KR20130078644A - One-pack composition for automotive clearcoat with improved chemical resistance, scratch resistance and scratch recovery property - Google Patents
One-pack composition for automotive clearcoat with improved chemical resistance, scratch resistance and scratch recovery property Download PDFInfo
- Publication number
- KR20130078644A KR20130078644A KR1020110147704A KR20110147704A KR20130078644A KR 20130078644 A KR20130078644 A KR 20130078644A KR 1020110147704 A KR1020110147704 A KR 1020110147704A KR 20110147704 A KR20110147704 A KR 20110147704A KR 20130078644 A KR20130078644 A KR 20130078644A
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- resistance
- acid
- resin
- glass transition
- Prior art date
Links
Classifications
-
- 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
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C09D7/20—Diluents or solvents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
Description
본 발명은 자동차 외장의 상도용 투명 도료의 조성물에 관한 것으로, 좀 더 상세하게는 도료 조성물 내에 내스크래치 기능성 아크릴 수지, 멜라민 수지, 블록이소시아네이트, 아크릴 폴리올, 촉매 등을 이용해 우수한 내스크래치성 및 스크래치 자기 복원력을 가짐과 동시에 내화학성 및 표면 경도가 양호한 1액형 자동차 상도용 투명 조성물에 관한 것이다.The present invention relates to a composition of a topcoat transparent coating for automobile exteriors, and more particularly, scratch resistance and scratch porcelain using a scratch functional acrylic resin, melamine resin, block isocyanate, acrylic polyol, catalyst, etc. in the paint composition. The present invention relates to a one-component automotive top transparent composition having restoring force and good chemical resistance and surface hardness.
종래의 기술중 스크래치 방지를 위한 문제점을 개선하기 위해서 일본 공개특허공보 제2000-293895호에서는 표면 처리된 실리카와 광경화 타입의 아크릴레이트를 이용하여 내스크래치 향상을 이룰 수 있었으나, 이미 흠집이 난 표면의 자기복원성은 나타내지 못할 뿐만 아니라 실리카의 도입으로 표면 외관의 광특성 및 표면 오염성이 저하되는 문제점을 드러냈다.In order to improve the problem for preventing scratches in the prior art, Japanese Unexamined Patent Publication No. 2000-293895 uses a surface-treated silica and photocurable acrylate to improve scratch resistance, but the surface is already scratched. Not only does it exhibit self-resilience, but the introduction of silica also reveals a problem of deteriorating optical properties and surface contamination of the surface appearance.
또한 대한민국 공개특허공보 제2000-0045053호에서는 실록산 변성 아크릴수지에 아크릴변성 폴리에스테르 폴리올, 멜라민 경화제로 구성된 수지조성물을 이용하여 자동차 상도 도료 내스크래치 개선을 이루고자 했으나 외부의 긁힘에 대한 스크래치 방지 성능을 높이지 못하여 만족할 만한 수준을 보이지 않았으며 특히 이미 긁힘이 발생한 표면 흠집에 대한 자기 복원성에 대한 물성은 발현시키지 못하는 문제점이 있다.In addition, Korean Patent Laid-Open Publication No. 2000-0045053 attempts to improve scratch resistance of automotive topcoats using a resin composition composed of an acrylic modified polyester polyol and a melamine curing agent in a siloxane-modified acrylic resin, but improves scratch resistance against external scratches. It did not show a satisfactory level, and in particular, there is a problem in that the physical properties for self-healing property for surface scratches that have already been scratched are not expressed.
또한 대한민국 공개특허공보 제2006-0103253호에서는 아크릴 수지, 지방족 폴리에스터 수지, 실리콘 변성 폴리아크릴레이트 수지, 폴리디메틸실록산 수지, 알콕시 실란화합물로 구성된 수지 조성물을 이용하여 내스크래치성 및 자기복원성 향상을 이룰 수 있었으나 자동차 도료의 구비조건인 외관 확보를 발현시키지 못하는 문제점이 있다.In addition, Korean Patent Laid-Open Publication No. 2006-0103253 utilizes a resin composition composed of an acrylic resin, an aliphatic polyester resin, a silicone-modified polyacrylate resin, a polydimethylsiloxane resin, and an alkoxy silane compound to improve scratch resistance and self-resilience. It could be, but there is a problem that does not express the appearance secured as a condition for the automobile paint.
현재 자동차 도료용으로 외관 및 물성이 확보되어 상용되는 내스크래치성 및 자기복원형 도료는 2액형 제품이므로 구매자(자동차 회사)의 신규 설비투자의 이유로 사용상 문제가 제기되고 있다. 또한 대부분의 내스크래치성 및 자기복원형 도료의 도막은 탄성을 가지며 유연한 특성으로 내용제성, 내산성, 표면경도가 취약해 사용에 많은 문제점을 가지며 또한 내스크래치성에 강하도록 도막에 미끄러운 성질을 부여하기 위해 도입된 실리카에 의해 재도장 부착성 및 오버베이킹 재도장 부착성이 취약했다. 따라서 2액형을 1액형으로 전환, 내화학성, 경도, 재도장 부착성 및 오버베이킹부착성 개선을 위해 경화제로 멜라민 대신 1액형 경화제로 상용중인 블록이소시아네이트를 사용해 해결하려 했으나 외관 저하, 황변 발생 및 블록이소시아네이트 단독 경화제 사용시 도료 원가의 상승으로 구매자의 욕구를 충분히 만족시키지 못하고 있는 실정이다. The scratch and self-recovering paints, which are commercially available for securing automotive appearance and physical properties, are two-component products, which are causing problems in use due to the purchaser's investment in new equipment. In addition, most of the scratch-resistant and self-resilient coatings have elasticity and flexible properties, which are poor in solvent resistance, acid resistance, and surface hardness, and have many problems in use. The re-adhesive and overbaking repaint adhesion was weak due to the introduced silica. Therefore, in order to improve the conversion of two-part to one-part, chemical resistance, hardness, repainting and overbaking adhesion, we tried to solve by using block isocyanate which is commercially available as one-part curing agent instead of melamine as curing agent. When the isocyanate single curing agent is used, the cost of the paint does not sufficiently satisfy the buyer's desire.
이에 본 발명자는 상기와 같은 문제점을 개선하기 위하여 연구 노력하던 중 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트로 구성되는 아크릴 수지를 자기복원성과 내스크래치성에 유리하도록 유리전이온도, 수산기가, 산가, 고형분 함량을 조정해 2종을 최종 선정하여 주 수지로 사용하였으며, 종래와 다른 상용중인 멜라민 및 블록이소시아네이트를 동시에 적절히 혼합하여 경화밀도 향상과 유연성을 동시에 가지며 경도, 내산성, 내용제성, 부착성, 재도장 부착성, 오버베이킹부착성이 우수한 자동차 상도용 투명 도료 조성물을 1액형으로 얻을 수 있었고 본 발명은 이에 기초하여 완성되었다. Accordingly, the present inventors have been working to improve the problems described above, so that the glass transition temperature, the hydroxyl value, the acid value, and the like of the acrylic resin composed of methacrylate containing polycaprolactone and hydroxyl group are advantageous for self-resilience and scratch resistance. By adjusting the solids content, two kinds were finally selected and used as the main resin.As the conventional melamine and block isocyanate are mixed properly and conventionally, the curing density is improved and the flexibility is improved simultaneously.The hardness, acid resistance, solvent resistance, adhesion, ash An automobile coating transparent coating composition excellent in paint adhesiveness and overbaking adhesiveness could be obtained in a one-part type, and the present invention was completed based on this.
본 발명의 목적은 경화밀도 향상과 유연성을 동시에 가져 내스크래치성 및 자기 복원성이 우수하며 선영성 및 내화학성이 우수한 1액형의 자동차 상도용 투명 도료 조성물을 제공하는 것이다. SUMMARY OF THE INVENTION An object of the present invention is to provide a one-component transparent coating composition for automotive topcoat having excellent curing resistance and self-healing properties and good anti-corrosion and chemical resistance with improved curing density and flexibility.
상기 목적을 달성하기 위해서, 본 발명은 자동차 상도용 투명 도료 조성물의 총 중량 기준으로, 고형분 함량 50∼70%, 수산기가 60∼80%, 산가 2∼5, 유리전이온도(Tg) 20∼40℃인 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지 A 20∼40 중량%; 고형분 함량 40∼60%, 수산기가 60∼80%, 산가 2∼5, 유리전이온도(Tg) 40∼60℃인 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지 B 5∼15 중량%; 고형분 함량 60∼80%, 수산기가 160∼200%, 유리전이온도(Tg) -10∼0℃인 스티렌모노머, 부틸아크릴레이트, 헥사에틸아크릴레이트, 메타메틸아크릴레이트로 구성된 아크릴 폴리올 2∼8 중량%; 메틸레이티드 멜라민 수지 또는 부틸레이티드 멜라민 수지 7∼30 중량%; 디메틸피라졸로 또는 디에틸말로네이트로 블록된 헥사메틸렌디이소시아네이트 경화제 15∼30 중량%; 용제 20∼30 중량%; 산 촉매 0.5∼3 중량%; 및 주석 촉매 0.1∼1 중량%를 포함하는 것을 특징으로 하는 1액형 자동차 상도용 투명 도료 조성물을 제공한다.In order to achieve the above object, the present invention is based on the total weight of the transparent coating composition for automotive top coat, solid content 50 ~ 70%, hydroxyl value 60 ~ 80%, acid value 2 ~ 5, glass transition temperature (Tg) 20 ~ 40 20 to 40% by weight of a methacrylate resin A containing a modified polycaprolactone and a hydroxyl group which is ℃; 5 to 15% by weight of a methacrylate resin B containing a modified polycaprolactone having a solid content of 40 to 60%, a hydroxyl value of 60 to 80%, an acid value of 2 to 5, and a glass transition temperature (Tg) of 40 to 60 ° C and a hydroxyl group; 2-8 weight of acrylic polyol consisting of styrene monomer, butyl acrylate, hexaethyl acrylate, methacrylate with 60-80% solids content, 160-200% hydroxyl group, glass transition temperature (Tg) -10-0 ° C %; 7-30% by weight of methylated melamine resin or butylated melamine resin; 15 to 30% by weight of hexamethylene diisocyanate curing agent blocked with dimethylpyrazole or diethylmalonate; Solvent 20-30 wt%; 0.5-3% by weight of acid catalyst; And 0.1 to 1% by weight of a tin catalyst provides a one-component automotive coating transparent coating composition.
본 발명에 따라 1액형 경화구조로 도료를 발명하기 위해 경화제인 멜라민과 블록이소시아네이트를 동시에 사용하며 또한 산촉매와 주석촉매의 듀얼 촉매(dual catalyst) 시스템 도입으로 도막의 유연성과 탄성을 가짐으로 내스크래치성 및 자기복원성이 우수하며 경화밀도의 증가로 우수한 외관, 경도 및 내화학성을 부여해 자동차 상도용 클리어로서 갖추어야 할 도료 도막의 환경에 우수한 기능성 및 내구성, 선영성 및 내화학성을 제공할 수 있다. According to the present invention, in order to invent a paint with a one-part cured structure, it simultaneously uses a curing agent melamine and block isocyanate, and also has a flexibility and elasticity of the coating film by introducing a dual catalyst system of an acid catalyst and a tin catalyst. And it is excellent in self-resilience and can increase the hardening density to provide excellent appearance, hardness and chemical resistance to provide excellent functionality and durability, sunscreen and chemical resistance to the environment of the coating film to be equipped as a clear for automotive top coat.
이하 본 발명을 상세히 설명하면 다음과 같다.
Hereinafter, the present invention will be described in detail.
전술한 바와 같이, 본 발명은 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트로 구성되는 아크릴 수지와 특정 경화제를 포함하는 우수한 내스크래치성, 자기복원성, 내산성, 내용제성, 경도를 가지는 1액형 자동차 상도용 투명 도료 조성물을 제공한다.
As described above, the present invention is a one-component automobile having excellent scratch resistance, self-resilience, acid resistance, solvent resistance, and hardness, including an acrylic resin composed of modified polycaprolactone and a methacrylate containing a hydroxyl group and a specific curing agent. It provides a transparent coating composition for top coat.
본 발명의 자동차 상도용 투명 도료 조성물은 아크릴 수지와 경화제, 용제, 촉매 및 기타 첨가제를 포함한다.
The transparent coating composition for automotive coatings of the present invention contains an acrylic resin and a curing agent, a solvent, a catalyst and other additives.
(1) 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지 A(1) methacrylate resin A containing modified polycaprolactone and hydroxyl groups
본 발명에서 사용하는 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지 A는 고형분 함량 50∼70%, 수산기가 60∼80%, 산가 2∼5, 유리전이온도(Tg) 20∼40℃, 임계 평균분자량 600∼800이며 100∼200℃의 반응온도에서 제조된다.The methacrylate resin A containing the modified polycaprolactone and hydroxyl group used in the present invention has a solid content of 50 to 70%, a hydroxyl value of 60 to 80%, an acid value of 2 to 5, a glass transition temperature (Tg) of 20 to 40 ° C, It has a critical average molecular weight of 600 to 800 and is prepared at a reaction temperature of 100 to 200 ° C.
이때 상기 메타아크릴레이트 수지 A 내 고형분 함량이 50% 미만이면 외관저하 및 내스크래치성, 내용제성, 경도 등의 물성 저하현상이 나타나고, 70% 이상이면 도장 작업성에 문제가 있다. 상기 메타아크릴레이트 수지 A의 임계분자량이 500∼800으로 500 미만이면 경화밀도가 증가해 도막의 탄성이 약해져 스크래치 복원력이 저하되고 800을 넘으면 도막이 너무 유연해져 경도 및 내화학성이 불량해지는 문제점이 있다.At this time, when the solid content in the methacrylate resin A is less than 50%, physical properties such as appearance deterioration and scratch resistance, solvent resistance, and hardness appear, and when 70% or more, there is a problem in coating workability. When the critical molecular weight of the methacrylate resin A is less than 500 to 500 to 800, the curing density is increased, the elasticity of the coating film is weakened, the scratch restoring force is lowered, and if it exceeds 800, the coating film is too flexible and the hardness and chemical resistance are poor.
메타아크릴레이트 수지 A는 전체 도료 조성물 중의 사용량이 20∼40 중량%인 것이 좋고 그 사용량이 20 중량% 미만일 경우 도료 상의 미반응 이소시아네이트 및 멜라민이 남아있어 내산성 및 내수성에 문제가 발생하고 40 중량%를 초과할 경우 도료상 미반응 OH기가 남아 있어서 내산성 등의 물성문제를 야기한다.
It is preferable that the amount of the methacrylate resin A is 20 to 40% by weight in the total coating composition, and when the amount is less than 20% by weight, the unreacted isocyanate and melamine remain on the paint, which causes problems in acid resistance and water resistance. If exceeded, unreacted OH groups remain on the paint, causing physical problems such as acid resistance.
(2) 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지 B(2) methacrylate resin B containing modified polycaprolactone and hydroxyl groups
본 발명에서 사용하는 또다른 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지 B는 고형분 함량이 40∼60% 수산기가 60∼80%, 산가 2∼5, 유리전이온도(Tg) 40∼60℃, 임계 평균분자량 300∼500이며 100∼200℃의 반응온도에서 제조된다.Another modified polycaprolactone and hydroxyl group-containing methacrylate resin B used in the present invention has a solid content of 40 to 60%, a hydroxyl group of 60 to 80%, an acid value of 2 to 5, and a glass transition temperature (Tg) of 40 to 60. It is prepared at a reaction temperature of 100-200 캜 with a critical average molecular weight of 300-500 캜.
이때 상기 메타아크릴레이트 수지 B 내 고형분 함량이 40% 미만이면 외관저하 및 내스크래치성, 내용제성, 경도 등의 물성 저하현상이 나타나고 60% 이상이면 도장 작업성에 문제가 있다. In this case, when the solid content in the methacrylate resin B is less than 40%, physical properties such as appearance deterioration and scratch resistance, solvent resistance, and hardness appear, and when 60% or more, there is a problem in coating workability.
또한 상기 메타아크릴레이트 수지 B의 임계분자량은 300∼500으로, 300 미만이면 경화밀도가 높아져 도막의 경도가 강해 스크래치 복원력이 전혀 없게 되고 500을 넘으면 도막에 탄성이 생겨 경화밀도가 낮아져 경도 및 내화학성이 불량해지고 작업성에 문제가 된다. 상기 메타아크릴레이트 수지 B의 유리전이 온도가 40℃ 미만이면 표면의 경도가 취약해지고 60℃ 이상이면 경도가 강해져 스크래치 복원성을 잃게된다. In addition, the critical molecular weight of the methacrylate resin B is 300 to 500, if less than 300, the curing density is high, the hardness of the coating film is strong, there is no scratch restoring force, and if it exceeds 500, the coating film has elasticity and the curing density is lowered, thus the hardness and chemical resistance This becomes poor and becomes a problem in workability. If the glass transition temperature of the methacrylate resin B is less than 40 ° C, the hardness of the surface is weak, and if the glass transition temperature is 60 ° C or more, the hardness becomes strong, and scratch recovery is lost.
메타아크릴레이트 수지 B는 전체 도료 조성물 중의 사용량이 5∼15 중량%인 것이 좋고 그 사용량이 5 중량% 미만일 경우 경화밀도가 취약해 경도 및 내용제성에서 문제가 발생하고 15 중량%를 초과할 경우 도료상 미반응 OH기로 내산성의 물성 문제를 야기한다.
It is preferable that the amount of the methacrylate resin B is 5 to 15% by weight in the total coating composition, and when the amount is less than 5% by weight, the curing density is weak, causing problems in hardness and solvent resistance. Phase unreacted OH groups cause problems of physical properties of acid resistance.
(3) 아크릴 폴리올 (3) acrylic polyol
본 발명에서 사용되는 아크릴 폴리올은 스티렌모노머, 부틸아크릴레이트, 헥사에틸아크릴레이트 및 메타메틸아크릴레이트로 구성되어 있으며 수산기가 160∼200, 유리전이온도가 -10∼0℃, 고형분 함량이 60∼80%인 것이다. The acrylic polyol used in the present invention is composed of styrene monomer, butyl acrylate, hexaethyl acrylate and methmethyl acrylate, having a hydroxyl group of 160 to 200, a glass transition temperature of -10 to 0 ° C, and a solid content of 60 to 80 %.
수산기가 160 이하이면 경화밀도를 높이지 못해 내수성, 내용제성 등의 문제가 발생할 수 있고 200이 넘으면 도막의 경도가 강해져 내치핑성, 내충격성등의 문제가 발생한다. 고형분이 60% 이하이면 도료의 고형분이 낮아져 흐름성이 저하될 수 있으며 고형분이 80% 이상이면 도료 점도의 증가로 외관에 좋지 않은 영향을 미친다. When the hydroxyl group is 160 or less, problems such as water resistance and solvent resistance may not occur due to the increase in curing density, and when it exceeds 200, the hardness of the coating film becomes stronger, resulting in problems such as chipping resistance and impact resistance. If the solid content is 60% or less, the solid content of the paint may be lowered and the flowability may be lowered. If the solid content is 80% or more, the paint viscosity may be increased to adversely affect the appearance.
아크릴 폴리올은 전체 도료 조성물 중의 사용량이 2∼8 중량%인 것이 좋고 그 사용량이 2 중량% 미만일 경우 경도 및 내용제성의 문제가 발생하고 8 중량%를 초과할 경우 내충격성의 물성문제를 야기한다. It is preferable that the amount of the acrylic polyol used in the entire coating composition is 2 to 8% by weight, and when the amount is less than 2% by weight, problems of hardness and solvent resistance occur, and when the amount exceeds 8% by weight, physical properties of impact resistance are caused.
(4) 경화제 (4) Hardener
본 발명에 따른 도료 조성물의 성분 중 가장 중요한 특징 중 하나는 경화제로 멜라민 수지와 블록이소시아네이트를 동시에 사용해 내스크래치성 및 내화학성이 우수한 경화시스템을 제공하는 것이다. One of the most important features of the components of the coating composition according to the present invention is to provide a curing system excellent in scratch resistance and chemical resistance by using a melamine resin and a block isocyanate simultaneously as a curing agent.
본 발명의 조성물 중 하나의 경화제인 멜라민 수지는 고형분 함량이 90∼100%이며, 경화온도가 130∼160℃인 메틸레이티드 멜라민 수지 또는 부틸레이티드 멜라민 수지가 좋다. Melamine resin, which is a curing agent of one of the compositions of the present invention, has a solid content of 90 to 100%, and a methylated melamine resin or a butylated melamine resin having a curing temperature of 130 to 160 ° C.
멜라민 수지는 전체 도료 조성물 중량 기준으로 7∼30 중량%로 사용할 수 있다. 그 사용량이 7 중량% 미만일 경우 경도 및 내용제성에서 문제가 발생하고 30 중량%를 초과할 경우 내수성 및 내충격성의 물성문제를 야기한다. Melamine resin can be used in 7 to 30% by weight based on the total weight of the coating composition. If the amount is less than 7% by weight, problems occur in hardness and solvent resistance, and in excess of 30% by weight, there is a problem in properties of water resistance and impact resistance.
바람직하게는 도료 조성물 내 전체 수지의 고형분 대비 15∼30 중량%로 첨가하는 것이 좋다. 수지들의 고형분 대비 15 중량% 미만이면 미경화된 아크릴 수지나 도막내 남아 내수성 및 내용제성이 취약하며 30 중량% 이상이면 선영성이 떨어져 외관을 저하시킨다. Preferably it is added at 15 to 30% by weight relative to the solid content of the total resin in the coating composition. Less than 15% by weight relative to the solids of the resins remain weak in the uncured acrylic resin or coating film, water resistance and solvent resistance, if more than 30% by weight is less sensibility and lowers the appearance.
또한 본 발명의 다른 경화제로는 디메틸피라졸 또는 디에틸말로네이트로 블록된 헥사메틸렌 디이소시아네이트로서 내산성 및 내용제성이 우수하고 도막의 선영성을 향상시켜 결국 외관 향상에 도움이 된다.In addition, another curing agent of the present invention is hexamethylene diisocyanate blocked with dimethylpyrazole or diethylmalonate, which is excellent in acid resistance and solvent resistance, and improves the screening properties of the coating film, thereby consequently improving the appearance.
디메틸피라졸 또는 디에틸말로네이트로 블록된 헥사메틸렌 디이소시아네이트는 전체 도료 조성물 중량 기준으로 15∼30 중량%로 사용할 수 있다. 그 사용량이 15 중량% 미만일 경우 잔존하는 미반응 OH기로 인한 내수성 문제가 발생하고 30 중량%를 초과할 경우 미반응 이소시아네이트기로 내산성 및 내수성 등의 물성문제를 야기한다 Hexamethylene diisocyanate blocked with dimethylpyrazole or diethylmalonate can be used in an amount of 15 to 30% by weight based on the total weight of the paint composition. If the amount is less than 15% by weight, water resistance problem occurs due to the remaining unreacted OH group, and if it exceeds 30% by weight, unreacted isocyanate groups cause physical problems such as acid resistance and water resistance.
또한, 본 발명의 도료 조성물에서 상기 2종의 아크릴 수지 내의 수산기와 블록이소시아네이트의 당량비는 0.9:1∼1.5:1이 되도록 첨가하는 것이 바람직하며, 아크릴의 비가 0.9 이하에서는 잔류된 블록이소시아네이트의 NCO기가 안개처럼 도막을 형성하여 외관 및 재도장 부착성에 문제가 되며 1.5 이상에서는 상기 아크릴 수지의 OH기 잔류로 내수성 및 내화학성이 취약해진다.
Further, in the coating composition of the present invention, the equivalent ratio of the hydroxyl group and the block isocyanate in the two acrylic resins is preferably added so as to be 0.9: 1 to 1.5: 1, and when the acrylic ratio is 0.9 or less, the NCO group of the residual block isocyanate is It forms a coating like fog, which is a problem in appearance and repaint adhesion, and at 1.5 or higher, water resistance and chemical resistance become weak due to the OH group residual of the acrylic resin.
(5) 용제(5) solvent
본 발명의 도료 조성물에서 용제는 자일렌과 같은 방향족 탄화수소계; 메틸아세테이트, 에틸아세테이트, 노말프로필아세테이트, 이소프로필아세테이트, 부틸아세테이트, 메틸셀로솔브아세테이트, 셀로솔브아세테이트, 부틸셀로솔브아세테이트 및 카비톨아세테이트와 같이 에스테르계; 및 에틸알콜, 노말프로판올, 이소프로판올, 노말부탄올, 이소부탄올 및 터셔리부탄올과 같은 알코올계 용제 등에서 선택된 1종 이상을 사용할 수 있다.In the coating composition of the present invention, the solvent may be an aromatic hydrocarbon type such as xylene; Esters such as methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate and carbitol acetate; And alcohol solvents such as ethyl alcohol, normal propanol, isopropanol, normal butanol, isobutanol and tert-butanol can be used.
본 발명에 따른 용제는 전체 도료 조성물의 중량 기준으로 20∼30 중량%로 첨가하는 것이 좋다. 20 중량% 미만이면 도료 표면에 핀홀이 발생하며 30 중량%를 초과하면 도료의 고형분 저하로 외관에 좋지 않은 영향을 미치는 단점이 있으며 흐름성에 문제가 발생한다.
The solvent according to the present invention is preferably added at 20 to 30% by weight based on the weight of the entire coating composition. If it is less than 20% by weight, the pinhole is generated on the surface of the paint, and if it exceeds 30% by weight, the solid content of the paint may have a disadvantage in adversely affecting the appearance and problems in flowability.
(6) 경화제 반응 촉진제(6) curing agent reaction accelerator
본 발명의 다른 기술적 특징은 경화제의 반응을 촉진하기 위해 산 촉매 및 주석 촉매를 동시에 사용하는 것이다. 산 촉매는 멜라민 수지의 경화제를 경화 촉진하며, 주석 촉매는 디메틸피라졸 또는 디에틸말로네이트로 블록된 헥사메틸렌디이소시아네이트 경화제를 경화 촉진한다. Another technical feature of the present invention is the simultaneous use of an acid catalyst and tin catalyst to promote the reaction of the curing agent. The acid catalyst accelerates the curing of the melamine resin and the tin catalyst accelerates the curing of the hexamethylene diisocyanate curing agent blocked with dimethylpyrazole or diethylmalonate.
본 발명의 산 촉매는 도데실벤젠설폰산(DDBSA), 다이노닐나프탈렌설폰산, 또는 다이노닐나프탈렌디설폰산을 바람직하게 사용할 수 있으며, 본 발명의 주석 촉매는 다이부틸틴 다이라우레이트(DBTDL)를 바람직하게 사용할 수 있다. The acid catalyst of the present invention may preferably use dodecylbenzenesulfonic acid (DDBSA), dinonylnaphthalenesulfonic acid, or dinonylnaphthalene disulfonic acid, the tin catalyst of the present invention is dibutyltin dilaurate (DBTDL) It can be used preferably.
본 발명의 산 촉매는 전체 도료 조성물의 중량 기준으로 0.5∼3 중량%로 첨가하는 것이 좋다. 0.5 중량% 미만이면 경도가 취약해져 내용제성 및 내산성의 문제를 야기할 수 있고 3 중량%를 초과하면 경도 증가로 내충격성 및 부착성이 취약해지는 단점이 있다. The acid catalyst of the present invention is preferably added at 0.5 to 3% by weight based on the total weight of the coating composition. If it is less than 0.5% by weight, the hardness is weak, which may cause problems of solvent resistance and acid resistance, and when it is more than 3% by weight, there is a disadvantage that the impact resistance and adhesion are weak due to the increase in hardness.
본 발명의 주석 촉매는 전체 도료 조성물의 중량 기준으로 0.1∼1 중량%로 첨가하는 것이 좋다. 0.1 중량% 미만이면 경도가 취약해져 내용제성 및 내산성의 문제를 야기할 수 있고 1 중량%를 초과하면 내충격성 및 부착성이 취약해지는 단점이 있다.
The tin catalyst of the present invention is preferably added at 0.1 to 1% by weight based on the total weight of the coating composition. If it is less than 0.1% by weight, the hardness is weak, which may cause problems of solvent resistance and acid resistance, and when it is more than 1% by weight, impact resistance and adhesion are weak.
(7) 기타 첨가제 (7) other additives
본 발명에는 외관 및 물성 조절을 위해 자외선 안정제, 흐름 방지제, 평활제 등을 선택적으로 첨가할 수 있으며, 필요에 따라 방향족 및 지방족 탄화수소계 용제를 신나용으로 사용하여 도료의 점도를 조절하는 것도 가능하다. 기타 첨가제는 통상적으로 사용되는 양으로 첨가될 수 있다.
In the present invention, UV stabilizers, flow inhibitors, leveling agents, and the like may be selectively added for controlling appearance and physical properties, and the viscosity of the paint may be adjusted by using aromatic and aliphatic hydrocarbon solvents for thinners as necessary. . Other additives may be added in amounts commonly used.
본 발명에 따른 투명 도료 조성물은 수용성 상도(베이스코트) 위에 적용되며 상기 도료는 자동차 도료에 상용적으로 적용되는 아크릴 멜라민 수지계를 사용하여 만들어진 도료를 말한다. 상술한 바와 같이 본 발명에 따른 투명 도료 조성물은 아크릴 수지의 물성(분자량, 유리전이온도 등)을 조절해 블록이소시아네이트와의 반응으로 생성된 우레탄 결합으로 유연성과 탄성을 가져 스크래치 복원성을 가지며 아크릴 수지와 멜라민의 결합으로 경화밀도를 향상시켜 경도 및 내화학성을 향상시켜 자동차 상도용 클리어로 갖추어야 할 우수한 내구성을 갖는다.
The transparent paint composition according to the present invention is applied on a water-soluble top coat (base coat) and the paint refers to a paint made using an acrylic melamine resin commercially applied to automotive paints. As described above, the transparent coating composition according to the present invention is a urethane bond produced by reaction with a block isocyanate by controlling physical properties (molecular weight, glass transition temperature, etc.) of the acrylic resin, having flexibility and elasticity, having scratch recovery properties, and having an acrylic resin and The combination of melamine improves the curing density, improves hardness and chemical resistance, and has excellent durability to be used as a clear coat for automobiles.
이하 본 발명을 실시예에 의하여 상세히 설명하나, 본 발명이 이에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
실시예Example 1∼4 및 1 to 4 and 비교예Comparative example 1∼5 1 to 5
다음 표 1에 나타난 조성(함량단위: g)으로 1L 플라스틱 비커를 준비하여 전자저울을 이용하여 아크릴 수지 및 멜라민 수지, 흐름방지제, 블록이소시아네이트와 아크릴폴리올 및 노말 부틸알콜 및 자일렌을 넣고 교반기(Disolver)를 이용하여 10분 정도 교반시킨다. 그 다음 첨가제, 촉매 순으로 넣고 20분 정도 교반하여 도료를 제조한다. 그 다음, 통상의 베이스코트(KCC사제품 , 에보니블랙)를 소지에 15㎛ 두께로 도포하고 실온에서 2분간 방치시킨 후 80℃에서 3분간 가열한다. 다음 상기의 실시예 1∼4, 비교예 1∼5의 조성물을 클리어 코트 두께가 45㎛ 정도가 되도록 도포하고 10분 정도 실온에 방치시킨다. 이후 도포된 피도물을 150℃ 오븐에서 30분 정도 열경화시킨다.
Next, prepare a 1L plastic beaker with the composition (content unit: g) shown in Table 1, add an acrylic resin and melamine resin, a flow inhibitor, block isocyanate and acryl polyol, normal butyl alcohol, and xylene using an electronic balance, and then use a stirrer (Disolver). Agitate for about 10 minutes. Then, the additives, followed by a catalyst and stirred for about 20 minutes to prepare a paint. Then, a conventional base coat (manufactured by KCC, Ebony Black) was applied to the substrate with a thickness of 15 占 퐉, left at room temperature for 2 minutes, and heated at 80 ° C for 3 minutes. Next, the compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were applied so as to have a clear coat thickness of about 45 μm and left at room temperature for about 10 minutes. The applied coating is then thermally cured for about 30 minutes in a 150 ℃ oven.
ingredient
(단위: 중량%)(Unit: wt%)
1) 메타아크릴레이트 수지 A: 고형분 함량 50%, 수산기가 70%, 산가 2.5, 유리전이 30℃인 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지(자체 합성)1) methacrylate resin A: methacrylate resin containing a modified polycaprolactone having a solid content of 50%, a hydroxyl value of 70%, an acid value of 2.5 and a glass transition of 30 ° C and a hydroxyl group (self-synthesis)
2) 메타아크릴레이트 수지 B: 고형분 함량 57%, 수산기가 70%, 산가 2.2, 유리전이온도 50℃인 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지(자체 합성) 2) methacrylate resin B: methacrylate resin containing a modified polycaprolactone and a hydroxyl group having a solid content of 57%, a hydroxyl value of 70%, an acid value of 2.2 and a glass transition temperature of 50 ° C. (self-synthesis)
3) 아크릴 폴리올 : 고형분 함량 70%, 수산기가 190%, 유리전이온도 -5℃인 스티렌 모노머, 부틸아크릴레이트, 헥사에틸아크릴레이트, 메타메틸아크릴레이트로 구성된 아크릴 폴리올(자체 합성)3) Acrylic polyol: Acrylic polyol composed of styrene monomer, butyl acrylate, hexaethyl acrylate and methmethyl acrylate having a solid content of 70%, a hydroxyl value of 190% and a glass transition temperature of -5 ° C.
4) 멜라민 수지: 부틸레이티드 멜라민(자체 합성)4) Melamine resin: Butylated melamine (self synthesis)
5) 흐름방지제: NUFLUX사 SETALUX C91756 5) Flow inhibitor: NUFLUX company SETALUX C91756
6) 블록이소시아네이트: 디메틸피라졸로 블록된 헥사메틸렌디이소시아네이트(BAYER PL-350)6) Block isocyanate: Hexamethylene diisocyanate blocked with dimethylpyrazole (BAYER PL-350)
7) 용제: 부틸알콜7) Solvent: Butyl Alcohol
8) 첨가제: 외관 향상을 위한 비실리콘계 소포제로서, BYK315 8) Additive: Non-silicone antifoaming agent for improving the appearance, BYK315
9) 자외선 안정제: BASF사 TINUVIN 384 제품9) UV stabilizer: BASF TINUVIN 384
10) 산 촉매: KING 사 NACURE-XP-221 제품10) Acid catalyst: KING company NACURE-XP-221 products
11) 주석촉매: 다이부틸틴 다이라우레이트
11) Tin catalyst: dibutyl tin dilaurate
상기 도막의 외관 및 물성은 다음과 같이 평가하였으며 그 결과를 하기 표 2에 나타내었다. The appearance and physical properties of the coating film were evaluated as follows, and the results are shown in Table 2 below.
1) 외관: 수평도막을 WAVE SCAN DUAL로 측정한 수치로서 수치가 높을수록 우수한 외관을 나타냄. 1) Appearance: The value of horizontal coating measured by WAVE SCAN DUAL. The higher the value, the better the appearance.
2) 내스크래치성: AMTEK사 CAR WASHER EQUIPMENT로 10회 왕복 후 20도 광택유지율을 측정하여 테스트전/후의 광택을 백분율로 나타냄.2) Scratch resistance: After 20 round trips with AMTEK's CAR WASHER EQUIPMENT, gloss retention rate was measured to express the gloss before and after the test as a percentage.
3) 자기복원성: Mistubish B 연필을 1 kg 추로 하중을 주면서 도막을 긁은 후 상온방치 2시간 후에 도막의 복원의 정도를 육안 및 현미경 관찰함. 3) Self-resilience: After scratching the coating film with a 1 kg weight of Mistubish B pencil, observe the degree of restoration of the coating film visually and under a microscope after 2 hours at room temperature.
4) 내용제성: 크실렌 스팟 테스트를 통하여 이상 유무를 육안으로 관찰.4) Solvent resistance: Visually observe the presence of abnormality through xylene spot test.
5) 내산성: 0.1N 황산 2ml를 도막위에 적하시킨 후 Gradient Oven에 온도를 37℃로 설정해 도막의 손상 정도를 비교평가함.5) Acid resistance: 2ml of 0.1N sulfuric acid was added dropwise onto the coating film, and the temperature was set to 37 ℃ in the gradient oven to evaluate the degree of damage of the coating film.
6) 내가솔린성: 자동차 가솔린 스팟으로 1시간 침적실험시 이상 유무를 육안으로 관찰함. 6) Soline resistance: Observed visually for 1 hour immersion test with automobile gasoline spot.
7) 연필경도: Mistubish 연필을 이용해 1kg 추로 하중을 주면서 도막에 긁히는 정도를 육안으로 판정함. 결과는 2B<B<HB<F<H 순으로 경도가 좋아짐.7) Pencil Hardness: Visually determine the degree of scratch on the coating film while applying a 1kg weight using a Mistubish pencil. The result is hardness in order of 2B <B <HB <F <H.
8) 재도장 부착성: 완성 도막 위 추가로 베이스코트 및 클리어코트를 각각 1회씩 도장해 바둑목법으로 시편을 절단 후 부착유무를 육안으로 확인함.8) Re-coating Adhesion: After coating the base coat and clear coat once more on the finished coating film, check the presence of adhesion after cutting the specimen by the wood-cut method.
9) 오버베이킹부착성: 완성 도막을 150℃ 오븐에서 1시간 방치 후 위 추가로 베이스코트 및 클리어코트를 각각 1회씩 도장해 바둑목법으로 시편을 절단 후 부착유무를 육안으로 확인함.9) Overbaking adhesiveness: After leaving the finished coating film in 150 ℃ oven for 1 hour, paint the base coat and clear coat once more each time and cut the specimen by the check method.
10) 내수성: 40℃ 온수에서 240시간 동안 도막을 침적시킨 후 이상 유무를 육안으로 관찰하고 바둑목법으로 부착유무를 관찰함.10) Water resistance: After immersing the coating film in hot water at 40 ℃ for 240 hours, observe the naked eye visually and observe the presence or absence of adhesion by using the monarch method.
11) 내치핑성: -20℃에서 3시간 방치시킨 후 치핑테스트를 수행함. 수치가 낮을수록 내치핑성이 우수하며, 등급 정도는 1급∼5급으로 나타냄.11) Chipping resistance: After leaving for 3 hours at -20 ℃, chipping test is performed. The lower the value, the better the chipping resistance, and the grade is shown as 1 ~ 5 grade.
Properties
이하2B
Below
이하2B
Below
이하2B
Below
이하2B
Below
부착성Overbaking
Attachment
상기 표 2의 결과로부터, 본 발명에 따른 도료 조성물은 실시예 1∼3에서와 같이 2종 아크릴 수지의 비율에서 아크릴 수지 B가 증가할수록 미세하게 경도가 증가하며 내스크래치성이 다소 취약해지는 경향을 보이나 외관 및 물성 전반적으로 가낭 우수한 결과를 나타내며, 실시예 4와 같이 아크릴 폴리올이 증가할수록 내산성, 내용제성, 내가솔린성 및 경도는 증가하나 내치핑성 및 내스크래치성이 미세하게 떨어지는 것을 볼 수 있다. 또한 비교예 1 및 2의 멜라민 또는 블록이소시아네이트의 단독 경화 구조보다는 실시예 1∼3에서와 같이 2종 경화제를 동시에 사용할 때 내스크래치성, 내화학성, 내산성, 내가솔린성이 좋은 결과를 보여주었다. 또한 비교예 4∼5에서 산촉매 및 주석촉매 단독으로 상용시 내용제성, 내산성, 경도, 재도장 부착성 등 제반물성이 불량해지는 결과가 나타났다.
From the results of Table 2, the coating composition according to the present invention tends to slightly increase the hardness and slightly scratch resistance as the acrylic resin B increases in the ratio of the two kinds of acrylic resin as in Examples 1 to 3 Although it shows excellent overall appearance and physical properties, as shown in Example 4, as the acrylic polyol increases, acid resistance, solvent resistance, gasoline resistance and hardness increase, but chipping resistance and scratch resistance can be seen to be inferior finely. . In addition, when using two types of curing agents at the same time as in Examples 1 to 3 rather than the single curing structure of melamine or block isocyanate of Comparative Examples 1 and 2 showed good results in scratch resistance, chemical resistance, acid resistance, and gasoline resistance. In Comparative Examples 4 to 5, the acid catalyst and the tin catalyst alone resulted in poor general properties such as solvent resistance, acid resistance, hardness, repaint adhesion, and the like.
Claims (5)
고형분 함량 50∼70%, 수산기가 60∼80%, 산가 2∼5, 유리전이온도(Tg) 20∼40℃인 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지 A 20∼40 중량%;
고형분 함량 40∼60%, 수산기가 60∼80%, 산가 2∼5, 유리전이온도(Tg) 40∼60℃인 변성 폴리카프로락톤과 수산기를 함유하는 메타아크릴레이트 수지 B 5∼15 중량%;
고형분 함량 60∼80%, 수산기가 160∼200%, 유리전이온도(Tg) -10∼0℃인 스티렌모노머, 부틸아크릴레이트, 헥사에틸아크릴레이트, 메타메틸아크릴레이트로 구성된 아크릴 폴리올 2∼8 중량%;
메틸레이티드 멜라민 수지 또는 부틸레이티드 멜라민 수지 7∼30 중량%;
디메틸피라졸 또는 디에틸말로네이트로 블록된 헥사메틸렌디이소시아네이트 경화제 15∼30 중량%;
용제 20∼30 중량%;
산 촉매 0.5∼3 중량%; 및
주석 촉매 0.1∼1 중량%를 포함하는 것을 특징으로 하는 1액형 자동차 상도용 투명 도료 조성물. Based on the total weight of the transparent coating composition for automotive topcoats,
20 to 40% by weight of a methacrylate resin A containing a modified polycaprolactone having a solid content of 50 to 70%, a hydroxyl value of 60 to 80%, an acid value of 2 to 5, and a glass transition temperature (Tg) of 20 to 40 ° C and a hydroxyl group;
5 to 15% by weight of a methacrylate resin B containing a modified polycaprolactone having a solid content of 40 to 60%, a hydroxyl value of 60 to 80%, an acid value of 2 to 5, and a glass transition temperature (Tg) of 40 to 60 ° C and a hydroxyl group;
2-8 weight of acrylic polyol consisting of styrene monomer, butyl acrylate, hexaethyl acrylate, methacrylate with 60-80% solids content, 160-200% hydroxyl group, glass transition temperature (Tg) -10-0 ° C %;
7-30% by weight of methylated melamine resin or butylated melamine resin;
15 to 30% by weight of hexamethylene diisocyanate curing agent blocked with dimethylpyrazole or diethylmalonate;
Solvent 20-30 wt%;
0.5-3% by weight of acid catalyst; And
0.1-1 weight% of tin catalyst, The transparent coating composition for one-component automotive tops characterized by the above-mentioned.
아크릴 수지 내 수산기와 경화제 내 이소시아네이트기의 당량비가 0.9:1∼1.5:1인 것을 특징으로 하는 1액형 자동차 상도용 투명 도료 조성물. The method of claim 1,
An equivalent ratio of a hydroxyl group in an acrylic resin and an isocyanate group in a curing agent is 0.9: 1 to 1.5: 1.
상기 메틸레이티드 멜라민 수지 또는 부틸레이티드 멜라민 수지 함량은 도료 조성물 내 전체 수지의 고형분 대비 15∼30 중량%인 것을 특징으로 하는 1액형 자동차 상도용 투명 도료 조성물. The method of claim 1,
The methylated melamine resin or butylated melamine resin content is 15 to 30% by weight relative to the solids of the total resin in the coating composition, characterized in that the one-component automotive top transparent paint composition.
상기 산 촉매는 도데실벤젠설폰산(DDBSA), 다이노닐나프탈렌설폰산, 또는 다이노닐나프탈렌디설폰산인 것을 특징으로 하는 1액형 자동차 상도용 투명 도료 조성물. The method of claim 1,
The acid catalyst is dodecyl benzene sulfonic acid (DDBSA), dinonyl naphthalene sulfonic acid, or dinonyl naphthalene disulfonic acid, characterized in that the one-component automotive top transparent coating composition.
상기 주석 촉매는 다이부틸틴 다이라우레이트(DBTDL)인 것을 특징으로 하는 1액형 자동차 상도용 투명 도료 조성물.
The method of claim 1,
The tin catalyst is dibutyltin dilaurate (DBTDL), characterized in that the transparent coating composition for one-component automotive tops.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110147704A KR101378336B1 (en) | 2011-12-30 | 2011-12-30 | One-pack composition for automotive clearcoat with improved chemical resistance, scratch resistance and scratch recovery property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110147704A KR101378336B1 (en) | 2011-12-30 | 2011-12-30 | One-pack composition for automotive clearcoat with improved chemical resistance, scratch resistance and scratch recovery property |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20130078644A true KR20130078644A (en) | 2013-07-10 |
| KR101378336B1 KR101378336B1 (en) | 2014-03-28 |
Family
ID=48991548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110147704A KR101378336B1 (en) | 2011-12-30 | 2011-12-30 | One-pack composition for automotive clearcoat with improved chemical resistance, scratch resistance and scratch recovery property |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101378336B1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101724918B1 (en) * | 2015-10-05 | 2017-04-07 | 현대자동차주식회사 | Clear paint composition for hot stamping film and painting method using the same |
| WO2017116118A1 (en) * | 2015-12-28 | 2017-07-06 | 주식회사 케이씨씨 | Highly scratch resistant one-pack type paint composition |
| WO2018056637A1 (en) * | 2016-09-23 | 2018-03-29 | 주식회사 케이씨씨 | Aqueous paint composition |
| KR20180106068A (en) * | 2017-03-17 | 2018-10-01 | 주식회사 케이씨씨 | Urethane top coating paint composition |
| WO2019088551A1 (en) * | 2017-10-30 | 2019-05-09 | 주식회사 케이씨씨 | Coating composition |
| WO2019107988A1 (en) * | 2017-12-01 | 2019-06-06 | (주)엘지하우시스 | Sheet |
| KR20190083917A (en) * | 2018-01-05 | 2019-07-15 | 주식회사 케이씨씨 | Paint composition |
| US10494543B2 (en) | 2015-12-14 | 2019-12-03 | Hyundai Motor Company | Shatter-proof glass coating composition, tempered shatter-proof glass using it and method for manufacturing tempered shatter-proof glass |
| WO2022186049A1 (en) * | 2021-03-05 | 2022-09-09 | 日本ペイント・オートモーティブコーティングス株式会社 | Clear coating composition and method for forming multilayer coating film |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100405824B1 (en) * | 2000-12-30 | 2003-11-14 | 주식회사 디피아이 | Polyester Painting Composition |
| KR20040075153A (en) * | 2003-02-20 | 2004-08-27 | 주식회사 금강고려화학 | The Composition of Clearcoat for Automotive |
| KR20050071168A (en) * | 2003-12-31 | 2005-07-07 | 주식회사 케이씨씨 | The composition of clearcoat for automotive |
| KR100576447B1 (en) * | 2003-12-31 | 2006-05-08 | 주식회사 케이씨씨 | Resin and composition for automotive solventbourne 1K clearcoat for automotive aqueous basecoat containing the same |
-
2011
- 2011-12-30 KR KR1020110147704A patent/KR101378336B1/en active IP Right Grant
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101724918B1 (en) * | 2015-10-05 | 2017-04-07 | 현대자동차주식회사 | Clear paint composition for hot stamping film and painting method using the same |
| US10011738B2 (en) | 2015-10-05 | 2018-07-03 | Hyundai Motor Company | Clear paint composition for hot stamping film and painting method using the same |
| US10494543B2 (en) | 2015-12-14 | 2019-12-03 | Hyundai Motor Company | Shatter-proof glass coating composition, tempered shatter-proof glass using it and method for manufacturing tempered shatter-proof glass |
| WO2017116118A1 (en) * | 2015-12-28 | 2017-07-06 | 주식회사 케이씨씨 | Highly scratch resistant one-pack type paint composition |
| US10683436B2 (en) | 2015-12-28 | 2020-06-16 | Kcc Corporation | One-component type paint composition with superior scratch resistance |
| CN109312189A (en) * | 2016-09-23 | 2019-02-05 | Ｋｃｃ公司 | Water-based paint compositions |
| KR20180032846A (en) * | 2016-09-23 | 2018-04-02 | 주식회사 케이씨씨 | Aqueous Paint Composition |
| WO2018056637A1 (en) * | 2016-09-23 | 2018-03-29 | 주식회사 케이씨씨 | Aqueous paint composition |
| CN109312189B (en) * | 2016-09-23 | 2021-07-20 | Ｋｃｃ公司 | Aqueous coating composition |
| KR20180106068A (en) * | 2017-03-17 | 2018-10-01 | 주식회사 케이씨씨 | Urethane top coating paint composition |
| WO2019088551A1 (en) * | 2017-10-30 | 2019-05-09 | 주식회사 케이씨씨 | Coating composition |
| CN111295425A (en) * | 2017-10-30 | 2020-06-16 | Ｋｃｃ公司 | Coating composition |
| WO2019107988A1 (en) * | 2017-12-01 | 2019-06-06 | (주)엘지하우시스 | Sheet |
| KR20190083917A (en) * | 2018-01-05 | 2019-07-15 | 주식회사 케이씨씨 | Paint composition |
| WO2022186049A1 (en) * | 2021-03-05 | 2022-09-09 | 日本ペイント・オートモーティブコーティングス株式会社 | Clear coating composition and method for forming multilayer coating film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101378336B1 (en) | 2014-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101378336B1 (en) | One-pack composition for automotive clearcoat with improved chemical resistance, scratch resistance and scratch recovery property | |
| US10604675B2 (en) | Quick-drying, energy-elastic, scratch-resistant and stable coating compounds | |
| EP2188341B1 (en) | Paint compositions, a method of finish-painting and painted objects | |
| KR101488316B1 (en) | Paint composition for scratch self-recovering | |
| JP5874971B2 (en) | Urethane coating composition and resin member | |
| CN109312189B (en) | Aqueous coating composition | |
| JP2012021111A (en) | Urethane coating composition and resin member | |
| KR20170130210A (en) | Clear Paint Composition | |
| KR101978060B1 (en) | 2-liquid type top coating paint for car using high solid Acrylic Polyol resin | |
| EP3239204B1 (en) | Highly elastic polyester modified urethane resin, and clear coat composition containing same | |
| US20040063851A1 (en) | Acrylate-based coating composition containing fluoromodified polymers | |
| KR101808389B1 (en) | Surfacer paint composition for reparing automobiles | |
| KR101435968B1 (en) | Anti-scratch clear paint composition and method of manufacturing paint film using the same | |
| KR20040077987A (en) | The composition of 2K clearcoat for automotive | |
| WO2009013576A1 (en) | Reactive diluents for modifying thermosetting paint compositions and paint compositions in which they are used. | |
| KR101540689B1 (en) | Transparent paint composition comprising acryl resin for hardener | |
| KR20140115828A (en) | Scratch self-recovering paint composite | |
| KR101928148B1 (en) | Paint composition | |
| KR102567352B1 (en) | Clear paint composition | |
| KR102347848B1 (en) | Coating composition for vehicle | |
| KR20020056025A (en) | Coating composition for automobile | |
| KR101163463B1 (en) | Water soluble Clear paint for Vacuum Ion Plating | |
| KR20170121884A (en) | 2 components acrylic urethane transparent paint composition containing cellulose esters | |
| JPH11148049A (en) | Coating composition, coated product and production of inorganic oxide sol | |
| KR20040075153A (en) | The Composition of Clearcoat for Automotive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20161229 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20200226 Year of fee payment: 9 |