WO2020262869A2 - Clear paint composition - Google Patents

Clear paint composition Download PDF

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Publication number
WO2020262869A2
WO2020262869A2 PCT/KR2020/007754 KR2020007754W WO2020262869A2 WO 2020262869 A2 WO2020262869 A2 WO 2020262869A2 KR 2020007754 W KR2020007754 W KR 2020007754W WO 2020262869 A2 WO2020262869 A2 WO 2020262869A2
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WO
WIPO (PCT)
Prior art keywords
acrylic resin
weight
resin
parts
coating
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PCT/KR2020/007754
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French (fr)
Korean (ko)
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WO2020262869A3 (en
Inventor
이수완
이종택
Original Assignee
주식회사 케이씨씨
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Publication of WO2020262869A2 publication Critical patent/WO2020262869A2/en
Publication of WO2020262869A3 publication Critical patent/WO2020262869A3/en

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present invention relates to a clear paint composition excellent in appearance characteristics and scratch resistance.
  • the vehicle body of an automobile is generally subjected to multiple coating treatments such as electrodeposition coating, intermediate coating, top coating and clear coating in order to protect the exterior and the surface from the external environment.
  • coating treatments such as electrodeposition coating, intermediate coating, top coating and clear coating
  • it is a common automotive painting process to apply and cure an intermediate paint after electrodeposition coating on a vehicle body, and to continuously coat a top paint and a clear paint on the intermediate coating layer, followed by drying and curing.
  • This automotive painting process is usually carried out by a 3 coat 2 bake (3C2B) coating method of primary curing after intermediate coating and secondary curing after clear paint coating.
  • 3C2B 3 coat 2 bake
  • the 3 coat 1 bake (3C1B) coating method consists of electrodeposition, middle coat, top coat, and clear coat, and coats medium coat, but coats top coat and clear coat with Wet on Wet without primary curing after medium coat.
  • the intermediate removal type coating method consists of electrodeposition, top coat and clear coat, and it is a painting method that eliminates the middle coat itself and implements the intermediate function in the top coat.
  • the clear coating composition used in the conventional 3C1B method has disadvantages such as lack of physical properties such as scratch resistance, impact resistance, and weather resistance, or appearance characteristics of the coating film prepared therefrom.
  • Patent Document 1 discloses a clear paint composition comprising two types of acrylic polyol resins, polyester polyol resins, isocyanate curing agents, and reactive silicone additives having different weight average molecular weight and hydroxyl value. have.
  • the clear coating composition of Patent Document 1 is not excellent in appearance and mechanical properties of the coating film to be used as an oily 3C1B clear, there is a limit to application for vehicle body painting.
  • the present invention can be applied to an oil-based 3C1B system to reduce coating costs, and provides a clear coating composition having excellent scratch resistance, impact resistance, weather resistance, and appearance characteristics of the manufactured coating film.
  • the present invention includes a first acrylic resin, a second acrylic resin, a polyester resin, a melamine resin, and an isocyanate compound, and the second acrylic resin has a lower glass transition temperature than the first acrylic resin, and has a higher weight average molecular weight.
  • a paint composition includes a first acrylic resin, a second acrylic resin, a polyester resin, a melamine resin, and an isocyanate compound, and the second acrylic resin has a lower glass transition temperature than the first acrylic resin, and has a higher weight average molecular weight.
  • the clear coating composition according to the present invention is excellent in appearance characteristics, scratch resistance, impact resistance and weather resistance of a coating film prepared including two types of acrylic resins and polyester resins having different glass transition temperatures and weight average molecular weights.
  • the clear coating composition according to the present invention can be applied to an oil-based 3C1B system, so that coating costs can be reduced and thus economical.
  • the "weight average molecular weight” is measured by a conventional method known in the art, for example, it can be measured by a gel permeation chromatograph (GPC) method.
  • the "glass transition temperature” is measured by a conventional method known in the art, and may be measured, for example, by differential scanning calorimetry (DSC).
  • functional values such as'acid value' and'hydroxyl value' may be measured by a method well known in the art, and may represent values measured by, for example, a titration method.
  • the clear paint composition according to the present invention includes a first acrylic resin, a second acrylic resin, a polyester resin, a melamine resin, and an isocyanate compound.
  • the first acrylic resin serves to improve the appearance characteristics, particularly gloss, of the produced coating film.
  • the first acrylic resin has a higher glass transition temperature (Tg) than the second acrylic resin and has a lower weight average molecular weight (Mw).
  • the composition according to the present invention includes two types of acrylic resins having different glass transition temperatures and weight average molecular weights, thereby having excellent mechanical properties and appearance.
  • the glass transition temperature of the first acrylic resin is 5 to 30 °C or 10 to 20 °C higher than the glass transition temperature of the second acrylic resin
  • the weight average molecular weight of the first acrylic resin is the second acrylic resin It is less than the weight average molecular weight of 2,000 to 6,000 g/mol or 3,000 to 5,000 g/mol.
  • the first acrylic resin has a glass transition temperature of 1 to 20°C, 5 to 15°C, or 8 to 13°C, and a weight average molecular weight of 5,000 g/mol or less, 1,000 to 5,000 g/mol, 3,000 to 5,000 g/mol , Or 4,000 to 5,000 g/mol.
  • glass transition temperature of the first acrylic resin is within the above range, weather resistance and hardness are excellent, and when the weight average molecular weight is within the above range, chemical resistance is excellent.
  • the first acrylic resin has a hydroxyl value (OHv) of 120 to 160 mgKOH/g, 125 to 155 mgKOH/g, or 130 to 150 mgKOH/g, and an acid value (Av) of 1 to 20 mgKOH/g, 5 To 15 mgKOH/g, or 8 to 12 mgKOH/g.
  • OHv hydroxyl value
  • Av acid value
  • the first acrylic resin may be included in an amount of 20 to 50 parts by weight based on 1 to 10 parts by weight of the second acrylic resin.
  • the first acrylic resin may be included in an amount of 25 to 40 parts by weight, or 28 to 37 parts by weight based on 1 to 10 parts by weight of the second acrylic resin.
  • the appearance and coating properties of the prepared coating film are excellent.
  • the second acrylic resin serves to improve the solid content in the composition, improve workability, and improve the appearance of the produced coating film.
  • the second acrylic resin has a lower glass transition temperature (Tg) and a higher weight average molecular weight (Mw) than the first acrylic resin.
  • the second acrylic resin has a glass transition temperature of -10 to -1 °C, -8 to -2 °C, or -6 to -4 °C, and a weight average molecular weight of 7,000 to 10,000 g/mol, 7,500 to 9,500 g/mol, 8,000 to 9,300 g/mol, or 8,500 to 9,000 g/mol.
  • the glass transition temperature of the second acrylic resin is within the above range, it is effective in leveling and excellent appearance formation, and when the weight average molecular weight is within the above range, there is an effect of excellent chemical resistance.
  • the second acrylic resin may have a hydroxyl value (OHv) of 50 to 110 mgKOH/g, 70 to 105 mgKOH/g, or 80 to 100 mgKOH/g.
  • OHv hydroxyl value
  • the clear paint composition may include the first acrylic resin and the second acrylic resin in a weight ratio of 3:1 to 8:1.
  • the clear paint composition may include the first acrylic resin and the second acrylic resin in a weight ratio of 4:1 to 7.5:1, or 4.5:1 to 7:1 by weight.
  • the second acrylic resin may be included in an amount of 1 to 10 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. Specifically, the second acrylic resin may be included in an amount of 3 to 9 parts by weight, or 5 to 8 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. When the content of the second acrylic resin is within the above range, adhesion and workability are excellent.
  • the polyester resin serves to improve mechanical properties such as cold chipping resistance and impact resistance to the manufactured coating film.
  • the polyester resin may be directly synthesized according to a known method, or a commercially available product may be used.
  • the polyester resin may have a weight average molecular weight (Mw) of 4,000 to 6,000 g/mol, and a glass transition temperature (Tg) of 1 to 20°C.
  • Mw weight average molecular weight
  • Tg glass transition temperature
  • the polyester resin may have a weight average molecular weight of 4,500 to 5,500 g/mol, or 4,800 to 5,300 g/mol, and a glass transition temperature of 1 to 15°C, or 3 to 10°C.
  • the weight average molecular weight of the polyester resin is within the above range, the appearance and elasticity are excellent, and when the glass transition temperature is within the above range, the coating properties and leveling properties are excellent.
  • the polyester resin may have an acid value (Av) of 15 to 30 mgKOH/g, and a hydroxyl value (OHv) of 110 to 160 mgKOH/g.
  • the polyester resin may have an acid value of 18 to 28 mgKOH/g, or 20 to 25 mgKOH/g, and a hydroxyl value of 120 to 150 mgKOH/g, or 130 to 145 mgKOH/g.
  • the polyester resin may be included in the composition in an amount of 1 to 10 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the polyester resin may be included in the composition in an amount of 1 to 8 parts by weight, or 2 to 6 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • Melamine resin is a curing agent and serves to cure the composition by crosslinking reaction with each component of the clear paint composition.
  • the melamine resin may be directly synthesized according to a known method, or a commercially available product may be used.
  • the melamine resin may include an alkoxy group.
  • the melamine resin may have a viscosity of 500 to 1,500 mPa ⁇ s at 25° C., an acid value (Av) of 0.1 to 5 mgKOH/g, and a weight average molecular weight (Mw) of 500 to 5,000 g/mol.
  • the melamine resin has a viscosity of 550 to 1,300 mPa ⁇ s, or 600 to 1,000 mPa ⁇ s at 25°C, an acid value of 0.2 to 4 mgKOH/g, or 0.3 to 3 mgKOH/g, and a weight average
  • the molecular weight may be 1,000 to 4,000 g/mol, or 2,000 to 3,000 g/mol.
  • the melamine resin may be included in the composition in an amount of 10 to 40 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the melamine resin may be included in the composition in an amount of 15 to 35 parts by weight, or 18 to 30 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the isocyanate compound serves to cure the composition by crosslinking reaction with other components in the composition containing it.
  • the isocyanate group of the isocyanate compound reacts with hydroxyl groups of other components in the coating composition to form urethane bonds, thereby curing the coating composition.
  • the isocyanate compound may be used without particular limitation as long as it is a conventional isocyanate compound that can be used in a curing agent for paint.
  • the isocyanate compound may be a hexamethylene diisocyanate (HMDI) system having excellent yellowing resistance and weather resistance.
  • HMDI hexamethylene diisocyanate
  • the isocyanate compound may be a block isocyanate compound in which an isocyanate group at the terminal is sealed.
  • the isocyanate compound may be a block aliphatic isocyanate compound in which an isocyanate group at the terminal is sealed.
  • the isocyanate compound may have a viscosity of 2,000 to 8,000 mPa ⁇ s at 25° C., and a solid content of 50 to 80% by weight based on the total weight of the resin.
  • the isocyanate compound has a viscosity at 25°C of 3,000 to 6,000 mPa ⁇ s, or 4,000 to 5,500 mPa ⁇ s, and a solid content of 55 to 75% by weight, or 58 to 68% by weight based on the total weight of the resin.
  • the isocyanate compound may be included in the composition in an amount of 1 to 10 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the isocyanate compound may be included in the composition in an amount of 3 to 9 parts by weight, or 5 to 8 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the clear paint composition may further contain a solvent.
  • the solvent controls the viscosity of the clear paint composition and controls the quick-drying property of the composition, and a conventional solvent used in the clear paint composition may be used.
  • the solvent may include, for example, at least one selected from the group consisting of alcohol-based, acetate-based, alkylbenzene-based, ketone-based, and carbonate-based.
  • the solvent may be a non-polar solvent such as n-heptane, toluene, xylene, petroleum compounds, and n-hexane; Butanol, ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dibasic ester, 3-methoxy butyl acetate, amyl acetate, butyl glycol acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, Polar solvents such as diisobutyl ketone, isophorone, and cyclohexanone; And a mixture of the non-polar solvent and the polar solvent, and the like, and may be
  • the solvent may be included in an amount of 10 to 30 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the solvent may be included in an amount of 12 to 28 parts by weight, or 15 to 25 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the clear paint composition may further include one or more additives selected from the group consisting of an anti-yellowing agent, a moisture absorbent, a surface modifier, a flow inhibitor, an ultraviolet absorber, an anti-pinhole agent, and an anti-oil agent.
  • additives selected from the group consisting of an anti-yellowing agent, a moisture absorbent, a surface modifier, a flow inhibitor, an ultraviolet absorber, an anti-pinhole agent, and an anti-oil agent.
  • the additive may be included in an amount of 2 to 20 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the additive may be included in an amount of 3 to 15 parts by weight, or 5 to 12 parts by weight based on 20 to 50 parts by weight of the first acrylic resin.
  • the clear paint composition according to the present invention as described above is excellent in appearance characteristics, scratch resistance, impact resistance, and weather resistance of a coating film prepared including two types of acrylic resins and polyester resins having different glass transition temperatures and weight average molecular weights. Do.
  • the clear coating composition according to the present invention can be applied to an oil-based 3C1B system, so that coating costs can be reduced and thus economical.
  • a clear paint composition was prepared by mixing a first acrylic polyol resin, a second acrylic polyol resin, a polyester resin, a melamine resin, an isocyanate compound, a solvent, and an additive according to the contents of Tables 1 and 2.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6 1st acrylic resin 32 36.7 28 39.2 32 31.5 2nd acrylic resin 6 5.3 6 5 9 7
  • Polyester resin 4 2 4 3 3.6 7.2
  • Melamine resin 25 25 25 25 25 25 25 25
  • Anti-yellowing agent 0.2 0.2 0.2 0.2 0.2 0.2 0.2
  • Moisture absorbent 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1
  • Surface modifier 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Flow inhibitor 3 3 3 3 3
  • ingredient Component physical property or compound name 1st acrylic resin Solid content: 60.3% by weight, Tg: 11.8°C, Mw: 4,600g/mol, Av: 9.3mgKOH/g, OHv: 145mgKOH/g 2nd acrylic resin Solid content: 60% by weight, Tg: -5°C, Mw: 8,784 g/mol, OHv: 92 mgKOH/g Polyester resin Solid content: 70% by weight, Tg: 6°C, Mw: 5,180g/mol, Av: 23mgKOH/g, OHv: 137mgKOH/g Melamine resin Solid content: 58% by weight, viscosity at 25°C: 800mPa ⁇ s, Av: 1mgKOH/g, Mw: 2,500g/mol Isocyanate compounds Block aliphatic polyisocyanate (viscosity at 25°C: 4,700 mPa ⁇ s, solid content: 63% by weight) Anti-yellowing agent Benzene propanoi
  • an oily primer paint (manufacturer: KCC, product name: FU2280) was applied to the specimen to a thickness of 20 ⁇ m, dried, and then an oily base paint (manufacturer: KCC, product name: TT6680) was applied to a thickness of 20 ⁇ m, and examples and comparisons
  • the clear coating composition of the example was applied to a thickness of 40 ⁇ m, dried and cured at 150° C. for 30 minutes to form a clear coating layer.
  • the CF value was measured using a Wave Scan DOI (BYK Gardner), which is an automobile exterior measuring instrument, and it was determined that the higher the CF value, the better the appearance characteristics of the coating film. Specifically, if the CF value was 70 or more, it was evaluated as excellent ( ⁇ ), if it was 65 or more and less than 70, good ( ⁇ ), if it was 60 or more and less than 65, it was evaluated as normal ( ⁇ ), and if it was less than 60, it was evaluated as bad ( ⁇ ).
  • the hardness of the clear coating film was measured by the pencil hardness method. Specifically, the maximum hardness that does not damage the clear coating film was measured using 3B, 2B, B, HB, F, H, 2H and 3H pencils (3B, 2B, B, HB, F, H, 2H , 3H: inferior ⁇ excellent).
  • the specimen was heat-treated and left at room temperature for 24 hours, and then the adhesion was evaluated by the Go wood method.
  • the Go method 100 squares of 2 mm in width and 2 mm in length were made on the surface of the clear coating film with a knife, and then the square was removed using a tape to measure adhesion. At this time, the measured adhesion is M-1 (excellent) when 100 squares are completely attached to 100%, M-2 (excellent) when the remaining squares are 70% or more and less than 100%, and M- when 50% or more and less than 70%. 3 (normal), 30% or more and less than 50% were expressed as M-4 (bad), and when less than 30%, M-5 (very poor).
  • the heat treatment was performed at 150° C. for 20 minutes and then left at room temperature for 20 minutes in 1 cycle, and a total of 3 cycles were repeated.
  • the specimen was immersed in a constant temperature water bath at 40° C. for 240 hours and left at room temperature for 1 hour, and then a peel test was performed in the same manner as in Item (3), and the evaluation criteria were also applied.
  • the 20° gloss of the specimen was measured (initial gloss measurement), and the surface of the specimen was reciprocated 10 times using a car wash resistance tester (manufactured by Amtec Kistler), and then 20° gloss was measured. After the initial gloss and gloss after surface treatment, the gloss retention rate was calculated using the following equation.
  • the coating films prepared from the clear coating compositions of Examples 1 to 9 were excellent in hardness, adhesion, water resistance, acid resistance, scratch resistance, and solvent resistance.
  • the coating film prepared from the composition of Comparative Example 1 not containing the first acrylic resin was poor in appearance characteristics, water resistance, acid resistance, and solvent resistance.
  • the coating film produced from the clear coating composition of Comparative Example 2 not containing the second acrylic resin was poor in adhesion, initial gloss, scratch resistance, and solvent resistance.
  • the coating film produced from the clear coating composition of Comparative Example 3 containing no polyester resin was poor in adhesion, water resistance, acid resistance, scratch resistance, and solvent resistance.
  • the coating film produced from the composition of Comparative Example 4 containing no melamine resin was poor in appearance characteristics, hardness, and scratch resistance.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

The present invention relates to a clear paint composition comprising: a first acrylic resin; a second acrylic resin; a polyester resin; a melamine resin; and an isocyanate compound, wherein the second acrylic resin has a lower glass transition temperature and a greater weight average molecular weight than the first acrylic resin.

Description

클리어 도료 조성물Clear paint composition
본 발명은 외관 특성 및 내스크래치성이 우수한 클리어 도료 조성물에 관한 것이다.The present invention relates to a clear paint composition excellent in appearance characteristics and scratch resistance.
자동차의 차체는, 외관 및 외부 환경으로부터 표면을 보호하기 위해, 일반적으로 전착 도장, 중도 도장, 상도 도장 및 클리어 도장과 같은 다회 도장 처리된다. 구체적으로, 차체에 전착 도장 후 중도 도료를 도포하고 경화하고, 중도 코팅층 상에 상도 도료와 클리어 도료를 연속적으로 도장한 후 건조 및 경화시키는 것이 보편화된 자동차 도장 공정이다. 이러한 자동차 도장 공정은 통상적으로 중도 도장 후 1차 경화 및 클리어 도료 도장 후 2차 경화하는 3코트2베이크(3C2B) 도장 공법으로 수행되는 것이 보편적이다.The vehicle body of an automobile is generally subjected to multiple coating treatments such as electrodeposition coating, intermediate coating, top coating and clear coating in order to protect the exterior and the surface from the external environment. Specifically, it is a common automotive painting process to apply and cure an intermediate paint after electrodeposition coating on a vehicle body, and to continuously coat a top paint and a clear paint on the intermediate coating layer, followed by drying and curing. This automotive painting process is usually carried out by a 3 coat 2 bake (3C2B) coating method of primary curing after intermediate coating and secondary curing after clear paint coating.
상술한 바와 같은 3C2B의 도장 공법에 대하여, 도장 공정의 설비 투자비, 설비 관리비 및 도장 비용 등의 비용을 절감하고 도료의 친환경성을 향상시키기 위해, 3코트1베이크(3C1B) 도장 공법, 중도 삭제형 도장 공법 등이 제안되었다. 3코트1베이크 도장 공법은 전착, 중도, 상도 및 클리어 코트로 구성되며, 중도 도료는 도장하지만 중도 도장 이후 1차 경화 없이 웨트 온 웨트(Wet on Wet)로 상도 도료와 클리어 도료를 도장하는 공법이고, 중도 삭제형 도장공법은 전착, 상도 및 클리어 코트로 구성되며, 중도 도장 자체를 삭제하고 중도의 기능을 상도 도막에서 구현하는 도장공법이다. 그러나, 종래 3C1B 공법에 이용되는 클리어 도료 조성물은 이로부터 제조된 도막의 내스크래치성, 내충격성 및 내후성 등의 물성이 부족하거나, 외관 특성이 부족한 단점이 있었다.For the 3C2B coating method as described above, in order to reduce costs such as equipment investment, facility management and coating costs in the coating process, and to improve the eco-friendliness of the paint, the 3 coat 1 bake (3C1B) coating method, intermediate removal type Painting method, etc. were proposed. The 3 coat 1 bake coating method consists of electrodeposition, middle coat, top coat, and clear coat, and coats medium coat, but coats top coat and clear coat with Wet on Wet without primary curing after medium coat. , The intermediate removal type coating method consists of electrodeposition, top coat and clear coat, and it is a painting method that eliminates the middle coat itself and implements the intermediate function in the top coat. However, the clear coating composition used in the conventional 3C1B method has disadvantages such as lack of physical properties such as scratch resistance, impact resistance, and weather resistance, or appearance characteristics of the coating film prepared therefrom.
구체적으로, 한국 등록특허 제1,655,621호(특허문헌 1)에는 중량평균분자량 및 수산기가가 상이한 2종의 아크릴릭 폴리올 수지, 폴리에스터 폴리올 수지, 이소시아네이트 경화제 및 반응성 실리콘 첨가제를 포함하는 클리어 도료 조성물이 개시되어 있다. 그러나, 특허문헌 1의 클리어 도료 조성물은 유성 3C1B용 클리어로 사용하기에는 도막의 외관 및 기계적 물성이 우수하지 않아 차체 도장용으로 적용하기에는 한계가 있었다.Specifically, Korean Patent Registration No. 1,655,621 (Patent Document 1) discloses a clear paint composition comprising two types of acrylic polyol resins, polyester polyol resins, isocyanate curing agents, and reactive silicone additives having different weight average molecular weight and hydroxyl value. have. However, since the clear coating composition of Patent Document 1 is not excellent in appearance and mechanical properties of the coating film to be used as an oily 3C1B clear, there is a limit to application for vehicle body painting.
따라서, 제조된 도막이 내스크래치성, 내충격성, 내후성 및 외관 특성이 우수한 3C1B용 클리어 도료 조성물에 대한 연구개발이 필요한 실정이다.Accordingly, there is a need for research and development on a clear coating composition for 3C1B that has excellent scratch resistance, impact resistance, weather resistance, and appearance characteristics of the manufactured coating film.
본 발명은 유성 3C1B 시스템에 적용 가능하여 도장 비용 절감이 가능하고, 제조된 도막이 내스크래치성, 내충격성, 내후성 및 외관 특성이 우수한 클리어 도료 조성물을 제공한다.The present invention can be applied to an oil-based 3C1B system to reduce coating costs, and provides a clear coating composition having excellent scratch resistance, impact resistance, weather resistance, and appearance characteristics of the manufactured coating film.
본 발명은 제1 아크릴 수지, 제2 아크릴 수지, 폴리에스터 수지, 멜라민 수지 및 이소시아네이트 화합물을 포함하고, 상기 제2 아크릴 수지는 제1 아크릴 수지보다 유리전이온도가 낮고, 중량평균분자량이 큰, 클리어 도료 조성물을 제공한다.The present invention includes a first acrylic resin, a second acrylic resin, a polyester resin, a melamine resin, and an isocyanate compound, and the second acrylic resin has a lower glass transition temperature than the first acrylic resin, and has a higher weight average molecular weight. Provides a paint composition.
본 발명에 따른 클리어 도료 조성물은 유리전이온도 및 중량평균분자량이 상이한 2종의 아크릴 수지 및 폴리에스터 수지를 포함하여 제조된 도막의 외관 특성, 내스크래치성, 내충격성 및 내후성이 우수하다. 또한, 본 발명에 따른 클리어 도료 조성물은 유성 3C1B 시스템에 적용 가능하여 도장 비용 절감이 가능하여 경제적이다.The clear coating composition according to the present invention is excellent in appearance characteristics, scratch resistance, impact resistance and weather resistance of a coating film prepared including two types of acrylic resins and polyester resins having different glass transition temperatures and weight average molecular weights. In addition, the clear coating composition according to the present invention can be applied to an oil-based 3C1B system, so that coating costs can be reduced and thus economical.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 명세서에서 사용된 "중량평균분자량"은 당업계에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 GPC(gel permeation chromatograph) 방법 등으로 측정할 수 있다. 또한, "유리전이온도"는 당업계에 알려진 통상의 방법에 의해 측정된 것이며, 예를 들어 시차주사열량분석법(differential scanning calorimetry, DSC) 등으로 측정할 수 있다. 또한, '산가' 및 '수산기가'와 같은 작용기가는 당업계에 잘 알려진 방법에 의해 측정할 수 있으며, 예를 들어 적정(titration)의 방법 등으로 측정한 값을 나타낼 수 있다.As used herein, the "weight average molecular weight" is measured by a conventional method known in the art, for example, it can be measured by a gel permeation chromatograph (GPC) method. In addition, the "glass transition temperature" is measured by a conventional method known in the art, and may be measured, for example, by differential scanning calorimetry (DSC). In addition, functional values such as'acid value' and'hydroxyl value' may be measured by a method well known in the art, and may represent values measured by, for example, a titration method.
본 발명에 따른 클리어 도료 조성물은 제1 아크릴 수지, 제2 아크릴 수지, 폴리에스터 수지, 멜라민 수지 및 이소시아네이트 화합물을 포함한다.The clear paint composition according to the present invention includes a first acrylic resin, a second acrylic resin, a polyester resin, a melamine resin, and an isocyanate compound.
제1 아크릴 수지1st acrylic resin
제1 아크릴 수지는 도료 조성물의 메인 수지로서, 제조된 도막의 외관 특성, 특히 광택을 향상시키는 역할을 한다.The first acrylic resin, as the main resin of the coating composition, serves to improve the appearance characteristics, particularly gloss, of the produced coating film.
상기 제1 아크릴 수지는 상기 제2 아크릴 수지보다 유리전이온도(Tg)가 높고 중량평균분자량(Mw)이 작다. 본 발명에 따른 조성물은 유리전이온도 및 중량평균분자량이 상이한 2종의 아크릴 수지를 포함함으로써, 기계적 물성 및 외관이 우수한 효과가 있다.The first acrylic resin has a higher glass transition temperature (Tg) than the second acrylic resin and has a lower weight average molecular weight (Mw). The composition according to the present invention includes two types of acrylic resins having different glass transition temperatures and weight average molecular weights, thereby having excellent mechanical properties and appearance.
예를 들어, 상기 제1 아크릴 수지의 유리전이온도는 상기 제2 아크릴 수지의 유리전이온도보다 5 내지 30 ℃ 또는 10 내지 20 ℃ 높고, 상기 제1 아크릴 수지의 중량평균분자량은 상기 제2 아크릴 수지의 중량평균분자량보다 2,000 내지 6,000 g/mol 또는 3,000 내지 5,000 g/mol 작다. For example, the glass transition temperature of the first acrylic resin is 5 to 30 °C or 10 to 20 °C higher than the glass transition temperature of the second acrylic resin, and the weight average molecular weight of the first acrylic resin is the second acrylic resin It is less than the weight average molecular weight of 2,000 to 6,000 g/mol or 3,000 to 5,000 g/mol.
상기 제1 아크릴 수지는 유리전이온도가 1 내지 20 ℃, 5 내지 15 ℃, 또는 8 내지 13 ℃이고, 중량평균분자량이 5,000g/mol 이하, 1,000 내지 5,000 g/mol, 3,000 내지 5,000 g/mol, 또는 4,000 내지 5,000 g/mol일 수 있다. 상기 제1 아크릴 수지의 유리전이온도가 상기 범위 내인 경우 내후성 및 경도가 우수한 효과가 있고, 중량평균분자량이 상기 범위 내인 경우, 내화학성이 우수한 효과가 있다.The first acrylic resin has a glass transition temperature of 1 to 20°C, 5 to 15°C, or 8 to 13°C, and a weight average molecular weight of 5,000 g/mol or less, 1,000 to 5,000 g/mol, 3,000 to 5,000 g/mol , Or 4,000 to 5,000 g/mol. When the glass transition temperature of the first acrylic resin is within the above range, weather resistance and hardness are excellent, and when the weight average molecular weight is within the above range, chemical resistance is excellent.
또한, 상기 제1 아크릴 수지는 수산기가(OHv)가 120 내지 160 mgKOH/g, 125 내지 155 mgKOH/g, 또는 130 내지 150 mgKOH/g이고, 산가(Av)가 1 내지 20 mgKOH/g, 5 내지 15 mgKOH/g, 또는 8 내지 12 mgKOH/g일 수 있다. 상기 제1 아크릴 수지의 수산기가가 상기 범위 내인 경우, 경화성 및 부착 물성이 우수한 효과가 있고, 산가가 상기 범위 내인 경우, 외관 및 저장 안정성이 우수한 효과가 있다.In addition, the first acrylic resin has a hydroxyl value (OHv) of 120 to 160 mgKOH/g, 125 to 155 mgKOH/g, or 130 to 150 mgKOH/g, and an acid value (Av) of 1 to 20 mgKOH/g, 5 To 15 mgKOH/g, or 8 to 12 mgKOH/g. When the hydroxyl value of the first acrylic resin is within the above range, there is an effect of excellent curability and adhesion properties, and when the acid value is within the above range, the appearance and storage stability are excellent.
상기 제1 아크릴 수지는 제2 아크릴 수지 1 내지 10 중량부에 대하여 20 내지 50 중량부의 함량으로 포함될 수 있다. 예를 들어, 상기 제1 아크릴 수지는 제2 아크릴 수지 1 내지 10 중량부에 대하여 25 내지 40 중량부, 또는 28 내지 37 중량부의 함량으로 포함될 수 있다. 상기 제1 아크릴 수지가 상기 범위 내로 포함되는 경우, 제조된 도막의 외관 및 코팅 물성이 우수한 효과가 있다.The first acrylic resin may be included in an amount of 20 to 50 parts by weight based on 1 to 10 parts by weight of the second acrylic resin. For example, the first acrylic resin may be included in an amount of 25 to 40 parts by weight, or 28 to 37 parts by weight based on 1 to 10 parts by weight of the second acrylic resin. When the first acrylic resin is included within the above range, the appearance and coating properties of the prepared coating film are excellent.
제2 아크릴 수지2nd acrylic resin
제2 아크릴 수지는 조성물에 고형분 함량을 향상시키고 작업성을 향상시키며, 제조된 도막에 외관을 향상시키는 역할을 한다.The second acrylic resin serves to improve the solid content in the composition, improve workability, and improve the appearance of the produced coating film.
상기 제2 아크릴 수지는 상기 제1 아크릴 수지보다 유리전이온도(Tg)가 낮고 중량평균분자량(Mw)이 크다. The second acrylic resin has a lower glass transition temperature (Tg) and a higher weight average molecular weight (Mw) than the first acrylic resin.
예를 들어, 상기 제2 아크릴 수지는 유리전이온도가 -10 내지 -1 ℃, -8 내지 -2 ℃, 또는 -6 내지 -4 ℃이고, 중량평균분자량이 7,000 내지 10,000 g/mol, 7,500 내지 9,500 g/mol, 8,000 내지 9,300 g/mol, 또는 8,500 내지 9,000 g/mol일 수 있다. 상기 제2 아크릴 수지의 유리전이온도가 상기 범위 내인 경우, 레벨링 및 우수한 외관 형성에 효과가 있고, 중량평균분자량이 상기 범위 내인 경우, 내화학성이 우수한 효과가 있다.For example, the second acrylic resin has a glass transition temperature of -10 to -1 °C, -8 to -2 °C, or -6 to -4 °C, and a weight average molecular weight of 7,000 to 10,000 g/mol, 7,500 to 9,500 g/mol, 8,000 to 9,300 g/mol, or 8,500 to 9,000 g/mol. When the glass transition temperature of the second acrylic resin is within the above range, it is effective in leveling and excellent appearance formation, and when the weight average molecular weight is within the above range, there is an effect of excellent chemical resistance.
또한, 상기 제2 아크릴 수지는 수산기가(OHv)가 50 내지 110 mgKOH/g, 70 내지 105 mgKOH/g, 또는 80 내지 100 mgKOH/g일 수 있다. 상기 제2 아크릴 수지의 수산기가가 상기 범위 내인 경우, 부착 물성이 우수한 효과가 있다.In addition, the second acrylic resin may have a hydroxyl value (OHv) of 50 to 110 mgKOH/g, 70 to 105 mgKOH/g, or 80 to 100 mgKOH/g. When the hydroxyl value of the second acrylic resin is within the above range, adhesion properties are excellent.
상기 클리어 도료 조성물은 상기 제1 아크릴 수지와 상기 제2 아크릴 수지를 3:1 내지 8:1의 중량비로 포함할 수 있다. 예를 들어, 상기 클리어 도료 조성물은 상기 제1 아크릴 수지와 상기 제2 아크릴 수지를 4:1 내지 7.5:1의 중량비, 또는 4.5:1 내지 7:1의 중량비로 포함할 수 있다. 상기 제1 아크릴 수지와 상기 제2 아크릴 수지의 혼합 중량비가 상기 범위를 벗어날 경우, 내수 변색 및 재도장 부착 문제를 초래할 수 있다.The clear paint composition may include the first acrylic resin and the second acrylic resin in a weight ratio of 3:1 to 8:1. For example, the clear paint composition may include the first acrylic resin and the second acrylic resin in a weight ratio of 4:1 to 7.5:1, or 4.5:1 to 7:1 by weight. When the mixing weight ratio of the first acrylic resin and the second acrylic resin is out of the above range, water discoloration and repainting may cause problems.
상기 제2 아크릴 수지는 제1 아크릴 수지 20 내지 50 중량부에 대하여 1 내지 10 중량부의 함량으로 포함될 수 있다. 구체적으로, 상기 제2 아크릴 수지는 제1 아크릴 수지 20 내지 50 중량부에 대하여 3 내지 9 중량부, 또는 5 내지 8 중량부의 함량으로 포함될 수 있다. 제2 아크릴 수지의 함량이 상기 범위 내일 경우, 부착성 및 작업성이 우수한 효과가 있다.The second acrylic resin may be included in an amount of 1 to 10 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. Specifically, the second acrylic resin may be included in an amount of 3 to 9 parts by weight, or 5 to 8 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. When the content of the second acrylic resin is within the above range, adhesion and workability are excellent.
폴리에스터 수지Polyester resin
폴리에스터 수지는 제조된 도막에 내한치핑성, 내충격성 등의 기계적 물성을 향상시키는 역할을 한다. 이때, 상기 폴리에스터 수지는 공지된 방법에 따라 직접 합성된 것을 사용하거나, 시판되는 제품을 사용할 수 있다.The polyester resin serves to improve mechanical properties such as cold chipping resistance and impact resistance to the manufactured coating film. In this case, the polyester resin may be directly synthesized according to a known method, or a commercially available product may be used.
또한, 상기 폴리에스터 수지는 중량평균분자량(Mw)이 4,000 내지 6,000 g/mol이고, 유리전이온도(Tg)가 1 내지 20 ℃일 수 있다. 예를 들어, 상기 폴리에스터 수지는 중량평균분자량이 4,500 내지 5,500 g/mol, 또는 4,800 내지 5,300 g/mol이고, 유리전이온도가 1 내지 15 ℃, 또는 3 내지 10 ℃일 수 있다. 상기 폴리에스터 수지의 중량평균분자량이 상기 범위 내일 경우, 외관 및 탄성이 우수한 효과가 있고, 유리전이온도가 상기 범위 내일 경우, 코팅 물성 및 레벨링성이 우수한 효과가 있다.In addition, the polyester resin may have a weight average molecular weight (Mw) of 4,000 to 6,000 g/mol, and a glass transition temperature (Tg) of 1 to 20°C. For example, the polyester resin may have a weight average molecular weight of 4,500 to 5,500 g/mol, or 4,800 to 5,300 g/mol, and a glass transition temperature of 1 to 15°C, or 3 to 10°C. When the weight average molecular weight of the polyester resin is within the above range, the appearance and elasticity are excellent, and when the glass transition temperature is within the above range, the coating properties and leveling properties are excellent.
상기 폴리에스터 수지는 산가(Av)가 15 내지 30 mgKOH/g이며, 수산기가(OHv)가 110 내지 160 mgKOH/g일 수 있다. 예를 들어, 상기 폴리에스터 수지는 산가가 18 내지 28 mgKOH/g, 또는 20 내지 25 mgKOH/g이며, 수산기가가 120 내지 150 mgKOH/g, 또는 130 내지 145 mgKOH/g일 수 있다. 상기 폴리에스터 수지의 산가가 상기 범위 내일 경우, 저장안정성 및 내한치핑성이 우수한 효과가 있고, 수산기가가 상기 범위 내일 경우, 부착 물성 및 외관이 우수한 효과가 있다.The polyester resin may have an acid value (Av) of 15 to 30 mgKOH/g, and a hydroxyl value (OHv) of 110 to 160 mgKOH/g. For example, the polyester resin may have an acid value of 18 to 28 mgKOH/g, or 20 to 25 mgKOH/g, and a hydroxyl value of 120 to 150 mgKOH/g, or 130 to 145 mgKOH/g. When the acid value of the polyester resin is within the above range, storage stability and cold chipping resistance are excellent, and when the hydroxyl value is within the above range, adhesion properties and appearance are excellent.
또한, 상기 폴리에스터 수지는 제1 아크릴 수지 20 내지 50 중량부에 대하여 1 내지 10 중량부의 함량으로 조성물에 포함될 수 있다. 예를 들어, 상기 폴리에스터 수지는 제1 아크릴 수지 20 내지 50 중량부에 대하여 1 내지 8 중량부, 또는 2 내지 6 중량부의 함량으로 조성물에 포함될 수 있다. 폴리에스터 수지의 함량이 상기 범위 내일 경우, 우수한 레벨링으로 인해 외관 및 내한치핑성이 우수한 효과가 있다.In addition, the polyester resin may be included in the composition in an amount of 1 to 10 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. For example, the polyester resin may be included in the composition in an amount of 1 to 8 parts by weight, or 2 to 6 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. When the content of the polyester resin is within the above range, the appearance and cold chipping resistance are excellent due to excellent leveling.
멜라민 수지Melamine resin
멜라민 수지는 경화제로서, 클리어 도료 조성물의 각 성분들과 가교 반응하여 조성물을 경화시키는 역할을 한다.Melamine resin is a curing agent and serves to cure the composition by crosslinking reaction with each component of the clear paint composition.
상기 멜라민 수지는 공지된 방법에 따라 직접 합성된 것을 사용하거나, 시판되는 제품을 사용할 수 있다. 예를 들어, 상기 멜라민 수지는 알콕시기를 포함할 수 있다.The melamine resin may be directly synthesized according to a known method, or a commercially available product may be used. For example, the melamine resin may include an alkoxy group.
또한, 상기 멜라민 수지는 25℃에서의 점도가 500 내지 1,500 mPa·s이고, 산가(Av)가 0.1 내지 5 mgKOH/g이며, 중량평균분자량(Mw)이 500 내지 5,000 g/mol일 수 있다. 예를 들어, 상기 멜라민 수지는 25℃에서의 점도가 550 내지 1,300 mPa·s, 또는 600 내지 1,000 mPa·s이고, 산가가 0.2 내지 4 mgKOH/g, 또는 0.3 내지 3 mgKOH/g이며, 중량평균분자량이 1,000 내지 4,000 g/mol, 또는 2,000 내지 3,000 g/mol일 수 있다. 멜라민 수지의 25℃에서의 점도가 상기 범위 내일 경우, 저장 안정성이 우수한 효과가 있고, 산가가 상기 범위 내일 경우, 저장 안정성 및 물성이 우수한 효과가 있으며, 중량평균분자량이 상기 범위 내일 경우, 도료의 가교 밀도 향상에 효과가 있다. In addition, the melamine resin may have a viscosity of 500 to 1,500 mPa·s at 25° C., an acid value (Av) of 0.1 to 5 mgKOH/g, and a weight average molecular weight (Mw) of 500 to 5,000 g/mol. For example, the melamine resin has a viscosity of 550 to 1,300 mPa·s, or 600 to 1,000 mPa·s at 25°C, an acid value of 0.2 to 4 mgKOH/g, or 0.3 to 3 mgKOH/g, and a weight average The molecular weight may be 1,000 to 4,000 g/mol, or 2,000 to 3,000 g/mol. When the viscosity of the melamine resin at 25° C. is within the above range, storage stability is excellent, and when the acid value is within the above range, storage stability and physical properties are excellent, and when the weight average molecular weight is within the above range, It is effective in improving the crosslinking density.
상기 멜라민 수지는 제1 아크릴 수지 20 내지 50 중량부에 대하여 10 내지 40 중량부의 함량으로 조성물에 포함될 수 있다. 예를 들어, 상기 멜라민 수지는 제1 아크릴 수지 20 내지 50 중량부에 대하여 15 내지 35 중량부, 또는 18 내지 30 중량부의 함량으로 조성물에 포함될 수 있다. 멜라민 수지의 함량이 상기 범위 내일 경우, 경도 향상 및 외관특성이 우수한 효과가 있다.The melamine resin may be included in the composition in an amount of 10 to 40 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. For example, the melamine resin may be included in the composition in an amount of 15 to 35 parts by weight, or 18 to 30 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. When the content of the melamine resin is within the above range, there is an effect of improving hardness and excellent appearance characteristics.
이소시아네이트 화합물Isocyanate compounds
이소시아네이트 화합물은 이를 포함하는 조성물 내의 다른 성분들과 가교 반응하여 조성물을 경화시키는 역할을 한다. 예를 들어, 상기 이소시아네이트 화합물의 이소시아네이트기는 도료 조성물 내의 다른 성분들의 수산기와 반응하여 우레탄 결합을 형성함으로써, 도료 조성물을 경화시킨다.The isocyanate compound serves to cure the composition by crosslinking reaction with other components in the composition containing it. For example, the isocyanate group of the isocyanate compound reacts with hydroxyl groups of other components in the coating composition to form urethane bonds, thereby curing the coating composition.
상기 이소시아네이트 화합물은 도료용 경화제에 사용될 수 있는 통상적인 이소시아네이트 화합물이라면 특별히 제한없이 사용할 수 있다. 예를 들어, 상기 이소시아네이트 화합물은 내황변성 및 내후성이 우수한 헥사메틸렌디이소시아네이트(HMDI)계를 사용할 수 있다. The isocyanate compound may be used without particular limitation as long as it is a conventional isocyanate compound that can be used in a curing agent for paint. For example, the isocyanate compound may be a hexamethylene diisocyanate (HMDI) system having excellent yellowing resistance and weather resistance.
한편, 상기 이소시아네이트 화합물은 말단의 이소시아네이트기가 봉지된 블록 이소시아네이트 화합물일 수 있다. 구체적으로, 상기 이소시아네이트 화합물은 말단의 이소시아네이트기가 봉지된 블록 알리파틱 이소시아네이트 화합물일 수 있다.Meanwhile, the isocyanate compound may be a block isocyanate compound in which an isocyanate group at the terminal is sealed. Specifically, the isocyanate compound may be a block aliphatic isocyanate compound in which an isocyanate group at the terminal is sealed.
또한, 상기 이소시아네이트 화합물은 25℃에서의 점도가 2,000 내지 8,000 mPa·s이고, 고형분 함량이 수지 총 중량에 대하여 50 내지 80 중량%일 수 있다. 예를 들어, 상기 이소시아네이트 화합물은 25℃에서의 점도가 3,000 내지 6,000 mPa·s, 또는 4,000 내지 5,500 mPa·s이고, 고형분 함량이 수지 총 중량에 대하여 55 내지 75 중량%, 또는 58 내지 68 중량%일 수 있다. In addition, the isocyanate compound may have a viscosity of 2,000 to 8,000 mPa·s at 25° C., and a solid content of 50 to 80% by weight based on the total weight of the resin. For example, the isocyanate compound has a viscosity at 25°C of 3,000 to 6,000 mPa·s, or 4,000 to 5,500 mPa·s, and a solid content of 55 to 75% by weight, or 58 to 68% by weight based on the total weight of the resin. Can be
상기 이소시아네이트 화합물의 25℃에서의 점도가 상기 범위 내일 경우, 제조된 도막이 적절한 레올로지 확보가 가능하고, 고형분 함량이 상기 범위 내일 경우, 작업성이 양호한 효과가 있다. When the viscosity at 25° C. of the isocyanate compound is within the above range, it is possible to ensure an appropriate rheology of the prepared coating film, and when the solid content is within the above range, there is an effect of good workability.
상기 이소시아네이트 화합물은 제1 아크릴 수지 20 내지 50 중량부에 대하여 1 내지 10 중량부의 함량으로 조성물에 포함될 수 있다. 예를 들어, 상기 이소시아네이트 화합물은 제1 아크릴 수지 20 내지 50 중량부에 대하여 3 내지 9 중량부, 또는 5 내지 8 중량부의 함량으로 조성물에 포함될 수 있다. 상기 이소시아네이트 화합물의 함량이 상기 범위 내일 경우, 제조된 도막의 외관 특성, 특히 광택, 및 기계적 물성 향상 효과가 있다.The isocyanate compound may be included in the composition in an amount of 1 to 10 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. For example, the isocyanate compound may be included in the composition in an amount of 3 to 9 parts by weight, or 5 to 8 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. When the content of the isocyanate compound is within the above range, there is an effect of improving appearance properties, particularly gloss, and mechanical properties of the prepared coating film.
용제solvent
상기 클리어 도료 조성물은 용제를 추가로 포함할 수 있다. 이때, 상기 용제는 클리어 도료 조성물의 점도를 조절하고 조성물의 속건성을 조절하는 역할을 하며, 클리어 도료 조성물에 사용되는 통상적인 용제를 사용할 수 있다. The clear paint composition may further contain a solvent. At this time, the solvent controls the viscosity of the clear paint composition and controls the quick-drying property of the composition, and a conventional solvent used in the clear paint composition may be used.
상기 용제는, 예를 들어, 알코올계, 아세테이트계, 알킬벤젠계, 케톤계 및 카보네이트계로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 다른 예로, 상기 용제는 n-헵탄, 톨루엔, 자일렌, 석유계 화합물 및 n-헥산 등의 비극성 용제; 부탄올, 에틸 아세테이트, n-부틸 아세테이트, 이소부틸 아세테이트, 에틸렌글리콜 모노에틸 에테르 아세테이트, 이염기성 에스테르, 3-메톡시 부틸 아세테이트, 아밀 아세테이트, 부틸글리콜 아세테이트, 메틸 에틸 케톤, 메틸 이소부틸 케톤, 아세톤, 디이소부틸 케톤, 이소포론 및 사이클로헥사논 등의 극성 용제; 및 상기 비극성 용제와 극성 용제의 혼합물 등을 들 수 있으며, 조성물에 포함되는 수지의 특성이나 휘발 속도에 따라 적절히 선택하여 사용할 수 있다.The solvent may include, for example, at least one selected from the group consisting of alcohol-based, acetate-based, alkylbenzene-based, ketone-based, and carbonate-based. In another example, the solvent may be a non-polar solvent such as n-heptane, toluene, xylene, petroleum compounds, and n-hexane; Butanol, ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dibasic ester, 3-methoxy butyl acetate, amyl acetate, butyl glycol acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, Polar solvents such as diisobutyl ketone, isophorone, and cyclohexanone; And a mixture of the non-polar solvent and the polar solvent, and the like, and may be appropriately selected and used depending on the characteristics of the resin contained in the composition and the volatilization rate.
또한, 상기 용제는 제1 아크릴 수지 20 내지 50 중량부에 대하여 10 내지 30 중량부의 함량으로 포함될 수 있다. 예를 들어, 상기 용제는 제1 아크릴 수지 20 내지 50 중량부에 대하여 12 내지 28 중량부, 또는 15 내지 25 중량부의 함량으로 포함될 수 있다. 용제의 함량이 상기 범위 내일 경우, 흐름성 및 작업성이 우수한 효과가 있다.In addition, the solvent may be included in an amount of 10 to 30 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. For example, the solvent may be included in an amount of 12 to 28 parts by weight, or 15 to 25 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. When the content of the solvent is within the above range, there is an effect of excellent flowability and workability.
첨가제additive
상기 클리어 도료 조성물은 황변방지제, 수분흡수제, 표면조정제, 흐름방지제, 자외선 흡수제, 핀홀방지제 및 유분방지제로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 추가로 포함할 수 있다.The clear paint composition may further include one or more additives selected from the group consisting of an anti-yellowing agent, a moisture absorbent, a surface modifier, a flow inhibitor, an ultraviolet absorber, an anti-pinhole agent, and an anti-oil agent.
상기 첨가제는 제1 아크릴 수지 20 내지 50 중량부에 대하여 2 내지 20 중량부의 함량으로 포함될 수 있다. 예를 들어, 상기 첨가제는 제1 아크릴 수지 20 내지 50 중량부에 대하여 3 내지 15 중량부, 또는 5 내지 12 중량부의 함량으로 포함될 수 있다. 첨가제의 함량이 상기 범위를 벗어날 경우, 제조된 도막의 외관 및 경화 밀도가 저하될 수 있다. The additive may be included in an amount of 2 to 20 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. For example, the additive may be included in an amount of 3 to 15 parts by weight, or 5 to 12 parts by weight based on 20 to 50 parts by weight of the first acrylic resin. When the content of the additive is out of the above range, the appearance and curing density of the manufactured coating film may be lowered.
상술한 바와 같은 본 발명에 따른 클리어 도료 조성물은 유리전이온도 및 중량평균분자량이 상이한 2종의 아크릴 수지 및 폴리에스터 수지를 포함하여 제조된 도막의 외관 특성, 내스크래치성, 내충격성 및 내후성이 우수하다. 또한, 본 발명에 따른 클리어 도료 조성물은 유성 3C1B 시스템에 적용 가능하여 도장 비용 절감이 가능하여 경제적이다.The clear paint composition according to the present invention as described above is excellent in appearance characteristics, scratch resistance, impact resistance, and weather resistance of a coating film prepared including two types of acrylic resins and polyester resins having different glass transition temperatures and weight average molecular weights. Do. In addition, the clear coating composition according to the present invention can be applied to an oil-based 3C1B system, so that coating costs can be reduced and thus economical.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 그러나 이들 실시예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 이들 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.
[실시예][Example]
실시예 1 내지 9 및 비교예 1 내지 4. 클리어 도료 조성물의 제조Examples 1 to 9 and Comparative Examples 1 to 4. Preparation of clear coating composition
제1 아크릴 폴리올 수지, 제2 아크릴 폴리올 수지, 폴리에스터 수지, 멜라민 수지, 이소시아네이트 화합물, 용제 및 첨가제를 표 1 및 2의 함량대로 혼합하여 클리어 도료 조성물을 제조하였다.A clear paint composition was prepared by mixing a first acrylic polyol resin, a second acrylic polyol resin, a polyester resin, a melamine resin, an isocyanate compound, a solvent, and an additive according to the contents of Tables 1 and 2.
성분(중량부)Ingredient (parts by weight) 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 실시예 6Example 6
제1 아크릴 수지1st acrylic resin 3232 36.736.7 2828 39.239.2 3232 31.531.5
제2 아크릴 수지2nd acrylic resin 66 5.35.3 66 55 99 77
폴리에스터 수지Polyester resin 44 22 44 33 3.63.6 7.27.2
멜라민 수지Melamine resin 2525 2525 2525 2525 2525 2525
이소시아네이트 화합물Isocyanate compounds 66 66 66 66 66 66
황변방지제Anti-yellowing agent 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2
수분흡수제Moisture absorbent 1.11.1 1.11.1 1.11.1 1.11.1 1.11.1 1.11.1
표면조정제Surface modifier 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3
흐름방지제Flow inhibitor 33 33 33 33 33 33
자외선 흡수제UV absorber 22 22 22 22 22 22
용제solvent 20.420.4 18.418.4 24.424.4 15.215.2 17.817.8 16.716.7
총량Total amount 100100 100100 100100 100100 100100 100100
성분 (중량부)Ingredients (parts by weight) 실시예 7Example 7 실시예 8Example 8 실시예 9Example 9 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예4Comparative Example 4
제1 아크릴 수지1st acrylic resin 18.518.5 31.631.6 29.229.2 -- 35.935.9 3636 4545
제2 아크릴 수지2nd acrylic resin 88 1212 33 1010 -- 77 99
폴리에스터 수지Polyester resin 66 33 1212 1010 88 -- 55
멜라민 수지Melamine resin 2525 2525 2525 3838 2525 2525 --
이소시아네이트 화합물Isocyanate compounds 66 66 66 66 66 66 1010
황변방지제Anti-yellowing agent 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2
수분흡수제Moisture absorbent 1.11.1 1.11.1 1.11.1 1.11.1 1.11.1 1.11.1 1.11.1
표면조정제Surface modifier 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3
흐름방지제Flow inhibitor 33 33 33 33 33 33 33
자외선 흡수제UV absorber 22 22 22 22 22 22 22
용제solvent 29.929.9 15.815.8 18.218.2 29.429.4 18.518.5 19.419.4 24.424.4
총량Total amount 100100 100100 100100 100100 100100 100100 100100
이하의 실시예 및 비교예에서 사용한 각 구성요소의 성분 및 제품명은 표 3에 나타냈다.Components and product names of each component used in the following Examples and Comparative Examples are shown in Table 3.
성분ingredient 구성 요소, 물성 또는 화합물명Component, physical property or compound name
제1 아크릴 수지1st acrylic resin 고형분: 60.3중량%, Tg: 11.8℃, Mw: 4,600g/mol, Av: 9.3mgKOH/g, OHv: 145mgKOH/gSolid content: 60.3% by weight, Tg: 11.8°C, Mw: 4,600g/mol, Av: 9.3mgKOH/g, OHv: 145mgKOH/g
제2 아크릴 수지2nd acrylic resin 고형분: 60중량%, Tg: -5℃, Mw: 8,784g/mol, OHv: 92mgKOH/gSolid content: 60% by weight, Tg: -5°C, Mw: 8,784 g/mol, OHv: 92 mgKOH/g
폴리에스터 수지Polyester resin 고형분: 70중량%, Tg: 6℃, Mw: 5,180g/mol, Av: 23mgKOH/g, OHv: 137mgKOH/gSolid content: 70% by weight, Tg: 6°C, Mw: 5,180g/mol, Av: 23mgKOH/g, OHv: 137mgKOH/g
멜라민 수지Melamine resin 고형분: 58중량%, 25℃에서의 점도: 800mPa·s, Av: 1mgKOH/g, Mw: 2,500g/molSolid content: 58% by weight, viscosity at 25°C: 800mPa·s, Av: 1mgKOH/g, Mw: 2,500g/mol
이소시아네이트 화합물Isocyanate compounds 블록 알리파틱 폴리이소시아네이트(25℃에서의 점도: 4,700mPa·s, 고형분: 63중량%)Block aliphatic polyisocyanate (viscosity at 25°C: 4,700 mPa·s, solid content: 63% by weight)
황변방지제Anti-yellowing agent 벤젠 프로판산(Benzene propanoic acid)Benzene propanoic acid
수분흡수제Moisture absorbent 트리메틸 오르소아세테이트(Trimethyl orthoacetate)Trimethyl orthoacetate
표면조정제Surface modifier 실리콘계 계면활성제(BYK-331)Silicone surfactant (BYK-331)
흐름방지제Flow inhibitor 제조사: Aerosil, 제품명: R-805Manufacturer: Aerosil, Product name: R-805
자외선 흡수제UV absorber 제조사: BASF, 제품명: TINUVIN5151Manufacturer: BASF, Product Name: TINUVIN5151
용제solvent 부탄올(코코졸 #100)Butanol (Cocosol #100)
시험예: 제조된 도막의 특성 평가Test Example: Evaluation of the properties of the manufactured coating film
실시예 및 비교예의 클리어 도료 조성물의 물성을 하기와 같은 방법으로 측정하였으며, 그 결과를 표 4에 나타냈다.The physical properties of the clear coating compositions of Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 4.
구체적으로, 시편에 유성 프라이머 도료(제조사: KCC, 제품명: FU2280)를 두께 20㎛로 도포하고 건조한 후 유성 베이스 도료(제조사: KCC, 제품명: TT6680)를 두께 20㎛로 도포하고, 실시예 및 비교예의 클리어 도료 조성물을 두께 40㎛로 도포하고 150℃에서 30분 동안 건조 및 경화하여 클리어 도막층을 형성하였다.Specifically, an oily primer paint (manufacturer: KCC, product name: FU2280) was applied to the specimen to a thickness of 20 μm, dried, and then an oily base paint (manufacturer: KCC, product name: TT6680) was applied to a thickness of 20 μm, and examples and comparisons The clear coating composition of the example was applied to a thickness of 40 μm, dried and cured at 150° C. for 30 minutes to form a clear coating layer.
(1) 도막 외관(1) Appearance of coating film
최종 도막을 대상으로 자동차 외관 측정기인 Wave Scan DOI(BYK Gardner)를 이용하여 CF값을 측정하였으며, 상기 CF값은 높을수록 도막의 외관 특성이 우수한 것으로 판단하였다. 구체적으로, CF값이 70 이상일 경우 우수(◎), 65 이상 70 미만일 경우 양호(○), 60 이상 65 미만일 경우 보통(△), 60 미만일 경우 불량(×)으로 평가하였다.For the final coating film, the CF value was measured using a Wave Scan DOI (BYK Gardner), which is an automobile exterior measuring instrument, and it was determined that the higher the CF value, the better the appearance characteristics of the coating film. Specifically, if the CF value was 70 or more, it was evaluated as excellent (◎), if it was 65 or more and less than 70, good (○), if it was 60 or more and less than 65, it was evaluated as normal (△), and if it was less than 60, it was evaluated as bad (×).
(2) 경도(2) hardness
연필 경도법으로 클리어 도막의 경도를 측정하였다. 구체적으로, 3B, 2B, B, HB, F, H, 2H 및 3H 각각의 연필을 이용하여 클리어 도막에 손상을 주지 않는 최대 경도를 측정하였다(3B, 2B, B, HB, F, H, 2H, 3H: 열세⇔우수). The hardness of the clear coating film was measured by the pencil hardness method. Specifically, the maximum hardness that does not damage the clear coating film was measured using 3B, 2B, B, HB, F, H, 2H and 3H pencils (3B, 2B, B, HB, F, H, 2H , 3H: inferior ⇔ excellent).
(3) 부착성(3) adhesion
시편을 열처리하고 상온에서 24시간 동안 방치한 후 바둑목법으로 부착성을 평가하였다.The specimen was heat-treated and left at room temperature for 24 hours, and then the adhesion was evaluated by the Go wood method.
구체적으로, 상기 바둑목법은 클리어 도막 표면을 칼로 가로 2mm 및 세로 2mm의 정사각형 100개를 만든 후 테이프를 사용하여 정사각형을 떼어내어 부착성을 측정하였다. 이때, 측정된 부착성은 100개의 정사각형이 100% 온전히 붙어있는 경우 M-1(매우 우수), 남은 정사각형이 70% 이상 100% 미만인 경우 M-2(우수), 50% 이상 70% 미만인 경우 M-3(보통), 30% 이상 50% 미만인 경우 M-4(나쁨), 30% 미만인 경우 M-5(매우 나쁨)로 나타냈다.Specifically, in the Go method, 100 squares of 2 mm in width and 2 mm in length were made on the surface of the clear coating film with a knife, and then the square was removed using a tape to measure adhesion. At this time, the measured adhesion is M-1 (excellent) when 100 squares are completely attached to 100%, M-2 (excellent) when the remaining squares are 70% or more and less than 100%, and M- when 50% or more and less than 70%. 3 (normal), 30% or more and less than 50% were expressed as M-4 (bad), and when less than 30%, M-5 (very poor).
또한, 상기 열처리는 150℃에서 20분간 열처리 후 상온에서 20분간 방치하는 것을 1사이클로, 총 3사이클 반복하였다.In addition, the heat treatment was performed at 150° C. for 20 minutes and then left at room temperature for 20 minutes in 1 cycle, and a total of 3 cycles were repeated.
(4) 내수성(4) water resistance
시편을 40℃ 항온수조에 240시간 동안 침적하고 1시간 동안 상온에서 방치한 후 항목 (3)의 바둑목법과 동일한 방법으로 박리 시험을 수행했으며, 평가 기준도 동일하게 적용하였다.The specimen was immersed in a constant temperature water bath at 40° C. for 240 hours and left at room temperature for 1 hour, and then a peel test was performed in the same manner as in Item (3), and the evaluation criteria were also applied.
(5) 내산성(5) acid resistance
시편의 도막 표면에 0.1N 황산을 0.2㎖ 적하한 후 40℃ 이상으로 예열된 오븐에서 150분 동안 처리했다. 이때 시편에 황산을 떨어뜨린 부분의 에칭(etching), 얼룩 또는 부풀음의 발생여부를 육안으로 관찰하여 시편에 손상이 생기지 않은 최고 온도를 내산성 온도로 판정했다.After 0.2 ml of 0.1N sulfuric acid was added dropwise to the coating surface of the specimen, it was treated in an oven preheated to 40°C or higher for 150 minutes. At this time, by visually observing whether or not etching, staining, or swelling occurred in the part where sulfuric acid was dropped on the specimen, the highest temperature at which no damage to the specimen occurred was determined as the acid resistance temperature.
(6) 내스크래치성(6) scratch resistance
시편의 20° 광택을 측정하고(초기 광택 측정), 내세차성 시험기(Amtec Kistler사 제품)를 이용하여 시편의 표면을 10회 왕복 처리한 후 20° 광택을 측정하였다. 이후 초기 광택과 표면처리 후 광택을 하기 수학식 1을 이용하여 광택유지율을 계산하였다. The 20° gloss of the specimen was measured (initial gloss measurement), and the surface of the specimen was reciprocated 10 times using a car wash resistance tester (manufactured by Amtec Kistler), and then 20° gloss was measured. After the initial gloss and gloss after surface treatment, the gloss retention rate was calculated using the following equation.
[수학식 1][Equation 1]
광택유지율 = 표면처리 후 광택 / 초기 광택 × 100Gloss retention rate = Gloss after surface treatment / Initial gloss × 100
(7) 내용제성(7) Solvent resistance
시편의 도막에 자일렌을 묻힌 면포를 올려둔 뒤 매 1분마다 2Kg 힘으로 4회 긁어 하층 도막면이 나타난 시간을 기록했다.After placing a cotton cloth moistened with xylene on the coating film of the specimen, it was scraped 4 times with a force of 2 kg every 1 minute to record the time when the lower layer coating surface appeared.
도막 외관Coating appearance 경도Hardness 부착성Adherence 내수성Water resistance 내산성Acid resistance 초기 광택Initial gloss 내스크래치성Scratch resistance 내용제성Solvent resistance
실시예 1Example 1 ◎◎ FF M-1M-1 M-1M-1 45℃45℃ 91%91% 65%65% 10분10 minutes
실시예 2Example 2 ◎◎ FF M-1M-1 M-1M-1 43℃43℃ 92%92% 65%65% 10분10 minutes
실시예 3Example 3 ◎◎ FF M-1M-1 M-1M-1 45℃45℃ 90%90% 64%64% 10분10 minutes
실시예 4Example 4 ○○ HBHB M-1M-1 M-2M-2 41℃41℃ 86%86% 62%62% 9분9 minutes
실시예 5Example 5 ○○ HBHB M-1M-1 M-2M-2 40℃40℃ 87%87% 62%62% 9분9 minutes
실시예 6Example 6 ○○ HBHB M-1M-1 M-2M-2 42℃42℃ 85%85% 60%60% 9분9 minutes
실시예 7Example 7 △△ BB M-1M-1 M-2M-2 39℃39℃ 84%84% 58%58% 8분8 minutes
실시예 8Example 8 ○○ BB M-2M-2 M-2M-2 38℃38℃ 86%86% 59%59% 8분8 minutes
실시예 9Example 9 △△ BB M-1M-1 M-2M-2 39℃39℃ 87%87% 57%57% 8분8 minutes
비교예 1Comparative Example 1 XX 2B2B M-2M-2 M-4M-4 36℃36℃ 80%80% 54%54% 5분5 minutes
비교예 2Comparative Example 2 △△ 2B2B M-3M-3 M-3M-3 35℃35℃ 77%77% 52%52% 4분4 minutes
비교예 3Comparative Example 3 △△ BB M-3M-3 M-4M-4 34℃34℃ 79%79% 52%52% 5분5 minutes
비교예 4Comparative Example 4 XX 2B2B M-3M-3 M-3M-3 35℃35℃ 75%75% 53%53% 5분5 minutes
표 4에서 보는 바와 같이, 실시예 1 내지 9의 클리어 도료 조성물으로부터 제조된 도막은 경도, 부착성, 내수성, 내산성, 내스크래치성 및 내용제성이 우수했다.As shown in Table 4, the coating films prepared from the clear coating compositions of Examples 1 to 9 were excellent in hardness, adhesion, water resistance, acid resistance, scratch resistance, and solvent resistance.
반면, 제1 아크릴 수지를 포함하지 않는 비교예 1의 조성물로부터 제조된 도막은 외관 특성, 내수성, 내산성 및 내용제성이 부족했다. 또한, 제2 아크릴 수지를 포함하지 않는 비교예 2의 클리어 도막 조성물로부터 제조된 도막은 부착성, 초기 광택, 내스크래치성 및 내용제성이 부족했다. 또한, 폴리에스터 수지를 포함하지 않는 비교예 3의 클리어 도막 조성물로부터 제조된 도막은 부착성, 내수성, 내산성, 내스크래치성 및 내용제성이 부족했다. 또한, 멜라민 수지를 포함하지 않는 비교예 4의 조성물로부터 제조된 도막은 외관 특성, 경도 및 내스크래치성이 부족했다.On the other hand, the coating film prepared from the composition of Comparative Example 1 not containing the first acrylic resin was poor in appearance characteristics, water resistance, acid resistance, and solvent resistance. In addition, the coating film produced from the clear coating composition of Comparative Example 2 not containing the second acrylic resin was poor in adhesion, initial gloss, scratch resistance, and solvent resistance. Further, the coating film produced from the clear coating composition of Comparative Example 3 containing no polyester resin was poor in adhesion, water resistance, acid resistance, scratch resistance, and solvent resistance. In addition, the coating film produced from the composition of Comparative Example 4 containing no melamine resin was poor in appearance characteristics, hardness, and scratch resistance.

Claims (6)

  1. 제1 아크릴 수지, 제2 아크릴 수지, 폴리에스터 수지, 멜라민 수지 및 이소시아네이트 화합물을 포함하고,Including a first acrylic resin, a second acrylic resin, a polyester resin, a melamine resin and an isocyanate compound,
    상기 제2 아크릴 수지는 제1 아크릴 수지보다 유리전이온도가 낮고, 중량평균분자량이 큰, 클리어 도료 조성물.The second acrylic resin has a lower glass transition temperature than the first acrylic resin and has a larger weight average molecular weight, a clear paint composition.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 아크릴 수지는 유리전이온도가 1 내지 20 ℃이고, 수산기가가 120 내지 160 mgKOH/g이며, 중량평균분자량이 5,000g/mol 이하인, 클리어 도료 조성물.The first acrylic resin has a glass transition temperature of 1 to 20° C., a hydroxyl value of 120 to 160 mgKOH/g, and a weight average molecular weight of 5,000 g/mol or less.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 제2 아크릴 수지는 유리전이온도가 -10 내지 -1 ℃이고, 수산기가가 50 내지 110 mgKOH/g이며, 중량평균분자량이 7,000 내지 10,000 g/mol인, 클리어 도료 조성물.The second acrylic resin has a glass transition temperature of -10 to -1 °C, a hydroxyl value of 50 to 110 mgKOH/g, and a weight average molecular weight of 7,000 to 10,000 g/mol, a clear paint composition.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 폴리에스터 수지는 중량평균분자량이 4,000 내지 6,000 g/mol이고, 산가가 15 내지 30 mgKOH/g이며, 유리전이온도가 1 내지 20 ℃인, 클리어 도료 조성물.The polyester resin has a weight average molecular weight of 4,000 to 6,000 g/mol, an acid value of 15 to 30 mgKOH/g, and a glass transition temperature of 1 to 20°C.
  5. 청구항 1에 있어서,The method according to claim 1,
    상기 멜라민 수지는 25℃에서의 점도가 500 내지 1,500 mPa·s이고, 산가가 0.1 내지 5 mgKOH/g이며, 중량평균분자량이 500 내지 5,000 g/mol인, 클리어 도료 조성물.The melamine resin has a viscosity of 500 to 1,500 mPa·s at 25° C., an acid value of 0.1 to 5 mgKOH/g, and a weight average molecular weight of 500 to 5,000 g/mol, a clear paint composition.
  6. 청구항 1에 있어서,The method according to claim 1,
    상기 조성물은 20 내지 50 중량부의 제1 아크릴 수지, 1 내지 10 중량부의 제2 아크릴 수지, 1 내지 10 중량부의 폴리에스터 수지, 10 내지 40 중량부의 멜라민 수지 및 1 내지 10 중량부의 이소시아네이트 화합물을 포함하는, 클리어 도료 조성물.The composition comprises 20 to 50 parts by weight of a first acrylic resin, 1 to 10 parts by weight of a second acrylic resin, 1 to 10 parts by weight of a polyester resin, 10 to 40 parts by weight of a melamine resin and 1 to 10 parts by weight of an isocyanate compound. , Clear paint composition.
PCT/KR2020/007754 2019-06-24 2020-06-16 Clear paint composition WO2020262869A2 (en)

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CN116042074B (en) * 2023-01-16 2024-05-14 Ppg涂料(天津)有限公司 Two-component coating composition

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