KR20030057784A - Polyester resin for automobile paints - Google Patents
Polyester resin for automobile paints Download PDFInfo
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- KR20030057784A KR20030057784A KR1020010087867A KR20010087867A KR20030057784A KR 20030057784 A KR20030057784 A KR 20030057784A KR 1020010087867 A KR1020010087867 A KR 1020010087867A KR 20010087867 A KR20010087867 A KR 20010087867A KR 20030057784 A KR20030057784 A KR 20030057784A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Wood Science & Technology (AREA)
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- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
본 발명은 자동차 중도 도료용 폴리에스테르 수지에 관한 것으로서, 더욱 상세하게는 2종 이상의 폴리에스테르를 지방족 디이소시아네이트로 변성시켜 도료로 사용할 때의 내한부착성(chipping)을 우수하게 개선시킨 자동차 중도 도료용 폴리에스테르 수지에 관한 것이다.The present invention relates to a polyester resin for automotive intermediate paints, and more particularly, to automotive intermediate paints, in which two or more polyesters are modified with aliphatic diisocyanate to improve the chipping resistance when used as a paint. It relates to a polyester resin.
일반적으로 자동차용 도료에 있어서 중도용 도료를 구성하는 수지로서는 폴리에스테르 수지나 폴리우레탄 수지가 사용되고 있는 바, 이중에서 폴리에스테르 수지는 저온에서 자갈이나 모래에 의해 충격을 받을 경우 부착성능이 떨어져서 공기중의 산소나 염분에 노출되기 때문에 차체의 부식이 빨라지게 되며, 폴리우레탄 수지는 내한 치핑성은 우수하나 경도와 평활성이 나쁘고 색상이 황색으로 변하는 폐단이 있다.Generally, polyester resins or polyurethane resins are used as resins for intermediate paints in automobile paints. Among them, polyester resins have poor adhesion when they are impacted by gravel or sand at low temperatures. Corrosion of the car body is accelerated because of exposure to oxygen or salts. Polyurethane resin has excellent cold resistance chipping resistance but poor hardness and smoothness.
이러한 문제점을 해결하기 위해서 종래에는 폴리에스테르를 폴리글리콜 또는 장쇄의 지방족 산으로 변성시키거나 2종이상의 폴리에스테르를 혼합하여 사용함으로써 내한 치핑성을 향상시키고자 하였으나(미국특허 제4,616,054호, 제4,532,177호, 제3,565,839호, 일본특허공개 소58-74349호,소61-23650호, 소62-151474호), 내한 치핑성의 개선효과에 한계가 있었다.In order to solve this problem, conventionally, it was intended to improve chipping resistance by modifying polyester with polyglycol or long-chain aliphatic acid or by mixing two or more polyesters (US Pat. Nos. 4,616,054 and 4,532,177). No. 3,565,839, Japanese Patent Application Laid-Open No. 58-74349, No. 61-23650, No. 62-151474), and the effect of improving cold resistance chipping resistance was limited.
따라서, 본 발명에서는 통상의 폴리에스테르에 지방족 디이소시아네이트로 합성하여 변성된 폴리에스테르를 혼용하여 사용함으로써, 내한 치핑성이 우수하게 개선된 도료용 폴리에스테르 수지를 제공하는 데 그 목적이 있다.Therefore, an object of the present invention is to provide a polyester resin for paints which is excellent in cold resistance chipping resistance by using a polyester synthesized by aliphatic diisocyanate and modified with ordinary polyester.
상기와 같은 목적을 달성하기 위한 본 발명의 자동차 중도 도료용 폴리에스테르 수지는 2관능성 카르복실산 또는 그의 에스테르 형성성 유도체 및 탄소수 2∼10의 알킬렌글리콜로 구성된 제1폴리에스테르 수지; 및 탄소수 2∼8의 지방족 직쇄상 카르복실산 및 탄소수 2∼10의 알킬렌 글리콜로 구성된 폴리에스테르 수지(폴리에스테르 수지 a)에 지방족 디이소시아네이트 및 폴리카프로락톤 폴리올 또는 폴리메타크릴레이트 디올을 첨가하여 변성시킨 제2폴리에스테르 수지로 이루어진 것임을 그 특징으로 한다.In order to achieve the above object, the polyester resin for automobile intermediate coating of the present invention comprises a first polyester resin composed of a bifunctional carboxylic acid or an ester-forming derivative thereof and an alkylene glycol having 2 to 10 carbon atoms; And aliphatic diisocyanate and polycaprolactone polyol or polymethacrylate diol to polyester resin (polyester resin a) composed of aliphatic linear carboxylic acid having 2 to 8 carbon atoms and alkylene glycol having 2 to 10 carbon atoms. It is characterized by consisting of the modified second polyester resin.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 내한부착성이 우수한 공중합 폴리에스테르 수지에 관한 것으로서, 본 발명에서는 폴리에스테르 수지로서 2종의 것을 혼용하여 도료에 적용하도록 한것이다.The present invention relates to a copolyester resin having excellent cold resistance, and in the present invention, two kinds of polyester resins are mixed and applied to a coating material.
본 발명에 따른 제1폴리에스테르 수지는 1종이상의 방향족 카르복실산과 1종이상의 지방족 카르복실산을 산성분으로 하며, 2종이상의 알킬렌글리콜을 글리콜 성분과 긴사슬의 (탄소수 6-18) 알킬기가 치환된 모노애시드 혹은 모노알코올 혹은 글리시딜 에스터로 합성한 공중합 폴리에스테르이다.The first polyester resin according to the present invention comprises at least one aromatic carboxylic acid and at least one aliphatic carboxylic acid as an acid component, and at least two alkylene glycols with a glycol component and a long-chain (carbon number 6-18) alkyl group. It is a copolyester synthesize | combined with monosubstituted monoacid, monoalcohol, or glycidyl ester.
상기 제1폴리에스테르 수지를 구성하는 산성분과 글리콜 성분을 구체적으로 살펴보면, 디카르복실산으로는 테레프탈산, 이소프탈산, 프탈산, 나프탈산, 디메틸테레프탈레이트, 디메틸이소프탈레이트, 무수프탈산, 옥산산, 말론산, 석신산, 아디프산, 글루탈산, 피말산, 수비산, 아젤라산, 세바스산, 무수 프탈산, 무수석신산, 도데시세닐 무수석신산 등을 사용하며, 사이클로 카르복실산으로는 1,4-사이클로헥산디애시드, 디메틸사이클로헥산 1,4-디카르본산 등을 들 수 있다.Looking at the acid component and glycol component constituting the first polyester resin in detail, as the dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalic acid, dimethyl terephthalate, dimethyl isophthalate, phthalic anhydride, oxane, malonic acid , Succinic acid, adipic acid, glutaric acid, pimalic acid, defensive acid, azelaic acid, sebacic acid, phthalic anhydride, succinic acid, dodecynyl succinic anhydride, and the like, and 1,4 as cyclocarboxylic acid -Cyclohexane diacid, dimethyl cyclohexane 1,4-dicarboxylic acid, etc. are mentioned.
또한 제1폴리에스테르 수지 제조시에 긴사슬의(탄소수 6-18) 지방족 모노카르복실산을 제1폴리에스테르 수지 중 25중량% 이내로 사용할 수 있다. 구체적인 예로는 옥타노익 애시드, 노나노익 애시드, 2-에틸헥사노익 애시드, 이소노나노익애시드, 데카노익애시드, 라우릭애시드, 팔미틱애시드, 이소스테아릭애시드 하이드록시스테아릭애시드, 벤조익애시드, 4-터트부틸 벤조익애시드로부터 선택된 단독 또는 그 혼합물을 들 수 있다.In addition, when manufacturing a 1st polyester resin, long chain (C6-C18) aliphatic monocarboxylic acid can be used in 25 weight% of a 1st polyester resin. Specific examples include octanoic acid, nonanoic acid, 2-ethylhexanoic acid, isononanoic acid, decanoic acid, lauric acid, palmitic acid, isostearic acid hydroxystearic acid, and benzoic acid. And single or mixture thereof selected from an acid and 4-tertbutyl benzoic acid.
또한, 탄소수 8∼18의 알킬기가 치환된 무수석신산 또는 석신산을 모노머로서 첨가할 수 있는 바, 첨가시 그 함량은 전체 제1폴리에스테르 수지 조성 중 25중량% 이내인 것이 바람직하다.In addition, since succinic anhydride or succinic acid substituted with an alkyl group having 8 to 18 carbon atoms can be added as a monomer, the content thereof is preferably within 25% by weight of the total first polyester resin composition.
상기 산성분과 반응되는 알킬렌글리콜 성분으로는 에틸렌글리콜, 1,2-프로필렌글리콜, 1,3-프로필렌글리콜, 2-메틸프로판 1,3-디올, 네오펜틸글리콜, 2-부틸2-에틸-1,3프로판디올, 1,2-부탄디올, 1,3-부탄디올, 1,4-사이클로헥산디올, 1,4-사이클로헥산디메티롤, 1,5펜탄디올, 3-메틸 펜탄디올, 1,6-헥산디올, 2,2,4-트리메틸펜??-1,3디올, 디메틸올 프로피오닉 애시드, 트리메틸올 프로판, 트리메틸올 에탄, 글리세롤, 1,2,6-헥산트리올, 트리메틸올 등을 사용할 수 있다.The alkylene glycol component reacted with the acid component may be ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methylpropane 1,3-diol, neopentyl glycol, 2-butyl2-ethyl-1 , 3 propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimetholol, 1,5 pentanediol, 3-methyl pentanediol, 1,6- Hexanediol, 2,2,4-trimethylphen ??-1,3diol, dimethylol propionic acid, trimethylol propane, trimethylol ethane, glycerol, 1,2,6-hexanetriol, trimethylol and the like can be used. Can be.
또한 긴사슬의(탄소수 6-18) 모노알코올을 전체 제1폴리에스테르 수지 중 20중량% 이내로 사용할 수 있는데, 예를들면 사이클로헥사놀, 2-에틸헥사놀, 스테아릴 알코올, 4-터트부틸 사이클로헥사놀 등을 들 수 있다.In addition, long chain (6-18 carbon atoms) monoalcohols can be used within 20% by weight of the total first polyester resin, e.g. cyclohexanol, 2-ethylhexanol, stearyl alcohol, 4-tertbutyl cyclo Hexanol and the like.
또한 긴사슬의(탄소수 5-18)의 모노카르복실산의 글리시딜에스테르 화합물도 사용할 수 있다. 예를들면 쉘(Shell)사의 CADURA E-10이 있다.Moreover, the glycidyl ester compound of the long-chain (carbon number 5-18) monocarboxylic acid can also be used. For example, Shell's CADURA E-10.
제1폴리에스테르수지는 유리전이온도가 -40℃∼20℃ 범위를 만족하는 것이 바람직하다.It is preferable that a 1st polyester resin satisfy | fills the glass transition temperature of -40 degreeC-20 degreeC.
한편, 상기 제1폴리에스테르 수지와 혼용되는 제2폴리에스테르 수지는 상기 제1폴리에스테르와 유사한 조성의 폴리에스테르 수지(폴리에스테르 수지 a)를 제조한 후, 여기에 지방족 디이오시아네이트로 폴리카프로락톤 폴리올 또는 폴리메타크릴레이트 디올을 변성시켜 얻어진 것이다.On the other hand, the second polyester resin mixed with the first polyester resin is produced a polyester resin (polyester resin a) of a composition similar to the first polyester, and then polycapro with aliphatic diiocyanate It is obtained by modifying lactone polyol or polymethacrylate diol.
이때, 지방족 디이소시아네이트로서는 헥사메틸렌 디이소시아네이트, 이소포론디이소시아네이트, 테트라메틸크실렌디이소시아네이트, 메틸렌 비스(4-사이클로헥실 이소시아네이트), 노보넨인디이소시아네이트, 이소포론 디이소시아네이트 트라이멀, 헥사메틸렌 디이소시아네이트 트라이머를 폴리에스테르 수지 a 100중량부에 대하여 3∼40중량부 되도록 사용할 수 있다.At this time, as aliphatic diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), norbornene in diisocyanate, isophorone diisocyanate trimal, hexamethylene diisocyanate trimer It can be used so that 3-40 weight part with respect to 100 weight part of polyester resin a.
만일, 그 사용량이 폴리에스테르 수지 a 100중량부에 대하여 3중량부 미만이면 내한 치핑성이 저하되고, 40중량부를 초과할 경우 외관(레벨링)이 저하된다.If the amount is less than 3 parts by weight with respect to 100 parts by weight of the polyester resin a, cold resistance chipping resistance is lowered, and when it exceeds 40 parts by weight, the appearance (leveling) is lowered.
변성용 폴리올로는 폴리카프로락톤 폴리올 혹은 폴리메타크릴레이트 디올을 사용하는 바, 그 사용량은 폴리에스테르 수지 a 100중량부에 대하여 10∼100중량부로 사용하는 것이 바람직하다.A polycaprolactone polyol or polymethacrylate diol is used as the modified polyol, and the amount thereof is preferably used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the polyester resin a.
이때, 변성용 폴리올의 첨가량이 폴리에스테르 수지 a 100중량부에 대하여 10중량부 미만이면 도막의 유연성이 저하되어 내한치핑성이 취약하고, 100중량부 초과면 도막이 너무 소프트(soft)해져서 경도, 샌딩성이 저하되는 문제가 있다.At this time, if the addition amount of the modified polyol is less than 10 parts by weight with respect to 100 parts by weight of the polyester resin a, the flexibility of the coating film is lowered and the cold resistance is weak, and if it is more than 100 parts by weight, the coating film is too soft to give hardness and sanding. There is a problem that the deterioration.
상기와 같이 얻어진 제1폴리에스테르 수지와 제2폴리에스테르 수지를 혼용할 때, 제1폴리에스테르 수지 70중량% 이하와 제2폴리에스테르 수지 10∼30중량%로 혼합하는 것이 바람직하다. 만일, 제2폴리에스테르 수지의 사용량이 30중량% 미만이면 내한 치핑성이 감소된다.When mixing the 1st polyester resin and 2nd polyester resin obtained as mentioned above, it is preferable to mix with 70 weight% or less of 1st polyester resin, and 10-30 weight% of 2nd polyester resins. If the amount of the second polyester resin is less than 30% by weight, cold resistance chipping resistance is reduced.
한편, 제1폴리에스테르 수지나 제2폴리에스테르 수지의 제조에 있어서 에스테르화시킬 때 촉매를 사용하는 것이 바람직한데, 그 촉매로서는 초산칼슘, 초산아연, 초산리튬, 네트라부톡시부탄 등을 사용하며, 중축합 촉매로서는 안티몬디옥사이드, 안티몬트리옥사이드 등을 사용하며, 제2폴리에스테르 수지 제조시 변성촉매로서는 티부틸틴라우릴레이트 등을 사용할 수 있다.On the other hand, it is preferable to use a catalyst when esterifying in the production of the first polyester resin or the second polyester resin, and as the catalyst, calcium acetate, zinc acetate, lithium acetate, netrabutoxybutane, etc. are used. Antimony dioxide, antimony trioxide, etc. are used as a polycondensation catalyst, A thibutyl tin laurate etc. can be used as a modification catalyst at the time of manufacture of a 2nd polyester resin.
본 발명에서 공히 폴리에스테르는 수평균 분자량이 1,000∼3,500인 것을 사용하는 바, 만일 분자량이 상기의 범위 미만이면 내한 부착성이 저하되고 초과하면 경도가 저하된다.In the present invention, the polyester has a number average molecular weight of 1,000 to 3,500, but if the molecular weight is less than the above range, the cold resistance is lowered and the hardness is lowered if exceeded.
이와같은 본 발명에 의해 제조된 폴리에스테르 수지는 내한 치핑성과 평활성이 우수하기 때문에 접착제, 도료, 잉크 등의 제조에 사용 가능하며, 특히 자동차 도료의 제조에 사용할 경우 내한 치핑성이 우수하기 때문에 부식을 방지하는 효과가 우수하다.Since the polyester resin prepared according to the present invention has excellent cold resistance chipping and smoothness, it can be used for the manufacture of adhesives, paints, inks, and the like. The effect of preventing is excellent.
이하, 본 발명을 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
하기 제조예 및 실시예에서 부는 중량부를 나타낸다.In the following preparations and examples, parts represent parts by weight.
합성예 1: 폴리에스테르 A-1의 제조Synthesis Example 1 Preparation of Polyester A-1
이소프탈산 373.5중량부, 아디프산 328.5중량부, 네오펜틸글리콜 374.4중량부, 1,6-헥산디올 92중량부, 1,4-사이클로헥산디메티롤 172중량부, 트리메티롤프로판 78중량부와 이소노나노익애시드 50중량부를 반응계에 넣고 210℃에서 반응시키면 부산물인 물이 생성되면서 올리고머가 생성된다. 이때 분자량을 2500 정도로 조정한다. 생성된 폴리에스테르를 셀로솔부 아세테이트에 고형분 70%가 되도록 녹였다. 얻어진 폴리에스테르 수지의 유리전이온도는 -15℃이다.373.5 parts by weight of isophthalic acid, 328.5 parts by weight of adipic acid, 374.4 parts by weight of neopentyl glycol, 92 parts by weight of 1,6-hexanediol, 172 parts by weight of 1,4-cyclohexanedimethol, 78 parts by weight of trimetholpropane When 50 parts by weight of isononanoic acid is added to the reaction system and reacted at 210 ° C., oligomer is generated while water is produced as a by-product. At this time, the molecular weight is adjusted to about 2500. The resulting polyester was dissolved in cellosol moiety to 70% solids. The glass transition temperature of the obtained polyester resin is -15 degreeC.
합성예 2: 폴리에스테르 A-2의 제조Synthesis Example 2: Preparation of Polyester A-2
이소프탈산 373.5중량부, 아디프산 328중량부, 네오펜틸글리콜 374.4중량부, 1,6-헥산디올 92중량부, 1,4-사이클로헥산디메티롤 172중량부, 트리메티롤프로판 78중??부와 도데세닐 무수석신산 50중량부를 반응계에 넣고 210℃에서 반응시키면부산물인 물이 생성되면서 올리고머가 생성된다. 이때 분자량을 2500 정도로 조정한다. 생성된 폴리에스테르를 셀로솔부 아세테이트에 고형분 70%가 되도록 녹였다. 얻어진 폴리에스테르 수지의 유리전이온도는 -15℃이다.373.5 parts by weight of isophthalic acid, 328 parts by weight of adipic acid, 374.4 parts by weight of neopentylglycol, 92 parts by weight of 1,6-hexanediol, 172 parts by weight of 1,4-cyclohexanedimethyrol, trimetholpropane 78 50 parts by weight of dodecenyl anhydrous succinic anhydride is added to the reaction system and reacted at 210 ° C., thereby producing an oligomer while producing byproduct water. At this time, the molecular weight is adjusted to about 2500. The resulting polyester was dissolved in cellosol moiety to 70% solids. The glass transition temperature of the obtained polyester resin is -15 degreeC.
합성예 3: 폴리에스테르 A-3의 제조Synthesis Example 3: Preparation of Polyester A-3
이소프탈산 373.5중량부, 아디프산 328.5중량부, 네오펜틸글리콜 374.4중량부, 1,6-헥산디올 92중량부, 1,4-사이클로헥산디메티롤 172중량부, 트리메티롤프로판 78중량부와 CARDURA E-10(쉘사 제품) 50중량부를 반응계에 넣고 210℃에서 반응시키면 부산물인 물이 생성되면서 올리고머가 생성된다. 이때 분자량을 2500 정도로 조정한다. 생성된 폴리에스테르를 셀로솔부 아세테이트에 고형분 70%가 되도록 녹였다. 얻어진 폴리에스테르 수지의 유리전이온도는 -15℃이다.373.5 parts by weight of isophthalic acid, 328.5 parts by weight of adipic acid, 374.4 parts by weight of neopentyl glycol, 92 parts by weight of 1,6-hexanediol, 172 parts by weight of 1,4-cyclohexanedimethol, 78 parts by weight of trimetholpropane 50 parts by weight of CARDURA E-10 (manufactured by Shell Company) is added to the reaction system and reacted at 210 ° C., thereby producing oligomer while producing byproduct water. At this time, the molecular weight is adjusted to about 2500. The resulting polyester was dissolved in cellosol moiety to 70% solids. The glass transition temperature of the obtained polyester resin is -15 degreeC.
합성예 4: 폴리에스테르 A-4의 제조Synthesis Example 4: Preparation of Polyester A-4
이소프탈산 373.5중량부, 아디프산 328.5중량부, 네오펜틸글리콜 374.4중량부, 1,6-헥산디올 92중량부, 1,4-사이클로헥산디메티롤 172중량부, 트리메티롤프로판 78중량부와 스테아릴 알코올 40중량부를 반응계에 넣고 210℃에서 반응시키면 부산물인 물이 생성되면서 올리고머가 생성된다. 이때 분자량을 2500 정도로 조정한다. 생성된 폴리에스테르를 셀로솔부 아세테이트에 고형분 70%가 되도록 녹였다. 얻어진 폴리에스테르 수지의 유리전이온도는 -15℃이다.373.5 parts by weight of isophthalic acid, 328.5 parts by weight of adipic acid, 374.4 parts by weight of neopentyl glycol, 92 parts by weight of 1,6-hexanediol, 172 parts by weight of 1,4-cyclohexanedimethol, 78 parts by weight of trimetholpropane When 40 parts by weight of stearyl alcohol is added to the reaction system and reacted at 210 ° C., oligomer is produced while producing byproduct water. At this time, the molecular weight is adjusted to about 2500. The resulting polyester was dissolved in cellosol moiety to 70% solids. The glass transition temperature of the obtained polyester resin is -15 degreeC.
합성예 5: 폴리에스테르 B-1의 제조Synthesis Example 5 Preparation of Polyester B-1
상기 합성예 1에서 얻어진 폴리에스테르 A-1 200중량부, 헥사메틸렌디 이소시아네이트 15중량부, 디부틸틴라우릴레이트 0.1중량부, 폴리카프로락톤 폴리올 40중량부를 반응계에 넣고 온도를 70℃까지 승온하여 약 5시간 정도 교반하며 반응시켰다.200 parts by weight of polyester A-1 obtained in Synthesis Example 1, 15 parts by weight of hexamethylene diisocyanate, 0.1 part by weight of dibutyltinlaurylate and 40 parts by weight of polycaprolactone polyol were added to a reaction system, and the temperature was raised to 70 ° C. The reaction was stirred for about 5 hours.
합성예 6: 폴리에스테르 B-2의 제조Synthesis Example 6 Preparation of Polyester B-2
상기 합성예 2에서 얻어진 폴리에스테르 A-2 200중량부, 헥사메틸렌디 이소시아네이트 15중량부, 디부틸틴라우릴레이트 0.1중량부, 폴리카프로락톤 폴리올 40중량부를 반응계에 넣고 온도를 70℃까지 승온하여 약 5시간 정도 교반하며 반응시켰다.200 parts by weight of polyester A-2 obtained in Synthesis Example 2, 15 parts by weight of hexamethylene diisocyanate, 0.1 part by weight of dibutyltinlaurylate, and 40 parts by weight of polycaprolactone polyol were added to a reaction system, and the temperature was raised to 70 ° C. The reaction was stirred for about 5 hours.
합성예 7: 폴리에스테르 B-3의 제조Synthesis Example 7: Preparation of Polyester B-3
상기 합성예 3에서 얻어진 폴리에스테르 A-3 200중량부, 헥사메틸렌디 이소시아네이트 15중량부, 디부틸틴라우릴레이트 0.1중량부, 폴리메틸메타크릴레이트 디올 40중량부를 반응계에 넣고 온도를 90℃까지 승온하여 약 5시간 정도 교반하며 반응시켰다.200 parts by weight of polyester A-3 obtained in Synthesis Example 3, 15 parts by weight of hexamethylene diisocyanate, 0.1 part by weight of dibutyltin laurylate, and 40 parts by weight of polymethylmethacrylate diol were added to the reaction system, and the temperature was raised to 90 ° C. The temperature was raised and allowed to react with stirring for about 5 hours.
합성예 8: 폴리에스테르 B-4의 제조Synthesis Example 8: Preparation of Polyester B-4
상기 합성예 4에서 얻어진 폴리에스테르 A-4 200중량부, 헥사메틸렌디 이소시아네이트 15중량부, 디부틸틴라우릴레이트 0.1중량부, 폴리부틸아크릴레이트 디올 40중량부를 반응계에 넣고 온도를 70℃까지 승온하여 약 5시간 정도 교반하며 반응시켰다.200 parts by weight of polyester A-4 obtained in Synthesis Example 4, 15 parts by weight of hexamethylene diisocyanate, 0.1 part by weight of dibutyltinlaurylate, and 40 parts by weight of polybutylacrylate diol were added to a reaction system, and the temperature was raised to 70 ° C. The reaction was stirred for about 5 hours.
비교합성예 1: 폴리에스테르 C-1의 제조Comparative Synthesis Example 1 Preparation of Polyester C-1
이소프탈산 373.5중량부, 아디프산 328.5중량부, 네오펜틸글리콜 374.4중량부, 1,6-헥산디올 92중량부, 1,4-사이클로헥산디메티롤 172중량부, 트리메티롤프로판 78중량부를 반응계에 넣고 210℃에서 반응시키면 부산물인 물이 생성되면서 올리고머가 생성된다. 이때 분자량을 2500 정도로 조정한다. 생성된 폴리에스테르를 셀로솔부 아세테이트에 고형분 70%가 되도록 녹였다.373.5 parts by weight of isophthalic acid, 328.5 parts by weight of adipic acid, 374.4 parts by weight of neopentyl glycol, 92 parts by weight of 1,6-hexanediol, 172 parts by weight of 1,4-cyclohexanedimethol, 78 parts by weight of trimetholpropane Into the reaction at 210 ℃ to produce the byproduct water oligomers. At this time, the molecular weight is adjusted to about 2500. The resulting polyester was dissolved in cellosol moiety to 70% solids.
비교합성예 2: 폴리에스테르 C-2의 제조Comparative Synthesis Example 2 Preparation of Polyester C-2
상기 비교합성예 1에서 앞에서 합성한 폴리에스테르 200중량부, 헥사메틸렌디 이소시아네이트 15중량부, 디부틸틴라우릴레이트 0.1중량부, 폴리카프로락톤 폴리올 50중량부를 반응계에 넣고 온도를 70℃까지 승온하여 약 5시간 정도 교반하며 반응시켰다.200 parts by weight of polyester, 15 parts by weight of hexamethylene diisocyanate, 0.1 parts by weight of dibutyl tin laurate, and 50 parts by weight of polycaprolactone polyol synthesized in Comparative Synthesis Example 1 were added to a reaction system, and the temperature was raised to 70 ° C. The reaction was stirred for about 5 hours.
실시예 1∼4 및 비교예 1∼2: 도료 제조Examples 1-4 and Comparative Examples 1-2: Paint Preparation
상기 합성예 1∼8 및 비교합성예 1∼2로부터 제조된 폴리에스테르로 하기 표1과 같은 배합으로 중도도료를 제조하여 도막 물성을 비교하였다. 그 결과는 하기 표 1과 같다.The intermediate coating materials were prepared by using the polyester prepared from Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 2 as shown in Table 1 below to compare coating properties. The results are shown in Table 1 below.
여기서, 내한치핑성은 -40℃에서 3시간 경과 후 4기압의 50g 암염으로 충격을 가한 후 도막의 손상정도를 파악한 것이며, 평활성은 도막의 평활성을 육안으로 확인한 것이며, 부착력은 도막에 칼로서 가로, 세로 11개의 금을 그은 후 점착테이프로 박리한 후 도막이 붙어있는 수를 측정하였고, 연필경도는 연필로서 경도시험한 것으로서 JIS-K 5401에 의거 측정하였다.Here, cold resistance chipping is to determine the degree of damage to the coating film after impacting with 50g rock salt of 4 atm after 3 hours at -40 ℃, smoothness is visually confirmed the smoothness of the coating film, adhesion strength is horizontal, After drawing 11 gold lengths, the adhesive tape was peeled off, and the number of coating films was attached thereto. The pencil hardness was measured according to JIS-K 5401 as a pencil hardness test.
상기 표 1의 결과로부터, 본 발명에 따른 수지를 포함하는 도막은 내한치핑성과 평활성 및 부착력 등이 매우 우수하며, 특히 내한치핑성이 월등히 향상되었음을 알 수 있고 광택성과 연필경도 등의 물성도 우수한 물성이 유지됨을 알 수 있다.From the results of Table 1, the coating film containing the resin according to the present invention is very excellent in cold resistance chipping, smoothness and adhesion, etc. In particular, it can be seen that the cold resistance chipping is significantly improved, and physical properties such as gloss and pencil hardness also excellent It can be seen that this is maintained.
이상에서 상세히 설명한 바와 같이, 본 발명에 따라 지방족 디이오시아네이트로 변성시킨 폴리에스테르 수지를 혼용하여 얻어진 폴리에스테르 수지는 통상의 자동차 도료용 폴리에스테르 수지에서 문제가 되는 내한치핑성의 문제를 해결하면서 외관, 부착력 등이 매우 우수하고 광택성과 연필경도 등은 동등 이상의 물성을유지하므로 자동차 중도 도료로서 유용하다.As described in detail above, the polyester resin obtained by mixing a polyester resin modified with an aliphatic diocyanate according to the present invention has an appearance while solving the problem of cold chipping, which is a problem in the polyester resin for automotive paints. It is very useful as a paint for automobiles because it has very good adhesion and adhesion, and its glossiness and pencil hardness maintains the same or more properties.
Claims (8)
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| KR1020010087867A KR20030057784A (en) | 2001-12-29 | 2001-12-29 | Polyester resin for automobile paints |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016104875A1 (en) * | 2014-12-24 | 2016-06-30 | 주식회사 케이씨씨 | Highly elastic polyester modified urethane resin, and clear coat composition containing same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016104875A1 (en) * | 2014-12-24 | 2016-06-30 | 주식회사 케이씨씨 | Highly elastic polyester modified urethane resin, and clear coat composition containing same |
| CN107108853A (en) * | 2014-12-24 | 2017-08-29 | 株式会社Kcc | The urethane resin of high resiliency polyester modification and the clear coating composition comprising it |
| EP3239204A4 (en) * | 2014-12-24 | 2017-12-06 | Kcc Corporation | Highly elastic polyester modified urethane resin, and clear coat composition containing same |
| US10239986B2 (en) | 2014-12-24 | 2019-03-26 | Kcc Corporation | Highly elastic polyester modified urethane resin and clear coat composition containing same |
| CN107108853B (en) * | 2014-12-24 | 2020-07-14 | 株式会社Kcc | High-elasticity polyester-modified urethane resin and clear coating composition comprising same |
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