KR20160080296A - One component low bake paint composition and acrylic polyol resin composition - Google Patents
One component low bake paint composition and acrylic polyol resin composition Download PDFInfo
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
- C08F8/16—Lactonisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- 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
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- 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
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- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/111—Polymer of unsaturated acid or ester
Abstract
Description
본 발명은 아크릴 폴리올 수지 조성물 및 이를 포함하는 저온소부가 가능한 도료 조성물에 관한 것으로서, 보다 상세하게는 수산기를 포함하는 아크릴 모노머에 락톤 변성을 통해 수지 골격 내에 -CH2- 반복구조를 형성시킨 올리고머를 적용한 아크릴 폴리올 수지 및 상기 아크릴 폴리올 수지를 포함함으로써, 반응성이 향상되어 저온소부로 경화시킨 경우에도 종래의 도료 조성물과 동등한 물성을 확보할 수 있는 도료 조성물에 관한 것이다.TECHNICAL FIELD The present invention relates to an acrylic polyol resin composition and a coating composition capable of forming a low temperature portion containing the acrylic polyol resin composition, and more particularly, to an acrylic polyol resin composition comprising an oligomer having a -CH 2 - repeating structure formed in a resin skeleton by lactone modification to an acrylic monomer containing a hydroxyl group The present invention relates to a coating composition which can ensure the same physical properties as those of a conventional coating composition even when the reactivity is improved and the composition is cured at a low temperature at a low temperature by including the acrylic polyol resin and the acrylic polyol resin.
자동차 생산공장에서 사용되는 대부분의 에너지는 도장 공장의 도장부스 및 오븐에서 소비된다. 저온 소부가 가능할 경우 도장 공장에서 소모되는 오븐 전력을 절감시킬 수 있기 때문에, 근래의 자동차 업계에서는 저온 경화가 가능한 도료의 개발을 요구해 오고 있다.Most of the energy used in automobile production plants is consumed in the paint booths and ovens of the painting factory. In recent years, the automotive industry has been demanding the development of paints that can be cured at low temperature, since the oven power consumed at the painting factory can be reduced if low-temperature baking is possible.
저온 소부가 가능한 아크릴 수지 혼합물이 개시된 바 있으나(예컨대, 일본 등록특허 제3929515호 및 제3249053호), 이는 이소시아네이트를 경화제로 사용하는 2액형 도료에 해당한다. 또한, 산/에폭시가 포함된 수지를 적용한 기술이 개시된 바 있으나(예컨대, 미국 등록특허 제5369178호), 1액형 도료로 사용하는 경우 도료의 유효기간이 제한적이라는 문제가 있다.An acrylic resin mixture capable of low temperature baking has been disclosed (for example, Japanese Patent No. 3929515 and Japanese Patent No. 3249053), which corresponds to a two-pack type paint using isocyanate as a curing agent. Further, although a technique using an acid / epoxy-containing resin has been disclosed (for example, US Patent No. 5369178), there is a problem that the effective period of the paint is limited when it is used as a one-pack type paint.
따라서, 저온 소부가 가능하며 1액형 도료로 사용할 수 있는 도료 조성물 및 이에 포함되는 주제 수지의 개발이 요구되고 있다.Therefore, it is required to develop a paint composition which can be used at low temperature and which can be used as a one-pack type paint, and a main resin included therein.
본 발명은 상기와 같은 종래기술의 문제점을 해결하고자 한 것으로, 수산기를 포함하는 아크릴 모노머에 락톤 변성을 통해 수지 골격 내에 -CH2- 반복구조를 형성시킨 올리고머를 적용한 아크릴 폴리올 수지 및 상기 아크릴 폴리올 수지를 포함함으로써, 반응성이 향상되어 저온소부로 경화시킨 경우에도 종래의 도료 조성물과 동등한 물성을 확보할 수 있는 도료 조성물을 제공하는 것을 기술적 과제로 한다.SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to provide an acrylic polyol resin in which an oligomer having a -CH 2 - repeating structure formed in a resin skeleton through lactone modification is applied to an acrylic monomer containing a hydroxyl group, It is an object of the present invention to provide a coating composition capable of securing the same physical properties as those of a conventional coating composition even when the curing is performed at a low temperature.
상기한 기술적 과제를 해결하고자 본 발명은, 수지 내 단량체 100 중량부를 기준으로 락톤 변성 아크릴레이트 올리고머 10 내지 80 중량부, 에틸렌성 불포화 모노머 10 내지 80 중량부, 개시제 0.1 내지 15 중량부를 중합하여 제조되고, 상기 락톤 변성 아크릴레이트 올리고머는, 수산기를 함유한 에틸렌성 불포화 모노머 1몰에 대하여 탄소수 4 내지 8의 링 탄소원자를 갖는 락톤 화합물 1 내지 5.5몰을 사용하여 고리열림 중합을 시켜 제조되고, 락톤-유래 알리파틱 선형 구조 및 다관능성의 하이드록실기를 갖는 것을 특징으로 하는, 아크릴 폴리올 수지를 제공한다.In order to solve the above-mentioned technical problem, the present invention provides a process for producing a polymer, which comprises polymerizing 10 to 80 parts by weight of a lactone-modified acrylate oligomer, 10 to 80 parts by weight of an ethylenically unsaturated monomer, and 0.1 to 15 parts by weight of an initiator based on 100 parts by weight of a monomer in a resin , The lactone modified acrylate oligomer is prepared by ring opening polymerization using 1 to 5.5 mol of a lactone compound having a ring carbon atom having 4 to 8 carbon atoms relative to 1 mol of an ethylenically unsaturated monomer containing a hydroxyl group, An acrylic polyol resin characterized by having an aliphatic linear structure and a polyfunctional hydroxyl group.
본 발명의 다른 측면에 따르면, 조성물 총 중량 100 중량부에 대해 아크릴 폴리올 수지 40 내지 90 중량부; 경화제 10 내지 50 중량부; 및 경화촉매 0.01 내지 10 중량부를 포함하고, 상기 아크릴 폴리올 수지의 고형분 함량이 40 내지 80 중량%이고, 상기 고형분의 중량을 기준으로 상기 아크릴 폴리올 수지의 수산기가는 80 내지 200 mgKOH인 도료 조성물이 제공된다.According to another aspect of the present invention, there is provided a composition comprising 40 to 90 parts by weight of an acrylic polyol resin per 100 parts by weight of the total composition; 10 to 50 parts by weight of a curing agent; And 0.01 to 10 parts by weight of a curing catalyst, wherein the acrylic polyol resin has a solid content of 40 to 80% by weight and a hydroxyl value of the acrylic polyol resin is 80 to 200 mgKOH based on the weight of the solid content, do.
본 발명에 따른 신규한 아크릴 폴리올 수지는 수산기를 포함하는 아크릴 모노머에 락톤 변성을 통해 상기 락톤-유래 알리파틱 선형구조를 부여하여 수지의 골격 내에 -CH2- 반복구조를 형성시킨 올리고머를 적용함으로써, 수지 골격에 유연성이 부여되고, 이를 포함하는 도료 조성물을 저온 소부 경화시킨 경우에 기존 소부 조건에서 경화시킨 종래 조성물과 동등한 물성을 확보할 수 있다.The novel acrylic polyol resin according to the present invention can be obtained by applying an oligomer having a lactone-derived aliphatic linear structure through lactone modification to an acrylic monomer containing a hydroxyl group to form a -CH 2 - repeating structure in the skeleton of the resin, Flexibility is imparted to the resin skeleton, and when the paint composition containing the resin composition is subjected to low temperature curing, it is possible to secure the same physical properties as the conventional composition cured under the existing baking conditions.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 아크릴 폴리올 수지는 수지 내 단량체 100 중량부를 기준으로 락톤 변성 아크릴레이트 올리고머 10 내지 80 중량부, 에틸렌성 불포화 모노머 10 내지 80 중량부, 개시제 0.1 내지 15 중량부를 중합하여 제조되고, 상기 락톤 변성 아크릴레이트 올리고머는, 수산기를 함유한 에틸렌성 불포화 모노머 1몰에 대하여 탄소수 4 내지 8의 링 탄소원자를 갖는 락톤 화합물 1 내지 5.5몰을 사용하여 고리열림 중합을 시켜 제조되고, 락톤-유래 알리파틱 선형 구조 및 다관능성의 하이드록실기를 갖는 것을 특징으로 한다.The acrylic polyol resin of the present invention is prepared by polymerizing 10 to 80 parts by weight of a lactone-modified acrylate oligomer, 10 to 80 parts by weight of an ethylenically unsaturated monomer and 0.1 to 15 parts by weight of an initiator based on 100 parts by weight of a monomer in the resin, The acrylate oligomer is prepared by ring opening polymerization using 1 to 5.5 mol of a lactone compound having a ring carbon atom of 4 to 8 carbon atoms relative to 1 mol of an ethylenically unsaturated monomer containing a hydroxyl group. The lactone-derived aliphatic linear structure And a polyfunctional hydroxyl group.
본 발명의 아크릴 폴리올 수지의 중합에 사용되는 락톤 변성 아크릴레이트 올리고머는 락톤 화합물을 사용하여 고리열림 중합을 시켜 락톤-유래 알리파틱 선형 구조 및 다관능성의 하이드록실기를 가질 수 있다.The lactone-modified acrylate oligomer used in the polymerization of the acrylic polyol resin of the present invention may have a lactone-derived aliphatic linear structure and a polyfunctional hydroxyl group by ring opening polymerization using a lactone compound.
여기서, 락톤 변성 아크릴레이트 올리고머란, 분자내 ―COO-를 함유하는 헤테로 고리화합물인 락톤화합물에 하이드록시기를 함유하는 아크릴레이트 모노머를 작용시켜 고리열림 중합을 함으로써 중합성 이중결합과 하이드록시기를 연결하는 직쇄상의 원소가 단일결합을 갖는 탄소구조가 반복되는 것을 특징으로 하는 것을 의미할 수 있다. Here, the lactone-modified acrylate oligomer refers to a lactone compound which is a heterocyclic compound containing -COO- in a molecule and is subjected to ring opening polymerization by reacting an acrylate monomer containing a hydroxy group to link a polymerizable double bond and a hydroxy group And the carbon structure in which the linear element has a single bond is repeated.
상기 락톤 화합물은, 본 발명의 락톤 변성 아크릴레이트 올리고머에 락톤-유래 알리파틱 선형구조 및 다관능성의 하이드록실기를 부여할 수 있다면 특별히 한정하지 않으나 ε-카프로 락톤, β-메틸-ζ-발레로 락톤, δ-카프로락톤, γ-카프로락톤 또는 γ-부티로락톤 및 이들의 조합으로부터 선택되는 것일 수 있다. The lactone compound is not particularly limited as long as it can impart a lactone-derived aliphatic linear structure and a polyfunctional hydroxyl group to the lactone-modified acrylate oligomer of the present invention, but is not limited to ε-caprolactone, β-methyl- Lactone,? -Caprolactone,? -Caprolactone or? -Butyrolactone, and combinations thereof.
전술한 바와 같이, 상기 락톤 화합물을 이용하여 고리열림 중합을 시킬 수 있는 바, 이때 고리 열림 중합을 위한 촉매를 더 포함시킬 수 있다. 상기 촉매는 락톤 변성 아크릴레이트 올리고머의 전체 중량에 대하여 1000 ppm 이하로 사용될 수 있다. 상기 촉매는 고리열림 중합시 촉매로 사용될 수 있는 것이라면 특별히 한정하지 않으나, 주석 화합물, 유기납 또는 망간 화합물류가 바람직하며, 구체적인 예에는 테트라 페닐 틴, 테트라 옥틸 틴, 디 페닐 틴 라우레이트, 디 메틸 틴 옥사드, 디 부틸틴 옥사이드, 리드 아세테이트 또는 마그네슘 아세테이트 등이 있다.As described above, the ring-opening polymerization can be carried out using the lactone compound. In this case, a catalyst for ring-opening polymerization can be further included. The catalyst may be used in an amount of up to 1000 ppm based on the total weight of the lactone-modified acrylate oligomer. The catalyst is not particularly limited as long as it can be used as a catalyst in the ring-opening polymerization, and tin compounds, organic lead or manganese compounds are preferable, and specific examples include tetraphenyl tin, tetraoctyl tin, diphenyl tin laurate, Tin oxides, dibutyl tin oxides, lead acetates or magnesium acetates.
본 발명의 락톤 변성 아크릴레이트를 중합하기 위해, 수산기를 함유한 에틸렌성 불포화 모노머 1몰에 대하여 탄소수 4 내지 8의 링 탄소원자를 갖는 락톤 화합물 1 내지 5.5몰을 사용할 수 있다.In order to polymerize the lactone-modified acrylate of the present invention, 1 to 5.5 mol of a lactone compound having a ring carbon atom of 4 to 8 carbon atoms can be used per 1 mol of the ethylenically unsaturated monomer containing a hydroxyl group.
구체적으로, 락톤 화합물 1몰 미만을 사용하는 경우 다량의 잔여 하이드록시기가 남아 경화반응에 참여하게 될 수 있고 5.5몰을 초과하는 경우 경화제와 경화반응을 할 수 있는 부위가 적어 경도를 저하시킬 수 있으며, 내습성, 내후성, 내화학성 등을 저하시킬 수 있으므로, 바람직하지 않다.Specifically, when less than 1 mole of the lactone compound is used, a large amount of residual hydroxy groups may remain to participate in the curing reaction. If it exceeds 5.5 moles, hardness may be lowered because there are few sites capable of curing reaction with the curing agent , Moisture resistance, weather resistance, chemical resistance, and the like.
본 발명의 아크릴 폴리올 수지를 중합하기 위해, 중합된 락톤 변성 아크릴 레이트 올리고머는 수지 내 단량체 100 중량부를 기준으로 10 내지 80 중량부를 사용할 수 있다. 10 중량부 미만인 경우 소망하는 효과를 기대하기 어렵고, 80 중량부를 초과하는 경우 경화제와 경화반응할 수 있는 부위가 적어 경도를 저하시키고, 이로인해 내습성, 내후성, 내화학성 등을 저하시킬 수 있으므로, 바람직하지 않다. In order to polymerize the acrylic polyol resin of the present invention, the polymerized lactone modified acrylate oligomer may be used in an amount of 10 to 80 parts by weight based on 100 parts by weight of the monomer in the resin. When the amount is less than 10 parts by weight, a desired effect can not be expected. When the amount is more than 80 parts by weight, hardness is lowered due to few sites capable of undergoing a curing reaction with the curing agent, which can lower the moisture resistance, weather resistance, It is not preferable.
본 발명의 아크릴 폴리올 수지의 중합에 사용되는 아크릴 폴리올 수지는, 특별히 한정하지 않으나 중량 평균 분자량은 5,000 내지 30,000이고, 수지 고형분 함량은 40 내지 90 중량% 이며, 수산기가는 고형분 중량 기준으로 80 내지 200mgKOH이다.The acrylic polyol resin used in the polymerization of the acrylic polyol resin of the present invention is not particularly limited, but has a weight average molecular weight of 5,000 to 30,000, a resin solid content of 40 to 90% by weight, a hydroxyl value of 80 to 200 mgKOH to be.
본 발명의 아크릴 폴리올 수지를 중합하기 위해 수지 내 단량체 100 중량부를 기준으로 에틸렌성 불포화 모노머 10 내지 80 중량부를 사용할 수 있다. 에틸렌성 불포화 모노머가 10 중량부 미만인 경우 락톤 변성 아크릴레이트 올리고머의 함량이 초과되어 과량의 경화제 및 경화촉매의 사용이 불가피하므로 기계적 물성 등을 확보하기 어려울 수 있다. 반면에, 에틸렌성 불포화 모노머가 80 중량부를 초과하는 경우 수지의 반응성이 향상되는 효과를 발휘하기 어려워 바람직하지 않다. In order to polymerize the acrylic polyol resin of the present invention, 10 to 80 parts by weight of the ethylenically unsaturated monomer may be used based on 100 parts by weight of the monomer in the resin. When the amount of the ethylenically unsaturated monomer is less than 10 parts by weight, the content of the lactone-modified acrylate oligomer is excessively large, and excessive use of the curing agent and the curing catalyst is inevitable, so that it may be difficult to secure mechanical properties. On the other hand, if the amount of the ethylenically unsaturated monomer exceeds 80 parts by weight, it is difficult to exert the effect of improving the reactivity of the resin, which is not preferable.
특별히 한정하지 않으나, 상기 에틸렌성 불포화 모노머는 스티렌, 메틸(메트) 아크릴레이트, 프로필(메트) 아크릴레이트, 노말부틸(메트) 아크릴레이트, 이소부틸(메트) 아크릴레이트, 터셔리부틸(메트) 아크릴레이트, 2-에틸헥실(메트) 아크릴레이트, 벤질(메트) 아크릴레이트, 이소보닐(메트) 아크릴레이트, 라우릴(메트) 아크릴레이트 및 이들의 조합로부터 선택되는 것일 수 있다.The ethylenically unsaturated monomer may be selected from the group consisting of styrene, methyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (Meth) acrylate, benzyl (meth) acrylate, isobonyl (meth) acrylate, lauryl (meth) acrylate, and combinations thereof.
본 발명의 아크릴 폴리올 수지를 중합하기 위해 개시제가 사용될 수 있으며, 상기 개시제는 수지 내 단량체 100 중량부를 기준으로 개시제 0.1 내지 15 중량부를 사용할 수 있다. An initiator may be used to polymerize the acrylic polyol resin of the present invention, and the initiator may be used in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the monomer in the resin.
상기 개시제로는 연쇄반응을 개시시킬 수 있다면 특별히 한정하지 않으나, 2,2’-아조비스(2-메틸부틸로니트릴), 2,2’-아조비스이소부틸로니트릴, 디벤조일 퍼옥사이드, 터셔리부틸퍼옥시 벤조에이트, 디터셔리부틸퍼옥사이드, 터셔리부틸퍼옥시-2-에틸헥사노에이트, 터셔리부틸퍼옥시 아세테이트, 터셔리아밀퍼옥시-2-에틸헥사노에이트, 디터셔리아밀퍼옥사이드, 큐밀하이드로퍼옥사이드, 디큐밀퍼옥사이드 및 이들의 조합을 사용할 수 있다.The initiator is not particularly limited, as long as it can initiate a chain reaction, and examples thereof include 2,2'-azobis (2-methylbutylonitrile), 2,2'-azobisisobutylonitrile, dibenzoyl peroxide Ethylhexanoate, tertiary butyl peroxybenzoate, ditertiary butyl peroxide, tertiary butyl peroxy-2-ethyl hexanoate, tertiary butyl peroxyacetate, tertiary amyl peroxy-2-ethyl hexanoate, Oxide, cumyl hydroperoxide, dicumyl peroxide, and combinations thereof.
또한, 분자량 조절을 위해 연쇄 이동제가 더 포함될 수 있는 바, 연쇄 이동제는 전체 중량에 대하여 10 중량부 이내로 포함될 수 있다. 연쇄 이동제로는 예를 들어 라우릴 메르캅탄, 글리시딜 메르캅탄, 메르캅토 초산, 2－메르캅토 에탄올, 티오 글리콜산, 티오글리콜산 2－에틸 헥실, 2, 3－디메르캅토 1－프로파놀 등의 조합일 수 있다.In addition, a chain transfer agent may be further included for controlling the molecular weight, and the chain transfer agent may be contained in an amount of 10 parts by weight or less based on the total weight. Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto- Phenol, and the like.
본 발명의 아크릴 폴리올 수지를 중합하는데 사용될 수 있는 용제는 반응에 악영향을 미치지 않는 한 특별히 제한되지 않으며, 예를 들어, 톨루엔, 크실렌과 같은 방향족 탄화수소계 용제; 메틸에틸케톤, 메틸프로필케톤, 메틸부틸케톤, 에틸프로필케톤과 같은 케톤계 용제; 메틸 아세테이트, 에틸 아세테이트, n-프로필 아세테이트, 이소프로필 아세테이트, 이소프로필, 부틸 아세테이트, 부틸셀로솔브 아세테이트와 같은 에스테르계 용제; 및 이들의 조합을 사용할 수 있다. 바람직하게는, 상기 용제는 에틸렌성 불포화 모노머 100 중량부를 기준으로 10 내지 60 중량부가 사용될 수 있다.The solvent which can be used for polymerizing the acrylic polyol resin of the present invention is not particularly limited so long as it does not adversely affect the reaction, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone and ethyl propyl ketone; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isopropyl, butyl acetate and butyl cellosolve acetate; And combinations thereof. Preferably, the solvent may be used in an amount of 10 to 60 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer.
본 발명의 다른 측면에 따르면, 조성물 총 중량 100 중량부에 대해 상기 아크릴 폴리올 수지 40 내지 90 중량부; 경화제 10 내지 50 중량부; 및 경화촉매 0.01 내지 10 중량부를 포함하고, 고형분 함량이 40 내지 80 중량%이고, 고형분의 중량을 기준으로 상기 아크릴 폴리올 수지의 수산기가는 80 내지 200 mgKOH인, 도료 조성물이 제공된다.According to another aspect of the present invention, there is provided a composition comprising: 40 to 90 parts by weight of the acrylic polyol resin relative to 100 parts by weight of the total composition; 10 to 50 parts by weight of a curing agent; And 0.01 to 10 parts by weight of a curing catalyst, wherein the solid content is 40 to 80% by weight and the hydroxyl value of the acrylic polyol resin is 80 to 200 mgKOH based on the weight of the solid content.
상기 아크릴 폴리올 수지는 락톤-유래 알리파틱 선형구조 및 다관능성의 하이드록실기를 갖는 락톤 변성 아크릴레이트 올리고머를 포함하는 것을 특징으로 하며, 이에 대한 상세한 설명은 전술하였으므로 생략한다.The acrylic polyol resin is characterized in that it contains a lactone-derived aliphatic linear structure and a lactone-modified acrylate oligomer having a polyfunctional hydroxyl group, and a detailed description thereof has been described above, so that the description is omitted.
상기 아크릴 폴리올 수지는 조성물 총 중량 100 중량부를 기준으로 40 내지 90 중량부가 사용될 수 있다. 40 중량부 미만이거나, 90 중량부를 초과하는 경우 기계적 물성, 내습성, 내후성, 내화학성, 제조 및 도장 작업성이 저하될 수 있다.The acrylic polyol resin may be used in an amount of 40 to 90 parts by weight based on 100 parts by weight of the total composition. If the amount is less than 40 parts by weight or exceeds 90 parts by weight, the mechanical properties, moisture resistance, weather resistance, chemical resistance, manufacturing and coating workability may be deteriorated.
특별히 한정하지 않으나, 상기 경화제는 헥사메틸올멜라민, 헥사메톡시메틸멜라민, 헥사부톡시메틸멜라민 및 이들의 조합으로부터 선택되는 것일 수 있다. 상기 경화제는 조성물 총 중량 100 중량부를 기준으로 10 내지 50 중량부가 사용될 수 있는데, 상기 범위를 벗어나는 경우 기계적 물성이 떨어질 수 있다.Although not particularly limited, the curing agent may be selected from hexamethylol melamine, hexamethoxymethyl melamine, hexabutoxymethyl melamine, and combinations thereof. The curing agent may be used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the total composition. If the curing agent is out of the range, mechanical properties may be deteriorated.
특별히 한정하지 않으나, 상기 경화촉매는 도데실벤젠술폰산, 술폰산, 디노닐나프탈렌디술폰산, 디노닐나프탈렌술폰산 및 이들의 조합으로부터 선택되는 것일 수 있다. 상기 경화촉매는 조성물 총 중량 100 중량부를 기준으로 0.01 내지 10 중량부가 사용될 수 있는데, 상기 범위를 벗어나는 경우 기계적 물성이 떨어질 수 있다.Although not particularly limited, the curing catalyst may be selected from dodecylbenzenesulfonic acid, sulfonic acid, dinonylnaphthalene disulfonic acid, dinonylnaphthalenesulfonic acid, and combinations thereof. The curing catalyst may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total composition. If the curing catalyst is out of the range, mechanical properties may be deteriorated.
본 발명의 도료 조성물은 레벨링제, 광안정제, 흐름성 조절제, 소포제, 흡습제 및 이들의 조합으로 이루어진 군으로부터 선택되는 것을 추가로 포함할 수 있다.
The coating composition of the present invention may further comprise one selected from the group consisting of a leveling agent, a light stabilizer, a flow control agent, a defoaming agent, a hygroscopic agent, and a combination thereof.
이하, 실시예 및 비교예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 본 발명의 범위가 이들로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.
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실시예Example
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합성예Synthetic example 1-1 : 락톤 변성 1-1: Lactone modification 아크릴레이트Acrylate 올리고머의Oligomeric 제조 Produce
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g과 하이드록시 에틸 아크릴레이트 206g을 사입한 후 80도까지 승온시켰다. 온도가 안정된 후, 입실론 카프로락톤 203g을 사입하고 130도까지 승온시켰다. 3시간 반응을 유지한 후, 60℃로 냉각하여 고형분 80%의 락톤 변성 아크릴레이트 올리고머를 얻었다.
103 g of coco sol # 100 and 206 g of hydroxyethyl acrylate were charged into a four-necked flask for synthesis having a thermometer and a stirrer, and the temperature was raised to 80 ° C. After the temperature was stabilized, 203 g of epsilon caprolactone was introduced and the temperature was raised to 130 ° C. After the reaction was maintained for 3 hours, the reaction solution was cooled to 60 DEG C to obtain a lactone-modified acrylate oligomer having a solid content of 80%.
합성예Synthetic example 1-2: 락톤 변성 1-2: lactone modification 아크릴레이트Acrylate 올리고머를Oligomer 적용한 아크릴 Acrylic applied 폴리올Polyol 수지(A)의 제조 Preparation of Resin (A)
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g을 사입한 후 환류온도까지 승온시켰다. 환류가 안정된 후, 합성예 1-1에서 제조한 락톤 변성 아크릴레이트 올리고머 512g, 스티렌모노머 309g, 부틸아크릴레이트 313g과 터셔리부틸페록시벤조에이트 62g, 코코졸#100 63g을 180분, 195분간 균일하게 분리 적가한 후, 60분간 환류 유지시켰다. 그 후, 반응물을 코코졸#100으로 희석한 후, 60℃로 냉각하여 고형분 70%의 아크릴폴리올 수지(A)를 얻었다.
103 g of Cocosol # 100 was introduced into a four-necked flask for synthesis, equipped with a thermometer and a stirrer, and then heated to the reflux temperature. After stabilizing the reflux, 512 g of the lactone-modified acrylate oligomer prepared in Synthesis Example 1-1, 309 g of styrene monomer, 313 g of butyl acrylate, 62 g of tertiary butyl peroxybenzoate and 63 g of cocosol # 100 were uniformly reacted for 180 minutes and 195 minutes The mixture was kept at reflux for 60 minutes. Thereafter, the reaction product was diluted with coco sol # 100 and then cooled to 60 캜 to obtain an acrylic polyol resin (A) having a solid content of 70%.
합성예Synthetic example 2-1 : 락톤 변성 2-1: lactone degeneration 아크릴레이트Acrylate 올리고머의Oligomeric 제조 Produce
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g과 하이드록시 에틸 아크릴레이트 175g을 사입한 후 80도까지 승온시켰다. 온도가 안정된 후, 입실론 카프로락톤 518g을 사입하고 130도까지 승온시켰다. 3시간 반응을 유지한 후, 60℃로 냉각하여 고형분 87%의 락톤 변성 아크릴레이트 올리고머를 얻었다.
A synthetic four-necked flask equipped with a thermometer and a stirrer was charged with 103 g of cocosol # 100 and 175 g of hydroxyethyl acrylate, and the mixture was heated to 80 ° C. After the temperature was stabilized, 518 g of epsilon caprolactone was charged and the temperature was raised to 130 ° C. After the reaction was maintained for 3 hours, the reaction solution was cooled to 60 DEG C to obtain a lactone-modified acrylate oligomer having a solid content of 87%.
합성예Synthetic example 2-2: 락톤 변성 2-2: Lactone degeneration 아크릴레이트Acrylate 올리고머를Oligomer 적용한 아크릴 Acrylic applied 폴리올Polyol 수지(B)의 제조 Preparation of Resin (B)
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g을 사입한 후 환류온도까지 승온시켰다. 환류가 안정된 후, 합성예 2-1에서 제조한 락톤 변성 아크릴레이트 올리고머 796g, 스티렌모노머 309g, 부틸아크릴레이트 30g과 터셔리부틸페록시벤조에이트 62g, 코코졸#100 63g을 180분, 195분간 균일하게 분리 적가한 후, 60분간 환류 유지시켰다. 그 후, 반응물을 코코졸#100으로 희석한 후, 60℃로 냉각하여 고형분 70%의 아크릴폴리올 수지(B)를 얻었다.
103 g of Cocosol # 100 was introduced into a four-necked flask for synthesis, equipped with a thermometer and a stirrer, and then heated to the reflux temperature. After stabilizing the reflux, 796 g of the lactone-modified acrylate oligomer prepared in Synthesis Example 2-1, 309 g of styrene monomer, 30 g of butyl acrylate, 62 g of tertiary butyl peroxybenzoate and 63 g of cocosol # 100 were uniformly reacted for 180 minutes and 195 minutes The mixture was kept at reflux for 60 minutes. Thereafter, the reaction product was diluted with coco sol # 100 and then cooled to 60 캜 to obtain an acrylic polyol resin (B) having a solid content of 70%.
합성예Synthetic example 3-1 : 락톤 변성 3-1: Lactone degeneration 아크릴레이트Acrylate 올리고머의Oligomeric 제조 Produce
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g과 하이드록시 에틸 아크릴레이트 118g을 사입한 후 80도까지 승온시켰다. 온도가 안정된 후, 입실론 카프로락톤 584g을 사입하고 130도까지 승온시켰다. 3시간 반응을 유지한 후, 60℃로 냉각하여 고형분 87%의 락톤 변성 아크릴레이트 올리고머를 얻었다.
A synthetic four-necked flask equipped with a thermometer and a stirrer was charged with 103 g of Cocosol # 100 and 118 g of hydroxyethyl acrylate, and the mixture was heated to 80 ° C. After the temperature was stabilized, 584 g of epsilon caprolactone was introduced and the temperature was raised to 130 degrees. After the reaction was maintained for 3 hours, the reaction solution was cooled to 60 DEG C to obtain a lactone-modified acrylate oligomer having a solid content of 87%.
합성예Synthetic example 3-2: 락톤 변성 3-2: Lactone degeneration 아크릴레이트Acrylate 올리고머를Oligomer 적용한 아크릴 Acrylic applied 폴리올Polyol 수지(C)의 제조 Preparation of Resin (C)
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g을 사입한 후 환류온도까지 승온시켰다. 환류가 안정된 후, 합성예 3-1에서 제조한 락톤 변성 아크릴레이트 올리고머 805g, 스티렌모노머 309g, 부틸아크릴레이트 20g과 터셔리부틸페록시벤조에이트 62g, 코코졸#100 63g을 180분, 195분간 균일하게 분리 적가한 후, 60분간 환류 유지시켰다. 그 후, 반응물을 코코졸#100으로 희석한 후, 60℃로 냉각하여 고형분 70%의 아크릴폴리올 수지(C)를 얻었다.
103 g of Cocosol # 100 was introduced into a four-necked flask for synthesis, equipped with a thermometer and a stirrer, and then heated to the reflux temperature. After stabilizing the reflux, 805 g of the lactone-modified acrylate oligomer prepared in Synthesis Example 3-1, 309 g of styrene monomer, 20 g of butyl acrylate, 62 g of tertiary butyl peroxybenzoate and 63 g of cocosol # 100 were uniformly stirred for 180 minutes and 195 minutes The mixture was kept at reflux for 60 minutes. Thereafter, the reaction product was diluted with coco sol # 100 and then cooled to 60 캜 to obtain an acrylic polyol resin (C) having a solid content of 70%.
합성예Synthetic example 4-1: 아크릴 4-1: Acrylic 폴리올Polyol 수지 (D)의 제조 Preparation of Resin (D)
하이드록시에틸아크릴레이트 206g, 스티렌모노머 309g, 부틸아크릴레이트 516g을 사용한 것을 제외하고, 합성예 1-2와 동일한 방법을 수행하여 고형분 70%의 아크릴 폴리올 수지(D)를 얻었다.
An acrylic polyol resin (D) having a solid content of 70% was obtained in the same manner as in Synthesis Example 1-2, except that 206 g of hydroxyethyl acrylate, 309 g of styrene monomer, and 516 g of butyl acrylate were used.
합성예Synthetic example 5-1 : 락톤 변성 5-1: Lactone degeneration 아크릴레이트Acrylate 올리고머의Oligomeric 제조 Produce
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g과 하이드록시 에틸 아크릴레이트 206g을 사입한 후 80도까지 승온시켰다. 온도가 안정된 후, 입실론 카프로락톤 101g을 사입하고 130도까지 승온시켰다. 3시간 반응을 유지한 후, 60℃로 냉각하여 고형분 75%의 락톤 변성 아크릴레이트 올리고머를 얻었다.
103 g of coco sol # 100 and 206 g of hydroxyethyl acrylate were charged into a four-necked flask for synthesis having a thermometer and a stirrer, and the temperature was raised to 80 ° C. After the temperature was stabilized, 101 g of epsilon caprolactone was charged and the temperature was raised to 130 ° C. The reaction was maintained for 3 hours and then cooled to 60 DEG C to obtain a lactone-modified acrylate oligomer having a solid content of 75%.
합성예Synthetic example 5-2: 락톤 변성 5-2: Lactone degeneration 아크릴레이트Acrylate 올리고머를Oligomer 적용한 아크릴 Acrylic applied 폴리올Polyol 수지(E)의 제조 Preparation of resin (E)
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g을 사입한 후 환류온도까지 승온시켰다. 환류가 안정된 후, 합성예 5-1에서 제조한 락톤 변성 아크릴레이트 올리고머 410g, 스티렌모노머 309g, 부틸아크릴레이트 414g과 터셔리부틸페록시벤조에이트 62g, 코코졸#100 63g을 180분, 195분간 균일하게 분리 적가한 후, 60분간 환류 유지시켰다. 그 후, 반응물을 코코졸#100으로 희석한 후, 60℃로 냉각하여 고형분 70%의 아크릴폴리올 수지(E)를 얻었다.
103 g of Cocosol # 100 was introduced into a four-necked flask for synthesis, equipped with a thermometer and a stirrer, and then heated to the reflux temperature. After stabilizing the reflux, 410 g of the lactone-modified acrylate oligomer prepared in Synthesis Example 5-1, 309 g of styrene monomer, 414 g of butyl acrylate, 62 g of tertiary butyl peroxybenzoate and 63 g of cocosol # 100 were uniformly stirred for 180 minutes and 195 minutes The mixture was kept at reflux for 60 minutes. Thereafter, the reaction product was diluted with coco sol # 100, and then cooled to 60 캜 to obtain an acrylic polyol resin (E) having a solid content of 70%.
합성예Synthetic example 6-1 : 락톤 변성 6-1: Lactone degeneration 아크릴레이트Acrylate 올리고머의Oligomeric 제조 Produce
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g과 하이드록시 에틸 아크릴레이트 103g을 사입한 후 80도까지 승온시켰다. 온도가 안정된 후, 입실론 카프로락톤 609g을 사입하고 130도까지 승온시켰다. 3시간 반응을 유지한 후, 60℃로 냉각하여 고형분 87%의 락톤 변성 아크릴레이트 올리고머를 얻었다.
103 g of cocosol # 100 and 103 g of hydroxyethyl acrylate were charged into a four-necked flask for synthesis having a thermometer and a stirrer, and the temperature was raised to 80 ° C. After the temperature was stabilized, 609 g of epsilon caprolactone was charged and the temperature was raised to 130 degrees. After the reaction was maintained for 3 hours, the reaction solution was cooled to 60 DEG C to obtain a lactone-modified acrylate oligomer having a solid content of 87%.
합성예Synthetic example 6-2: 락톤 변성 6-2: Lactone degeneration 아크릴레이트Acrylate 올리고머를Oligomer 적용한 아크릴 Acrylic applied 폴리올Polyol 수지(F)의 제조 Preparation of resin (F)
온도계, 교반장치를 구비한 합성용 4구 플라스크에 코코졸#100 103g을 사입한 후 환류온도까지 승온시켰다. 환류가 안정된 후, 합성예 6-1에서 제조한 락톤 변성 아크릴레이트 올리고머 815g, 스티렌모노머 309g, 부틸아크릴레이트 10g과 터셔리부틸페록시벤조에이트 62g, 코코졸#100 63g을 180분, 195분간 균일하게 분리 적가한 후, 60분간 환류 유지시켰다. 그 후, 반응물을 코코졸#100으로 희석한 후, 60℃로 냉각하여 고형분 70%의 아크릴폴리올 수지(F)를 얻었다.
103 g of Cocosol # 100 was introduced into a four-necked flask for synthesis, equipped with a thermometer and a stirrer, and then heated to the reflux temperature. After stabilizing the reflux, 815 g of the lactone-modified acrylate oligomer prepared in Synthesis Example 6-1, 309 g of styrene monomer, 10 g of butyl acrylate, 62 g of tertiary butyl peroxybenzoate and 63 g of cocosol # 100 were uniformly stirred for 180 minutes and 195 minutes The mixture was kept at reflux for 60 minutes. Thereafter, the reaction product was diluted with coco sol # 100 and then cooled to 60 캜 to obtain an acrylic polyol resin (F) having a solid content of 70%.
도료조성물 제조Preparation of coating composition
표 1에 나타낸 바와 같은 조성으로 1500rpm으로 20분 이상 교반 혼합하여 실시예 1 내지 3과 비교예 1 내지 3의 도료 조성물을 각각 제조하였다.The coating compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were each prepared by mixing at a speed of 1500 rpm for 20 minutes or more with the composition shown in Table 1.
노즐 구경이 1.5mm인 핸드건 스프레이(Handgun spray)로 공기압을 4.5kgf/cm2 내외로 일정하게 유지하고, 노즐입구와 시편의 거리를 2~30cm 범위에서 일정하게 유지하여 수평으로 40~50cm/sec 속도로 등속으로 움직이며 도장하였다. 도장 후, 130℃에서 20분간 소부 경화 후, 도막 물성 (경도, 부착성,내수성,내산성, 내알카리성, 내용제성)을 다음과 같이 측정하여 표 2에 나타내었다.
The air pressure was kept constant at about 4.5 kgf / cm 2 with a handgun spray having a nozzle diameter of 1.5 mm, and the distance between the nozzle inlet and the specimen was kept constant in the range of 2 to 30 cm, sec. < / RTI > The properties of the coating films (hardness, adhesion, water resistance, acid resistance, alkali resistance and solvent resistance) were measured as follows after coating and curing at 130 캜 for 20 minutes.
(1) 경도: 연필 경도법으로 측정 (3B, 2B, B, HB, F, H, 2H, 3H 각각의 연필로 도막에 손상을 주지 않는 경도 측정)(1) Hardness: Measured by pencil hardness method (hardness measurement not to damage the coating film with each pencil of 3B, 2B, B, HB, F, H,
(2) 부착성: 상도 도장까지 완성된 도장시편을 열처리 CYCLE로 처리한 뒤 상온 24시간 방치 후 바둑목법으로 부착력 측정한다. 열처리 CYCLE은 150℃x20분, 20분 상온방치의 과정을 3번 반복하였다. (2) Adhesion: Completely coated paint is treated with heat-treated CYCLE for 24 hours at room temperature. Heat treatment CYCLE was repeated three times at 150 ℃ for 20 minutes and 20 minutes at room temperature.
(3) 내수성: 시편을 40℃ 항온수조에 240시간 동안 침적시킨 후, 1시간 동안 상온에서 방치한 뒤, 바둑목 부착성 평가로 박리시험을 행하여 외관의 이상 유무를 육안 관찰하였다. 시험 후의 외관은 연화, 백화, 광택불량, 벗겨짐, 부풀음, 변색 등이 없어야하며, 침적부와 미침적부의 외관 차이가 없어야 하고 부착성 평가를 실시하여 총 박리면적이 5% 미만이어야 한다. (3) Water resistance: The specimens were immersed in a constant temperature water bath at 40 DEG C for 240 hours, left standing at room temperature for 1 hour, and subjected to peeling test for evaluation of sticky wood adhesion to observe visually abnormalities. The appearance after the test shall be free of softening, whitening, gloss defects, peeling, swelling, discoloration, etc., and there shall be no difference in appearance between the immersed portion and the untreated portion and the total peeled area should be less than 5% by performing the adhesion evaluation.
(4) 내산성: 시편에 0.1N 황산 0.2mL씩 적하한 후. Gradient Oven의 온도를 35~40℃로 설정하여 150분간 가열하였다. 황산용액을 떨어뜨린 시편의 부위에 육안으로 에칭(etching), 얼룩, 부풀음의 발생 여부를 확인하여 손상이 생기지 않은 최고 온도를 내산성 온도로 판정하였다.(4) Acid resistance: 0.2 mL of 0.1 N sulfuric acid was added dropwise to the specimen. The temperature of the gradient oven was set to 35 to 40 DEG C and the mixture was heated for 150 minutes. The area of the specimen from which the sulfuric acid solution was dropped was visually inspected for the occurrence of etching, staining and blistering, and the highest temperature at which no damage occurred was determined as the acid resistance temperature.
(5) 내알카리성: 시편에 0.1N 수산화나트륨 용액을 2mL 적하한 후, 55℃ Oven에 4시간 가열하였다. 수산화나트륨 용액을 떨어뜨린 시편의 부위에 육안으로 에칭(etching), 얼룩, 부풀음의 발생 여부를 확인하였다. (5) Alkali resistance: 2 mL of 0.1 N sodium hydroxide solution was added dropwise to the specimen, and then heated in an oven at 55 ° C for 4 hours. The presence or absence of etching, staining, and blistering was visually observed at the site of the specimen where the sodium hydroxide solution was dropped.
(6) 내용제성: 시편에 시험용 용제(XYLENE)를 묻힌 면포를 올려둔 뒤, 매 1분마다 손톱으로 2Kg의 힘으로 4회 긁어 하층 도막면이 나타난 시간을 기록하였다.(6) Solvent resistance: After putting the test cloth with the test solvent (XYLENE) on it, it was scratched 4 times with a force of 2Kg every ninety minutes to record the time when the lower layer coat appeared.
상기 표 2에 나타난 바와 같이, 본 발명의 아크릴 폴리올 수지를 사용한 실시예의 도료 조성물의 내산성, 내알카리성, 내용제성 등의 물성은, 비교예 1 내지 3에 비해 우수함을 확인할 수 있었다. As shown in Table 2, it was confirmed that the coating compositions of the examples using the acrylic polyol resin of the present invention had better physical properties such as acid resistance, alkali resistance and solvent resistance than Comparative Examples 1 to 3.
더욱이, 본 발명의 실시예에 따른 아크릴 폴리올 수지를 사용한 경우 130℃에서 경화시킨 경우에도, 기존 소부온도(150℃)로 경화시킨 경우와 동등한 수준의 물성을 가지므로, 경화에 소모되는 에너지를 절감하는데 유용하게 사용될 수 있음을 알 수 있었다.Further, even when the acrylic polyol resin according to the embodiment of the present invention is cured at 130 ° C, it has the same level of physical properties as the case of curing at the existing baking temperature (150 ° C), thereby reducing the energy consumed in curing The results of this study are summarized as follows.
Claims (5)
상기 락톤 변성 아크릴레이트 올리고머는, 수산기를 함유한 에틸렌성 불포화 모노머 1몰에 대하여 탄소수 4 내지 8의 링 탄소원자를 갖는 락톤 화합물 1 내지 5.5몰을 사용하여 고리열림 중합을 시켜 제조되고, 락톤-유래 알리파틱 선형 구조 및 다관능성의 하이드록실기를 갖는 것을 특징으로 하는, 아크릴 폴리올 수지.10 to 80 parts by weight of a lactone-modified acrylate oligomer, 10 to 80 parts by weight of an ethylenically unsaturated monomer, and 0.1 to 15 parts by weight of an initiator, based on 100 parts by weight of the monomer in the resin,
The lactone-modified acrylate oligomer is prepared by ring-opening polymerization using 1 to 5.5 mol of a lactone compound having a ring carbon atom of 4 to 8 carbon atoms relative to 1 mol of an ethylenically unsaturated monomer containing a hydroxyl group, An acrylic polyol resin having a pastic linear structure and a polyfunctional hydroxyl group.
상기 아크릴 폴리올 수지의 고형분 함량이 40 내지 80 중량%이고, 상기 고형분의 중량을 기준으로 상기 아크릴 폴리올 수지의 수산기가는 80 내지 200 mgKOH인 1액형 도료 조성물.40 to 90 parts by weight of the acrylic polyol resin of any one of claims 1 to 4 relative to 100 parts by weight of the total weight of the composition; 10 to 50 parts by weight of a curing agent; And 0.01 to 10 parts by weight of a curing catalyst,
Wherein the acrylic polyol resin has a solid content of 40 to 80% by weight and the hydroxyl value of the acrylic polyol resin is 80 to 200 mgKOH based on the weight of the solid content.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5369178A (en) * | 1991-07-05 | 1994-11-29 | Mitsui Toatsu Chemicals, Inc. | Resin composition for thermosetting coating |
| KR20010057896A (en) * | 1999-12-23 | 2001-07-05 | 이계안 | Fuel cell stack for fuel cell car |
| JP3249053B2 (en) * | 1996-09-30 | 2002-01-21 | トヨタ自動車株式会社 | One-component low-temperature curing clear coating |
| JP3929515B2 (en) * | 1994-07-28 | 2007-06-13 | ビー・エイ・エス・エフ、コーポレーション | Coating composition comprising a high Tg acrylic polymer for low temperature cure and good corrosion resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5369178A (en) * | 1991-07-05 | 1994-11-29 | Mitsui Toatsu Chemicals, Inc. | Resin composition for thermosetting coating |
| JP3929515B2 (en) * | 1994-07-28 | 2007-06-13 | ビー・エイ・エス・エフ、コーポレーション | Coating composition comprising a high Tg acrylic polymer for low temperature cure and good corrosion resistance |
| JP3249053B2 (en) * | 1996-09-30 | 2002-01-21 | トヨタ自動車株式会社 | One-component low-temperature curing clear coating |
| KR20010057896A (en) * | 1999-12-23 | 2001-07-05 | 이계안 | Fuel cell stack for fuel cell car |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018056637A1 (en) * | 2016-09-23 | 2018-03-29 | 주식회사 케이씨씨 | Aqueous paint composition |
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