl group of the acrylic resin is modified with a glycidyl ester is obtained as a result of the reaction and is used as an auxiliary resin in the clear paint composition of the present invention, the storage stability of the paint can be ensured and the glass transition temperature (T) is optimized as a result of the optimizationg) The fluidity and leveling are improved, and thus the appearance quality of the clear paint can be improved. In addition, since the long-chain polyol is introduced into the acrylic resin, low-temperature hardening is achieved, and thus the appearance quality of the oil-based clear paint can be improved.
The weight average molecular weight of the modified acrylic polyol resin may be 5,000g/mol to 15,000g/mol, but the present invention is not limited thereto.
The modified acrylic polyol resin may be included in an amount of 10 to 25 wt% with respect to the total weight of the clear paint composition.
When the content of the modified acrylic polyol resin is less than 10 wt%, the appearance quality of the paint may not be improved, and when the content of the modified acrylic polyol resin is more than 25 wt%, the fluidity and leveling property of the paint may be deteriorated.
The modified acrylic polyol resin may have a glass transition temperature (T) of 0 ℃ or less, -10 ℃ or more and 0 ℃ or less, or-5 ℃ or more and 0 ℃ or lessg). When the glass transition temperature of the modified acrylic polyol resin satisfies the above range, the fluidity and leveling property of the paint composition can be improved.
The modified acrylic polyol resin may have a hydroxyl value of 100mgKOH/g to 150mgKOH/g or 100mgKOH/g to 120 mgKOH/g. When the hydroxyl value of the modified acrylic polyol resin is less than 100mgKOH/g, weather resistance may also be adversely affected due to poor adhesion, and when the hydroxyl value is more than 150mgKOH/g, the appearance quality of the modified acrylic polyol resin may be reduced.
The modified acrylic polyol resin may have an acid value of from 10mgKOH/g to 15 mgKOH/g. When the acid value of the modified acrylic polyol resin is less than 10mgKOH/g, the adhesion of the paint may be reduced, and when the acid value is more than 15mgKOH/g, the appearance quality of the paint may be reduced.
The modified acrylic polyol resin may have a viscosity of 70cP to 110cP at 25 ℃. When the viscosity of the modified acrylic polyol resin satisfies this range, a coating film having excellent appearance quality can be obtained due to the improvement in fluidity and leveling property of the resulting clear paint composition. When the viscosity of the modified acrylic polyol resin is less than 70cP at 25 ℃, scratch resistance, gloss and weather resistance of the paint may be deteriorated, and when the viscosity is more than 110cP, chipping resistance may be deteriorated.
< polyester polyol resin >
The clear paint composition of the present invention may further comprise a polyester polyol resin.
The polyester polyol resin is used to improve adhesion and weather resistance of paint, and when the polyester polyol resin is used in addition to the acrylic polyol resin, flexibility of a coating film and adhesion of paint can be improved, and gloss and appearance quality can be improved.
The polyester polyol resin may be prepared by a condensation reaction of an acid monomer and an alcohol monomer. For example, the polyester polyol can be prepared by dehydration-condensation reaction of a dibasic acid (adipic acid) and a diol or triol. The characteristics and properties of the polyester polyols may vary depending on the type of acid used as well as the type and molecular weight of the polyol.
The polyester polyol resin may be included in an amount of 1 to 10 wt% or 1 to 5 wt% with respect to the total weight of the clear paint composition.
The polyester polyol resin can have a resin solids content of 60 to 80 wt%, a viscosity of 1,500 to 3,500cP at 25 ℃, an acid value of 20 to 25mgKOH/g, a hydroxyl value of 130 to 150mgKOH/g, a glass transition temperature of 0 to 10 ℃, and a weight average molecular weight of 3,000 to 8,000 g/mol. When the properties of the polyester polyol resin satisfy the above ranges, the flexibility of the coating film and the adhesion of paint may be improved, and the gloss and appearance quality of the coating film may be improved.
< curing agent >
The clear paint composition of the present invention comprises a hardener.
As the hardening agent of the present invention, any hardening agent may be used without limitation as long as it can be crosslinked with the hydroxyl group of the acrylic polyol resin or the modified acrylic polyol resin.
As the hardener, one or more selected from melamine compounds and urethane compounds may be used.
The type of melamine compound is not particularly limited, but the melamine compound may be, for example, hexamethylolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, or the like.
The melamine compound can have a solids content of 56 wt% to 60 wt%, a viscosity of 600 mPa-s to 1,000 mPa-s at 25 ℃, a hessian scale (color) of 50 or less, an acid value of 1mg KOH/g or less, and a weight average molecular weight of 1,000g/mol to 4,000 g/mol.
As the urethane compound, any urethane compound that can be used for clear paints may be used without limitation, and the urethane compound may be prepared by reacting an alcohol with a polyisocyanate.
The alcohol may be ethylene glycol, 1, 2-propanediol, 1, 4-propanediol, 1, 5-pentanediol, 1, 2-butanediol, 1, 2-hexanediol, bisphenol a, bisphenol F, ethoxylated bisphenol a, benzene diol, etc., but the present invention is not limited thereto.
The polyisocyanate may be an aliphatic or aromatic isocyanate, and may be: an aliphatic polyisocyanate selected from the group consisting of tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate and isophorone diisocyanate; aromatic polyisocyanates selected from the group consisting of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, p-phenylene isocyanate, diphenylmethane-4, 4 '-diisocyanate, polymethylene polyphenyl isocyanate and triphenylmethane-4, 4', 4 "-triisocyanate; or mixtures thereof, but the invention is not limited thereto.
The urethane compound may have a solid content of 73 to 77 wt%, a viscosity of 2,800 mPa-s to 5,800 mPa-s at 25 ℃, and a hainson scale (color) of 50 or less.
The hardener component may be included in an amount of 20 to 50 wt% with respect to the total weight of the clear paint composition. When the content of the hardener component is less than 20 wt%, properties such as solvent resistance of the paint may be affected since incomplete hardening occurs when the hardener component reacts with the main resin, and when the content of the hardener component is more than 50 wt%, excessive hardening may occur, properties such as adhesion and impact resistance of the paint are affected, and unreacted hardener may remain in the paint and adversely affect other properties.
< organic solvent >
The clear paint composition of the present invention may comprise an organic solvent.
The organic solvent is not particularly limited as long as it does not cause a problem in polymerization of the acrylic polyol resin. For example, the organic solvent may be: aromatic hydrocarbon-based solvents such as toluene or xylene; ketone-based solvents such as dimethyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone, or methyl aryl ketone; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl cellosolve acetate, butyl cellosolve acetate, or carbitol acetate; alcohol-based solvents such as n-propanol, isopropanol, n-butanol, isobutanol, or tert-butanol; and the like.
The organic solvent may be included in an amount of 5 to 20 wt% with respect to the total weight of the clear paint composition. When the content of the organic solvent is less than 5 wt%, it may be difficult to produce paint, and when the content of the organic solvent is more than 20 wt%, coating workability may be reduced.
< additives >
The clear paint composition of the present invention may further comprise additives.
The additives may include one or more selected from the group consisting of surface modifiers, light stabilizers, weather resistant additives, drying agents, appearance modifiers, defoamers, and UV absorbers. The additive may be included in an amount of 0.1 to 5 wt% with respect to the total weight of the clear paint composition.
Hereinafter, the present invention will be described in more detail by way of exemplary embodiments. However, these exemplary embodiments are provided only to facilitate understanding of the present invention, and the scope of the present invention is not limited to the exemplary embodiments in any way.
< Synthesis example >
< preparation example 1> modified acrylic polyol auxiliary resin A
After 239g of xylene and 90g of butanol were introduced into a synthetic four-necked flask equipped with a thermometer and a stirrer and the temperature was raised to a reflux temperature, a mixture of 64g of styrene monomer, 100g of butyl methacrylate, 123g of 2-hydroxyethyl acrylate, 251g of butyl acrylate, 35g of methacrylic acid and 36g of t-butyl peroxyacetate was uniformly added dropwise over five hours. After completion of the dropwise addition, the resultant was kept at the reflux temperature for two hours, and then cooled to 120 ℃ while the viscosity was not changed. 65g of Cardura E10P glycidyl ester was added dropwise for two hours and the reaction was continued until the acid value was unchanged, thereby obtaining a modified acrylic polyol auxiliary resin A having a solid content of 50 wt%, a Gardner-Holdt viscosity of C-D and an acid value of 13 mgKOH/g.
< preparation example 2> modified acrylic polyol auxiliary resin B
After 239g of xylene and 90g of butanol were introduced into a synthetic four-necked flask equipped with a thermometer and a stirrer and the temperature was raised to a reflux temperature, a mixture of 64g of styrene monomer, 135g of butyl methacrylate, 83g of 2-hydroxyethyl acrylate, 254g of butyl acrylate, 35g of methacrylic acid and 36g of t-butyl peroxyacetate was uniformly added dropwise over five hours. After completion of the dropwise addition, the resultant was kept at the reflux temperature for two hours, and then cooled to 120 ℃ while the viscosity was not changed. 65g of Cardura E10P glycidyl ester was added dropwise for two hours and the reaction was continued until the acid value was unchanged, thereby obtaining a modified acrylic polyol auxiliary resin B having a solids content of 50 wt%, a-a Gardner-Holter viscosity and an acid value of 13 mgKOH/g.
< preparation example 3> modified acrylic polyol auxiliary resin C
After 239g of xylene and 90g of butanol were introduced into a synthetic four-necked flask equipped with a thermometer and a stirrer and the temperature was raised to a reflux temperature, a mixture of 64g of styrene monomer, 253g of butyl methacrylate, 97g of 2-hydroxyethyl acrylate, 97g of butyl acrylate, 35g of methacrylic acid and 36g of t-butyl peroxyacetate was uniformly added dropwise over five hours. After completion of the dropwise addition, the resultant was kept at the reflux temperature for two hours, and then cooled to 120 ℃ while the viscosity was not changed. 65G of Cardura E10P glycidyl ester was added dropwise for two hours and the reaction was continued until the acid value was unchanged, thereby obtaining a modified acrylic polyol auxiliary resin C having a solid content of 50 wt%, a Gardner-Holter viscosity of G-H, and an acid value of 13 mgKOH/G.
< preparation example 4> modified acrylic polyol auxiliary resin D
After 243g of xylene and 91g of butanol were introduced into a synthetic four-necked flask equipped with a thermometer and a stirrer and the temperature was raised to the reflux temperature, a mixture of 65g of styrene monomer, 101g of butyl methacrylate, 125g of 2-hydroxyethyl acrylate, 256g of butyl acrylate, 36g of methacrylic acid and 18g of t-butyl peroxyacetate was uniformly added dropwise over five hours. After completion of the dropwise addition, the resultant was kept at the reflux temperature for two hours, and then cooled to 120 ℃ while the viscosity was not changed. 66g of Cardura E10P glycidyl ester was added dropwise for two hours and the reaction was continued until the acid value was unchanged, thereby obtaining a modified acrylic polyol auxiliary resin D having a solids content of 50 wt%, a Gardner-Holter viscosity of R and an acid value of 13 mgKOH/g.
< preparation example 5> modified acrylic polyol auxiliary resin E
After 239g of xylene and 90g of butanol were introduced into a synthetic four-necked flask equipped with a thermometer and a stirrer and the temperature was raised to a reflux temperature, a mixture of 64g of styrene monomer, 131g of butyl methacrylate, 138g of 2-hydroxyethyl acrylate, 247g of butyl acrylate, 24g of methacrylic acid and 36g of t-butyl peroxyacetate was uniformly added dropwise over five hours. After completion of the dropwise addition, the resultant was kept at the reflux temperature for two hours, and then cooled to 120 ℃ while the viscosity was not changed. 32g of Cardura E10P glycidyl ester was added dropwise for two hours and the reaction was continued until the acid value was unchanged, thereby obtaining a modified acrylic polyol auxiliary resin E having a solids content of 50 wt%, a Gardner-Holter viscosity of F and an acid value of 13 mgKOH/g.
< preparation example 6> acrylic polyol auxiliary resin F
After 239g of xylene and 90g of butanol were introduced into a synthetic four-necked flask equipped with a thermometer and a stirrer and the temperature was raised to the reflux temperature, a mixture of 64g of styrene monomer, 164g of butyl methacrylate, 152g of 2-hydroxyethyl acrylate, 243g of butyl acrylate, 13g of methacrylic acid and 36g of t-butyl peroxyacetate was uniformly added dropwise over five hours. After completion of the dropwise addition, the resultant was kept at the reflux temperature for two hours, and then cooled while the viscosity was not changed, thereby obtaining an acrylic polyol auxiliary resin F having a solid content of 50% by weight, a Gardner-Holter viscosity of H-I, and an acid value of 13 mgKOH/g.
The properties of the modified acrylic polyol auxiliary resins of preparation examples 1 to 5 and the acrylic polyol auxiliary resin of preparation example 6 are shown in table 1 below.
[ Table 1]
< examples 1 to 3>
Clear paint compositions were prepared by mixing the components according to the compositions shown in table 2 and stirring at 1,500rpm for at least 20 minutes.
< comparative examples 1 to 8>
Clear paint compositions were prepared by mixing the components according to the compositions shown in table 2 and stirring at 1,500rpm for at least 20 minutes.
[ Table 2]
Preparation of clear paint composition (content: wt%)
1) Acrylic polyol resin A (principal resin) (KCC Co., Ltd.)
Solid content: 60 wt%; gardner-holter viscosity: w to Z; acid value: 10 mgKOH/g; glass transition temperature: 12 ℃; hydroxyl value: 140 mgKOH/g; weight average molecular weight: 15,000g/mol
2) Acrylic polyol resin B (auxiliary resin: flatting agent) (KCC company)
Solid content: 50 wt%; gardner-holter viscosity: a2 to A; glass transition temperature: 15 ℃; weight average molecular weight: 6,000g/mol
3) Polyester polyol resin A (auxiliary resin) (KCC Co., Ltd.)
Solid content: 70 wt%; gardner-holter viscosity: y to Z1; acid value: 22 mgKOH/g; glass transition temperature: 5 ℃; hydroxyl value: 135 mgKOH/g; weight average molecular weight: 5,000g/mol
4) Melamine (hardener) (Luperox012, BASF SE)
Solid content: 56 to 60 wt%; viscosity at 25 ℃: 600 to 1,000 mPas; color: 50 hasen or less; acid value: 1mgKOH/g or less; weight average molecular weight: 1,000 to 4,000 g/mol; appearance: is transparent
5) Carbamate (hardener) (Desmodur PL350, Covestro Ag)
Solid content: 73 to 77 wt%; viscosity at 25 ℃: 2,800 mPas to 5,800 mPas; color: 100 hassen or less than 100 hassen; appearance: is transparent
6) Additive (Tinuvin 5151, BASF SE)
Light transmittance: 85% or more; appearance: is transparent
< Experimental example >
After applying the clear paint compositions of examples 1 to 3 and comparative examples 1 to 8 prepared by mixing the components of the compositions shown in table 2 and obtaining hardened products thereof, paint properties were measured under the following conditions, and the results are shown in table 3 below.
< coating conditions >
Spraying with pistols
Nozzle diameter: 1.5 mm; air pressure: kept constant at about 4.5kgf/cm2
The coating is performed by horizontally moving the nozzle at a constant speed of 40 cm/sec to 50 cm/sec while constantly maintaining the distance between the nozzle tip and the sample at 20cm to 30 cm.
After coating and subsequent bake hardening at 130 ℃ for 20 minutes, the properties of the coating films (DOI, scratch resistance, gloss, hardness, weathering resistance, chipping resistance) were measured.
< evaluation method >
1) Image clarity (DOI) was measured by evaluating the appearance of the top-coated samples using a WaveScan DUAL instrument according to MS653-01-SPEC, which evaluates how good the appearance of the coating is. (CF: combination factor)
2) The scratch resistance was evaluated using the CAR WASHER method according to MS653-01 SPEC, which evaluates the gloss retention in coating films damaged by car wash equipment.
3) The gloss, which means the gloss quality level of the coating film, was evaluated by the KCC-7-28-0022 method according to MS653-01 SPEC.
(KCC-7-28-0022: after the dried sample was completely cooled, 20 ℃ gloss at 30 μm/40 μm/50 μm was measured and recorded using a specified gloss meter (micro gloss meter manufactured by BYK-Gardner))
4) The hardness of the coating film was evaluated by evaluating the hardness according to KCC-7-28-3000 method of MS653-01 SPEC.
(KCC-7-28-3000 method:
a) the tip of the pencil lead is leveled using sandpaper.
b) The pencil was held so that the tip of the pencil lead was at a 45 angle to the sample.
c) Each pencil type was made to draw five lines on the surface of a test specimen prepared according to the prescribed conditions with an appropriate force.
d) Here, the force with which the pencil presses the test piece was about 500g/cm2。
Note 1) erase the test area with an eraser, but in order to reduce errors caused by scratching, the eraser should be rubbed at right angles to the test direction.
Note 2) since the coating film thickness, temperature, humidity, and the like have a significant influence on the hardness, the test was performed under standard conditions.
Note 3) the intensity of the pencil became high in the order H > F > HB > B > 2B.
Evaluation criteria: after erasing the test area with an eraser, the number of lines in which two or more recognizable pencil marks do not appear was recorded. )
5) Weather resistance, which is an index of durability (weather resistance) of the coating film, becomes higher as the adhesion of the coating film becomes higher, and is evaluated by KCC-7-28-3403 method according to MS-653-01 SPEC.
(KCC-7-28-3403 method:
< WOM Equipment Condition >
Light intensity: 0.35 +/-0.01W/m at 340nm2
Temperature of the sample: 63 ℃. + -. 1 ℃, humidity: -50% +/-5%
Spraying: 102 minutes of light, then 18 minutes of light and spray
< measuring method >
a) A 6cm x 15cm sample (specimen, clay, etc.) was inserted into the holder and mounted on the stand.
b) The balance cycle button was pressed to warm the device for about 5 minutes.
c) After pressing the operating button, the lamp ignition button is pressed to start the device.
d) The test was performed for 3,600 hours.
Note 1) regarding weather resistance, adhesion becomes good in the order of M-1.0> M-1.5> M-2.0> M-2.5> M-3.0. )
6) Regarding chipping resistance, cold chipping resistance was evaluated in terms of MS653-01 SPEC, which refers to the degree to which a coating film resists chipping by stone.
[ Table 3]
Referring to table 3, it can be seen that the coatings formed from the clear paint compositions of examples 1 to 3 exhibited similar levels of hardness and chipping resistance, and exhibited excellent DOI, scratch resistance, gloss, weather resistance and chipping resistance, as compared to the coatings formed from the clear paint compositions of comparative examples 1 to 8.
In particular, it can be seen that the coatings formed from the clear paint compositions of examples 1 to 3 have superior properties, in particular DOI, scratch resistance and gloss, compared to the coatings formed from the clear paint compositions of comparative examples 1 to 5.
Further, it can be seen that the coatings formed from the clear paint compositions of examples 1 to 3 exhibited superior DOI, scratch resistance, gloss and weather resistance, compared to the coatings formed from the clear paint composition of comparative example 6 containing less than 10 wt% of the modified acrylic polyol resin or the clear paint composition of comparative example 7 containing more than 25 wt% of the modified acrylic polyol resin.
In addition, the coatings formed from the transparent paint compositions of examples 1 to 3 having the modified acrylic polyol resin as an auxiliary resin exhibited excellent DOI, scratch resistance, gloss and weather resistance, compared to the coating formed from the transparent paint composition of comparative example 8 having only the modified acrylic polyol resin as a main resin.
Therefore, paints based on the one-component clear paint composition comprising the modified acrylic polyol resin of the present invention have excellent DOI, scratch resistance, gloss and weather resistance.
Although some exemplary embodiments of the present invention have been described in detail above, it is apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and variations are encompassed within the scope of the appended claims.
Claims (9)
1. A one-component clear paint composition comprising:
one or more acrylic polyol resins;
a modified acrylic polyol resin produced by the reaction of an acrylic resin containing carboxyl groups and hydroxyl groups with a glycidyl ester; and
a hardening agent which is a mixture of a hardening agent,
wherein the modified acrylic polyol resin is included in an amount of 10 wt% to 25 wt% with respect to the total weight of the clear paint composition, and has a viscosity of 70cP to 110cP at 25 ℃.
2. The one-component clear paint composition according to claim 1, wherein the glycidyl ester has a chemical structure represented by the following chemical formula 1.
[ chemical formula 1]
(Here, R is a C1 to C30 alkyl group.)
3. The one-component clear paint composition according to claim 1, wherein the modified acrylic polyol resin has a glass transition temperature (T) of 0 ℃ or lessg) A hydroxyl value of from 100 to 150mgKOH/g, and an acid value of from 10 to 15 mgKOH/g.
4. The one-component clear paint composition according to claim 1, wherein the one or more acrylic polyol resins are included in an amount of 30 to 70 wt% with respect to the total weight of the clear paint composition, and the hardener is included in an amount of 20 to 50 wt% with respect to the total weight of the clear paint composition.
5. The one-component clear paint composition according to claim 1, wherein the one or more acrylic polyol resins have a glass transition temperature of 10 ℃ to 50 ℃.
6. The one-part clear paint composition of claim 1, wherein the one or more acrylic polyol resins comprise a first acrylic polyol resin and a second acrylic polyol resin.
7. The one-component clear paint composition according to claim 6, wherein the first acrylic polyol resin is included in an amount of 20 to 69.9 wt% with respect to the total weight of the clear paint composition, and the second acrylic polyol resin is included in an amount of 0.1 to 30 wt% with respect to the total weight of the clear paint composition.
8. The one-part clear paint composition according to claim 6, wherein the first acrylic polyol resin has a resin solids content of 55 to 70 wt%, a viscosity of 950 to 2,400cP at 25 ℃, an acid value of 5 to 15mgKOH/g, a hydroxyl value of 120 to 170mgKOH/g, a glass transition temperature of 10 to 20 ℃, and a weight average molecular weight of 10,000 to 30,000 g/mol.
9. The one-part clear paint composition of claim 6, wherein the second acrylic polyol resin has a resin solids content of 40 to 60 wt%, a viscosity of 20 to 55cP at 25 ℃, a glass transition temperature of 10 to 50 ℃, and a weight average molecular weight of 3,000 to 15,000 g/mol.
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| KR10-2018-0008964 | 2018-01-24 | ||
| KR1020180008964A KR102080936B1 (en) | 2018-01-24 | 2018-01-24 | Clear paint composition |
| PCT/KR2018/016058 WO2019146911A1 (en) | 2018-01-24 | 2018-12-17 | Clear paint composition |
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| KR102389713B1 (en) * | 2022-02-17 | 2022-04-22 | 율천공업(주) | top coat coating method for agricultural machine |
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| CN103890036A (en) * | 2011-10-19 | 2014-06-25 | 迈图专业化学股份有限公司 | Acrylic polyol resins compositions |
| KR20140079986A (en) * | 2012-12-20 | 2014-06-30 | (주)노루페인트 | Anti-scratch clear paint composition and method of manufacturing paint film using the same |
| CN105237688A (en) * | 2015-10-30 | 2016-01-13 | 江门市珍图新材料有限公司 | Water dilution type polyester modified acrylic polyol resin |
| CN106280913A (en) * | 2015-06-26 | 2017-01-04 | 株式会社Kcc | Nonferrous metal base coating compositions |
| KR20170130210A (en) * | 2016-05-18 | 2017-11-28 | 주식회사 케이씨씨 | Clear Paint Composition |
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| JPH09296149A (en) * | 1996-04-30 | 1997-11-18 | Kanegafuchi Chem Ind Co Ltd | Curable composition for top coating, and coated product using the same |
| JP4836542B2 (en) | 2004-10-29 | 2011-12-14 | 関西ペイント株式会社 | Paint composition |
| KR101725784B1 (en) | 2010-04-27 | 2017-04-13 | 주식회사 케이씨씨 | High solid and two fluid type paint composition for repairing vehicles |
| KR20130013452A (en) * | 2011-07-28 | 2013-02-06 | 주식회사 케이씨씨 | A transparent paint composition for repairing a vehicle |
| US20140287252A1 (en) * | 2011-10-19 | 2014-09-25 | Momentive Specialty Chemicals Inc. | Polyester polyol resins compositions |
| KR101724918B1 (en) | 2015-10-05 | 2017-04-07 | 현대자동차주식회사 | Clear paint composition for hot stamping film and painting method using the same |
| KR102060079B1 (en) * | 2016-04-21 | 2019-12-30 | (주)엘지하우시스 | Dual curing type hard coating composition and decoration sheet using the same and method of manufacturing the decoration sheet |
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- 2018-01-24 KR KR1020180008964A patent/KR102080936B1/en active IP Right Grant
- 2018-12-17 WO PCT/KR2018/016058 patent/WO2019146911A1/en active Application Filing
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890036A (en) * | 2011-10-19 | 2014-06-25 | 迈图专业化学股份有限公司 | Acrylic polyol resins compositions |
| KR20140079986A (en) * | 2012-12-20 | 2014-06-30 | (주)노루페인트 | Anti-scratch clear paint composition and method of manufacturing paint film using the same |
| CN106280913A (en) * | 2015-06-26 | 2017-01-04 | 株式会社Kcc | Nonferrous metal base coating compositions |
| CN105237688A (en) * | 2015-10-30 | 2016-01-13 | 江门市珍图新材料有限公司 | Water dilution type polyester modified acrylic polyol resin |
| KR20170130210A (en) * | 2016-05-18 | 2017-11-28 | 주식회사 케이씨씨 | Clear Paint Composition |
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| KR102080936B1 (en) | 2020-02-25 |
| WO2019146911A1 (en) | 2019-08-01 |
| CN111630120B (en) | 2021-12-21 |
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