KR100427706B1 - Method for producing acrylic resin for use in top coating for cars having excellent pigment dispersibility, clearness, heat resistance, chemical resistance and weather resistance, acrylic resin obtained therefrom and top coating for cars based on the same resin - Google Patents

Method for producing acrylic resin for use in top coating for cars having excellent pigment dispersibility, clearness, heat resistance, chemical resistance and weather resistance, acrylic resin obtained therefrom and top coating for cars based on the same resin Download PDF

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KR100427706B1
KR100427706B1 KR1019950068608A KR19950068608A KR100427706B1 KR 100427706 B1 KR100427706 B1 KR 100427706B1 KR 1019950068608 A KR1019950068608 A KR 1019950068608A KR 19950068608 A KR19950068608 A KR 19950068608A KR 100427706 B1 KR100427706 B1 KR 100427706B1
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monomer
acrylic resin
acid
group
resin
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KR970042624A (en
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전태성
윤홍선
김종문
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고려화학 주식회사
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/04Polymerisation in solution
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers 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 an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/08Styrene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers 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 an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/12Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/20Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/34Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10Homopolymers or copolymers of methacrylic acid esters

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
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Abstract

PURPOSE: Provided is a method for producing an acrylic resin for use in top coating for cars having balanced structural and formal changeability, molecular weight and crosslinking rate of the resin and showing excellent pigment dispersibility, clearness, chemical resistance, heat resistance and weather resistance. CONSTITUTION: The method comprises carrying out solution polymerization of: (a) a compound represented by the following formula 1; (b) a compound represented by the formula of R-C=CH2 (wherein R is an aromatic vinyl compound); and (c) a monomer mixture including at least one long-chain hydroxy-containing monomer selected from a functional monomer obtained by epoxy ring-opening of glycidyl ester with an active hydrogen compound and a monomer obtained by epoxy ring-opening of glycidyl ester with a mercaptan acid or polyester monomer, a hydroxy monomer, and a monomer having an acid or amino group, in the weight ratio of (a):(b):(c) of 50-85:5-20:10-30. In formula 1, R1 is H or CH3, and R2 is a C1-C14 alkyl.

Description

아크릴 수지의 제조방법, 이로부터 얻어진 아크릴 수지 및 이를 주재로 한 자동차 상도용 도료Method for producing acrylic resin, acrylic resin obtained therefrom and automotive top coat based on the same

본 발명은 아크릴 수지를 함유하는 도료에 관한 것으로서, 보다 상세하게는 레올로지 조절제를 사용하지 않으면서 고기능의 도막 물성 즉, 안료 분산성, 광택 보지율 등이 매우 우수한 아크릴 수지의 제조 방법과 그를 주재로 한 자동차 상도용 도료에 관한 것이다.The present invention relates to a coating material containing an acrylic resin, and more particularly, to a method for producing an acrylic resin having excellent high-performance coating properties, that is, pigment dispersibility, gloss retention, and the like without using a rheology modifier, It relates to a paint for automotive top coat.

종래의 자동차 도료용 수지는 사용 용도에 따라 여러 종류가 있으나, 자동차 코팅용으로는 폴리에스테르, 알키드, 열경화성 아크릴 수지를 주재로 사용하면서 안료 분산용 수지 및 안료 입자의 오리엔테이션 증진을 위해 레올로지 조절제를 사용하고 있다.There are various types of resins for automobile paints according to the intended use. However, rheology control agents are used to improve the orientation of pigment dispersion resins and pigment particles while using polyester, alkyd and thermosetting acrylic resins as main materials for automotive coatings. I use it.

그러나 이와 같이 레올로지 조절제를 사용하게 되면 안료 입자의 오리엔테이션은 양호하나 도료의 저장성이 불량해져 외관 즉, 도막의 선영성이 취약해질 우려가 크다. 또한 레올로지 조절제를 각 안료마다 분산시키는 공정을 도입 및 별도의 안료분산용 수지를 사용하여야 하며, 이로 인해 제조 원가의 상승이 불가피하였다.However, when the rheology control agent is used in this way, the orientation of the pigment particles is good, but the storage property of the paint is poor, so that the appearance, ie, the selectivity of the coating film, is high. In addition, a process for dispersing the rheology control agent for each pigment should be introduced and a separate pigment dispersion resin should be used, thereby increasing the manufacturing cost.

따라서 본 발명은 상기와 같은 단점을 해결하기 위한 것으로, 그 목적은 수지의 구조 및 형태 변화, 수지의 분자량, 가교 결합 반응 속도 등이 균형을 이루어 양호한 안료 분산성, 외관의 선영성, 내약품성, 내열성, 내후성이 우수한 자동차 상도용 도료를 제공하는 데 있다.Accordingly, the present invention is to solve the above disadvantages, the purpose is to balance the structure and shape of the resin, the molecular weight of the resin, the crosslinking reaction rate and the like, good pigment dispersibility, clarity of appearance, chemical resistance, It is to provide an automotive top coat with excellent heat resistance and weather resistance.

또한 본 발명의 다른 목적은 자동차 상도용 아크릴 수지의 제조방법을 제공하는 데 있다.In addition, another object of the present invention to provide a method for producing an acrylic resin for automotive top coat.

상기 본 발명의 목적을 달성하기 위한 자동차 상도용 도료는 기존의 아크릴 수지로는 한계가 있으므로 안료 분산성이 우수한 관능기 및 속건형 용제와 클리어 도료와 웨트-온-웨트(wet-on-wet) 도장 시스템에서 레올로지 조절제 없이도 안료입자의 오리엔테이션과 외관의 선영성을 부여하기 위해 수지의 폴리머 구조와 분자량을 높인 형태의 수지를 제조하는 데에 그 특징이 있다.Automotive topcoat paints to achieve the object of the present invention is limited to the conventional acrylic resin, so excellent pigment dispersibility, functional groups and quick-drying solvents and clear paints and wet-on-wet (wet-on-wet) coating The system is characterized by the production of resins in which the polymer structure and molecular weight of the resin are increased in order to give the orientation and appearance of the pigment particles without the rheology control agent.

좀더 상세히 설명하면 본 발명에서 사용하는 아크릴 수지는 비점이 낮은 용제와 분자량 분포도 조절을 위한 메르캅탄류를 사용하고 모노머의 이중결합을 개시제로 래디칼 반응시켜 제조한 것으로, 산가 5∼30mgKOH/g, 하이드록시기가 30∼100mgKOH/g, 수평균 분자량 5000∼30000, 유리전이온도(Tg)는 20∼70℃이다.More specifically, the acrylic resin used in the present invention is prepared by using a solvent having a low boiling point and mercaptans for molecular weight distribution control and radical reaction of a double bond of a monomer with an initiator, and an acid value of 5 to 30 mgKOH / g, The oxy group is 30-100 mgKOH / g, the number average molecular weight 5000-30000, and glass transition temperature (Tg) are 20-70 degreeC.

상기 아크릴 수지를 주재로 한 자동차 상도용 도료는 아크릴 수지 제조시 긴 사슬 하이드록시 모노머와 긴 사슬 카르복실산 및 아민기 즉, 안료와의 입체적인 장애 효과를 줄이고 도료 저장시 씨드(seed) 및 엉김(Flocculation)을 최소화하기 위한 아로마틱 계통의 관능기를 갖는 수지를 사용하며 분자량을 증가시켜 셀룰로스 아세테이트 부틸레이트 계통과 마이크로겔 등의 레올로지 조절제를 사용하지 않고자동차 상도용 도료와 클리어 도료를 웨트-온-웨트 시스템으로 도장할 수 있도록 한 것이다.Automotive topcoat paints based on acrylic resins reduce the steric hindrance effect of long chain hydroxy monomers and long chain carboxylic acid and amine groups, i.e., pigments, in the manufacture of acrylic resins. We use resins with aromatic functional groups to minimize flocculation and increase the molecular weight to wet-on-wet paints and clear coatings for automotive topcoats without using rheology modifiers such as cellulose acetate butyrate systems and microgels. The system can be painted.

또한 도장시 상도 도료를 속건형으로 유도하여 도막에 선영성을 부여하였으며, 안료 분산성, 광택 보지율, 내후성, 내열성, 내약품성 등이 우수한 특징을 지닌다.In addition, by applying the top coat paint in a quick-drying type during coating, the coating film has been given goodness, it has excellent characteristics such as pigment dispersibility, gloss retention, weather resistance, heat resistance, chemical resistance.

본 발명을 단계별로 상세히 설명한다.The present invention will be described in detail step by step.

1. 아크릴 수지의 제조1. Preparation of Acrylic Resin

아크릴 수지의 제조 방법에는 여러 가지 방법이 있으나 가장 보편화된 방법인 용액 중합을 이용하는 것이 가장 바람직하다.There are various methods for producing the acrylic resin, but it is most preferable to use solution polymerization, which is the most common method.

본 발명에 따른 아크릴 수지의 제조방법은 크게 두 가지의 방법으로 나눌 수 있는데, 궁극적으로 모든 방법은 아크릴 수지에 긴 사슬 하이드록시기를 도입하고자 한 것이다.The method for producing an acrylic resin according to the present invention can be broadly divided into two methods. Ultimately, all the methods are intended to introduce long chain hydroxyl groups into the acrylic resin.

(1)제 1 방법(1) The first method

그 방법의 첫 번째는, 다음의 일반식 (1)로 표시되는 아크릴 모노머, 일반식 (2)로 표시되는 아크릴 모노머와 관능성 모노머를 용액중합시키는 방법으로서, 이때 관능성 모노머라 함은 긴사슬 하이드록시기를 갖는 모노머, 하이드록시 모노머 및 산기 또는 아미노기를 갖는 모노머의 혼합물이다.The first of the methods is a method of solution polymerization of an acrylic monomer represented by the following general formula (1), an acrylic monomer represented by the general formula (2) and a functional monomer, wherein the functional monomer is a long chain It is a mixture of the monomer which has a hydroxyl group, a hydroxyl monomer, and the monomer which has an acidic group or an amino group.

여기서, R1은 수소원자 또는 메틸기이고, R2는 탄소수가 1∼14인 알킬기이다.R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 1 to 14 carbon atoms.

여기서, R은 방향족 비닐 화합물이다.Wherein R is an aromatic vinyl compound.

상기 일반식 (1)에 해당되는 모노머는 메틸아크릴레이트, 에틸아크릴레이트, 프로필아크릴레이트, n-부틸아크릴레이트, 이소부틸아크릴레이트, t-부틸아크릴레이트, 2-에틸헥실아크릴레이트, 라우릴아크릴레이트, 메틸메타아크릴레이트, 에틸메타아크릴레이트, 프로필메타아크릴레이트, n-부틸메타아크릴레이트, t-부틸메타아크릴레이트, 2-에틸헥실메타아크릴레이트, 라우릴메타아크릴레이트, 씨클로헥실아크릴레이트, 씨클로헥실메타아크릴레이트, 셀로솔브메타아크릴레이트 등이 있으며, 이들의 적정 함량은 50∼85중량%이며, 60∼80중량%로 사용하는 것이 보다 바람직하다.Monomers corresponding to the general formula (1) are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acryl Latex, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl acrylate, Cyclohexyl methacrylate, cellosolve methacrylate, and the like, and an appropriate content thereof is 50 to 85% by weight, more preferably 60 to 80% by weight.

그 이유는 이들 아크릴 모노머가 50% 이상 사용되어야 소지와의 접착력이 향상되고 아크릴 기본 물성 특성을 가지게 되기 때문이다. 즉, 아크릴 모노머가 가지는 고유한 물성은 유리전이온도(Tg)를 적절히 조절하여 유연성과 경도, 외관, 안료 분산성 등이 상호 보완되도록 적정량을 선택해야 한다. 만약 이들 모노머들을 85% 이상 사용하는 경우에는 도막이 필요 이상으로 딱딱해져 유연성이 부족하고 치핑성에 문제가 발생하게 된다.The reason for this is that when the acrylic monomers are used at least 50%, the adhesion to the substrate is improved and the acrylic basic physical properties are obtained. That is, the inherent physical properties of the acrylic monomer should be appropriately selected so as to complement the flexibility and hardness, appearance, pigment dispersibility, etc. by appropriately adjusting the glass transition temperature (Tg). If more than 85% of these monomers are used, the coating film becomes harder than necessary, resulting in insufficient flexibility and chipping problems.

상기 일반식 (2)에 해당되는 모노머로는 스타이렌, α-메틸스타이렌, 벤질(메타)아크릴레이트, 페닐(메타)아크릴레이트, 비닐톨루엔 등이 있으며, 이들은 단독 또는 다른 것과 혼합하여 사용하며, 이들의 적절한 함량은 5∼20중량%이다. 만약 20중량% 이상으로 사용하게 되면 오히려 도막의 내후성 및 안료 분산성을 저하시키게 된다.Monomers corresponding to the general formula (2) include styrene, α-methylstyrene, benzyl (meth) acrylate, phenyl (meth) acrylate, vinyltoluene, and the like, which are used alone or in combination with others. And their proper content is 5 to 20% by weight. If it is used in more than 20% by weight, the weather resistance and pigment dispersibility of the coating film is rather reduced.

관능성 모노머는 10∼30중량%로 사용하는 것이 적절하며, 구체적으로 살피면 다음과 같다:Functional monomers are suitably used in an amount of 10 to 30% by weight.

a)긴 사슬 하이드록실기를 갖는 모노머a) monomers with long chain hydroxyl groups

긴 사슬 하이드록실기를 갖는 모노머로는 다음과 같은 두 가지의 방법을 통해 얻어진 모노머를 사용할 수 있다.As a monomer having a long chain hydroxyl group, a monomer obtained through the following two methods can be used.

a-1)활성수소 화합물로 글리시딜 에스테르의 에폭시 링을 개환시키는 방법을 통해 얻어진 모노머a-1) Monomer obtained by ring-opening an epoxy ring of glycidyl ester with an active hydrogen compound

(메타)아크릴산, 크로토닉산, 이타코닉산, 푸마린산과 같은 아크릴 모노머와 파라아미노벤조익산, 파라니트로벤조익산과 같은 산기로 글리시딜 에스테르와 반응시켜 제조한다.It is prepared by reacting glycidyl ester with an acrylic monomer such as (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, and an acid group such as paraaminobenzoic acid and paranitrobenzoic acid.

이때, 글리시딜 에스테르로는 글리시딜부틸레이트, 글리시딜팔미테이트, 글리시딜 라우레이트, 글리시딜 스테아레이트를 사용할 수 있으며, 일반적으로 쉘(Shell)사 제품인 카두라 이 시리즈(CADURA E Series)를 사용한다.In this case, glycidyl ester may be glycidyl butyrate, glycidyl palmitate, glycidyl laurate, glycidyl stearate, and generally the CADURA E series manufactured by Shell. Series).

반응은 산기와 에폭시기 간의 당량비를 1:0.8~1.2가 되게 투입하고 130℃ 이하에서 반응시켜 하이드록시기를 갖는 모노머를 제조한다.In the reaction, an equivalent ratio between an acid group and an epoxy group is 1: 0.8 to 1.2, and the reaction is carried out at 130 ° C. or less to prepare a monomer having a hydroxyl group.

a-2)메르캅탄류 산 또는 폴리에스테르 모노머로 글리시딜 에스테르의 에폭시링을 개환시키는 방법을 통해 얻어진 모노머a-2) Monomer obtained by ring-opening the epoxy ring of glycidyl ester with a mercaptanic acid or a polyester monomer

메르캅탄 프로피온산, 티오글리콜산 등과 같은 메르캅탄류 산과 디메틸을 프로피온산, (메틸)헥사프탈릭 언하이드라이드 등과 같은 폴리에스테르 모노머를 사용하여 글리시딜 에스테르의 에폭시 링을 개환시킨다.Mercaptanic acids such as mercaptan propionic acid, thioglycolic acid, and dimethyl are ring-opened with epoxy monomers of glycidyl esters using polyester monomers such as propionic acid, (methyl) hexaphthalic anhydride and the like.

이때, 글리시딜 에스테르로는 글리시딜(메타)아크릴레이트, 메틸글리시딜(메타)아크릴레이트, 앨리(ally) 글리시딜 에스테르 등을 사용할 수 있다.In this case, as the glycidyl ester, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, allyl glycidyl ester, or the like can be used.

상기의 반응은 1차 반응으로 글리시딜 에스테르를 아크릴 수지 골격에 부가반응시키고 2차 반응으로 메르캅탄류 산 및 폴리에스테르 산과 반응시킨다. 이때 산과 에폭시의 당량비가 1:0.8~1.2가 되게 투입하고 150℃ 이하의 온도에서 반응시켜 하이드록시기를 갖는 모노머를 제조한다.In the above reaction, the glycidyl ester is added to the acrylic resin skeleton in the first reaction and the mercaptanic acid and the polyester acid are reacted in the second reaction. In this case, an equivalent ratio of acid and epoxy is 1: 0.8 to 1.2, and the monomer is reacted at a temperature of 150 ° C. or less to prepare a monomer having a hydroxyl group.

이렇게 제조된 폴리머는 브랜치 또는 그래프트 구조를 갖는다.The polymer thus prepared has a branch or graft structure.

상기 a-1)과 a-2)의 모노머를 제조함에 있어서 글리시딜 에스테르는 산과 반응하여 긴사슬 하이드록시기를 생성시키는 역할을 한다. 산 또한 에폭시기와 반응하여 긴사슬 하이드록시기를 생성하는 역할을 한다.In preparing the monomers of a-1) and a-2), the glycidyl ester serves to generate a long chain hydroxy group by reacting with an acid. Acids also react with the epoxy groups to produce long chain hydroxyl groups.

b)하이드록시 모노머b) hydroxy monomer

하이드록시 모노머는 차후로 아크릴 수지를 도료에 적용시 멜라민 경화제와 반응할 수 있는 사이트를 부여하기 위해 사용되는 것으로서, 구체적으로는 하이드록시 에틸(메타)아크릴레이트, 하이드록시 프로필(메타)아크릴레이트, 하이드록시부틸(메타)아크릴레이트 등을 들 수 있다.The hydroxy monomer is used to give a site capable of reacting with the melamine curing agent when the acrylic resin is subsequently applied to the paint, specifically, hydroxy ethyl (meth) acrylate, hydroxy propyl (meth) acrylate, Hydroxybutyl (meth) acrylate etc. are mentioned.

c)산기 또는 아미노기를 갖는 모노머c) monomers having an acid group or an amino group

산기를 갖는 모노머로는 다음 일반식(3)의 화합물을 포함한다.As a monomer which has an acidic radical, the compound of following General formula (3) is included.

여기서, R1은 수소 또는 메틸기이고, R2는 아로메틱 링 또는 탄소수가 1∼8인 알킬기이며, n은 1∼4의 정수이다.R 1 is hydrogen or a methyl group, R 2 is an aromatic ring or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4 here.

구체적으로, 산기 또는 아미노기를 갖는 모노머로는 (메타)아크릴산, 크로토닉산, 이타코닉산, 푸마린산, 모노메타크릴로일옥시에틸프탈레이트(International Speciality Chemical사 제품 BISOMER EMP), 디메틸아미노에틸메타아크릴레이트, 디에틸아미노에틸메타아크릴레이트, 이소부톡시메틸아크릴레이트, n-부톡시메틸아크릴아미드, 아크릴아미드 등을 들 수 있다.Specifically, examples of the monomer having an acid group or an amino group include (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, monomethacryloyloxyethyl phthalate (BISOMER EMP manufactured by International Specialty Chemical), dimethylaminoethylmetha Acrylate, diethylaminoethyl methacrylate, isobutoxymethyl acrylate, n-butoxymethyl acrylamide, acrylamide and the like.

이들 반응성 모노머들은 도료 제조 도중 안료 분산 효과를 높이고, 내식성 증대, 상용성 향상 및 슬리핑성, 스크래치성을 좌우하게 된다. 또한 수지에는 하이드록시 그룹 10∼30중량%, 산기 1∼10중량%, 아미노기 1∼10중량% 정도를 사용하는 것이 적절하다.These reactive monomers will increase the pigment dispersion effect during paint preparation, increase corrosion resistance, improve compatibility and sleepability, scratch resistance. Moreover, it is suitable to use about 10-30 weight% of hydroxy groups, 1-10 weight% of acidic groups, and about 1-10 weight% of amino groups for resin.

(2)제 2 방법(2) second method

본 발명에 따라 아크릴 수지에 긴 사슬 하이드록시기를 도입하는 다른 방법으로는, 상기에 (1)제 1 방법에 예시된 일반식 (1)의 아크릴 모노머, 일반식 (2)의 아크릴 모노머, 하이드록시 모노머 및 산기 또는 아미노기를 갖는 모노머를 상기와 같은 비로써 용액중합하여 산 코폴리머 수지를 제조한 다음 여기에 글리시딜 에스테르를 첨가하여 에폭시 링을 개환시켜 브랜치 또는 그래프트 중합하는 방법을 들수 있다.As another method for introducing a long-chain hydroxy group into the acrylic resin according to the present invention, the acrylic monomer of the general formula (1) exemplified in the first method (1) above, the acrylic monomer of the general formula (2), hydroxy A method of producing an acid copolymer resin by solution polymerization of a monomer and a monomer having an acid group or an amino group in the above ratio, followed by branching or graft polymerization by adding an glycidyl ester to ring-open an epoxy ring.

용액중합하여 얻어진 산 코폴리머 수지는 산가가 40∼80mgKOH/g이며, 이것을 사용하여 글리시딜 에스테르의 에폭시 링을 개환시켜 브랜치 또는 그래프트 구조를 갖는 수지를 제조한다. 이때 산과 에폭시간의 당량비는 1:0.8∼1.2가 되게 하고 150℃ 이하의 온도에서 반응시킨다.The acid copolymer resin obtained by solution polymerization has an acid value of 40-80 mgKOH / g, and uses this to ring-open the epoxy ring of glycidyl ester, and manufactures resin which has a branch or graft structure. At this time, the equivalent ratio between acid and epoxy is 1: 0.8 to 1.2 and reacted at a temperature of 150 ° C. or less.

산 코폴리머 수지의 주재인 산기 모노머로는 (메타)아크릴산, 크로토닉산, 이타코닉산, 푸마린산을 사용하고, 글리시딜 에스테르로는 글리시딜 부틸레이트, 글리시딜팔미테이트, 글리시딜 라우레이트, 글리시딜 스테아레이트 등을 사용할 수 있다.(Meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid are used as the acidic monomer which is the main agent of the acid copolymer resin, and glycidyl butyrate, glycidyl palmitate, glycid as glycidyl ester Cydyl laurate, glycidyl stearate and the like can be used.

제 1 방법이나 제 2 방법을 통해 아크릴 수지를 제조함에 있어서 용액중합시 개시제로는 아조비스이소부티로니트릴, 아조비스디메틸발레로니트릴과 같은 아조화합물과 벤조일퍼옥사이드, 라우로디퍼옥사이드 등과 같은 퍼옥사이드계 유기 개시제를 사용한다.In preparing the acrylic resin through the first method or the second method, the initiators during solution polymerization include azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, and fur such as benzoyl peroxide and laurodiperoxide. Oxide organic initiators are used.

용제로는 지방족 혹은 방향족 하이드로카본계 용제를 사용하며, 구체적으로는 헵탄, 톨루엔, 크실렌 등의 탄화수소 용제와 에틸아세테이트, n-부틸아세테이트, 이소부틸아세테이트 등의 아세테이트류, 에탄올, 이소프로판올, n-부탄올, sec-부탄올, 이소부탄올 등의 알콜류를 단독 또는 조합하여 사용한다.As the solvent, an aliphatic or aromatic hydrocarbon solvent is used. Specifically, hydrocarbon solvents such as heptane, toluene and xylene, acetates such as ethyl acetate, n-butyl acetate and isobutyl acetate, ethanol, isopropanol and n-butanol alcohols such as, sec-butanol and isobutanol are used alone or in combination.

용액 중합은 보통 그 용매의 환류 온도내에서 반응하는 데, 반응시간은 일반적으로 5∼15시간 내외이다. 이때 분자량이 필요 이상으로 증대되는 것을 막기 위해 메르캅탄류를 중합 조절제로 사용할 수 있다. 사용 가능한 메르캅탄류로는 n-부틸메르캅탄, n-도데실메르캅탄, t-부틸메르캅탄, n-옥틸메르캅탄 등이 있으며, 일반적으로 0.05∼0.1중량% 정도로 첨가한다.Solution polymerization usually reacts at the reflux temperature of the solvent, and the reaction time is generally about 5 to 15 hours. At this time, in order to prevent the molecular weight from increasing more than necessary, mercaptans can be used as a polymerization regulator. The mercaptans that can be used include n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, n-octyl mercaptan and the like, and are generally added at 0.05 to 0.1% by weight.

상기와 같은 방법으로 제조된 산가 5∼30mgKOH/g, 말단의 하이드록시기의 수 1∼2개, 하이드록시가 30∼100mgKOH/g인 아크릴 수지를 도료에 적용한다. 그 이유는 산가가 5 이하이면 경화 및 부착강도 등에 문제가 발생하고 30 이상이면 내수성이 취약하게 되며, 하이드록시가가 30이하이면 가교 밀도가 떨어져 경도, 내약품성 및 내식성이 떨어지고 100 이상이면 가교 밀도가 높아져 도막에 크랙이 발생하거나 치핑성에 문제가 될 수 있기 때문이다.An acrylic resin having an acid value of 5 to 30 mgKOH / g, 1 to 2 of hydroxyl groups at the end, and a hydroxyl of 30 to 100 mgKOH / g prepared by the above method is applied to the paint. The reason is that if the acid value is 5 or less, problems occur in curing and adhesion strength, and if it is 30 or more, the water resistance becomes weak. If the hydroxyl value is 30 or less, the crosslinking density is low, and the hardness, chemical resistance and corrosion resistance are poor. This is because it may cause cracks in the coating film or chipping problems.

2. 도료 제조2. Paint manufacturer

도료 제조는 상기의 제 1 방법이나 제 2 방법을 통해 긴 사슬 하이드록시기가 도입된 아크릴 수지와 경화제를 사용하고 여기에 무기 및 유기 안료, 레벨링제, 자외선 흡수제 및 용제를 혼합하면 된다.Coating preparation may use the acrylic resin and hardening | curing agent in which the long-chain hydroxyl group was introduce | transduced through said 1st method or 2nd method, and may mix an inorganic and organic pigment, a leveling agent, a ultraviolet absorber, and a solvent.

도료 제조시 경화제로는 알콕시 메틸 멜라민 수지를 사용한다. 이로는 메틸레이티드 멜라민 수지, n-부틸레이티드 멜라민 수지, 이소부틸레이티드 멜라민 수지 등이 있고, 알콕시기로는 에톡시기, n-부톡시기, 이소부톡시기를 사용한다. 이중에 가장 바람직한 것은 n-부틸레이티드 멜라민 수지와 이소부틸레이티드 멜라민 수지를 사용하는 것이다.Alkoxy methyl melamine resin is used as a curing agent in the production of paint. Examples thereof include methylated melamine resin, n-butylated melamine resin, isobutylated melamine resin and the like, and an ethoxy group, n-butoxy group and isobutoxy group are used as the alkoxy group. Most preferred of these is the use of n-butylated melamine resins and isobutylated melamine resins.

이때 용제는 속건형을 사용하며, 도장시 상도 도료와 클리어 도료 간을 층분리시켜 경화 후 맑기감을 우수하게 한다.At this time, the solvent uses a quick-drying type, and when the coating is separated between the top coat and clear paint to excellent after clearing after curing.

도료의 경화는 160℃ 이하의 온도에서 50분 이하로 반응시킨다.Curing of the paint is carried out at a temperature of 160 ° C. or less for 50 minutes or less.

본 발명의 도료는 긴 사슬의 관능기를 사용하므로 안료분산성 수지를 사용할 필요가 없으며, 안료 입자의 오리엔테이션을 위해 캡(CAB) 또는 마이크로겔 등과 같은 레올로지 조절제를 사용할 필요가 없다.Since the paint of the present invention uses a long chain functional group, it is not necessary to use a pigment dispersible resin, and there is no need to use a rheology modifier such as a cap (CAB) or a microgel for the orientation of the pigment particles.

그리고 본 발명의 도료는 기존의 것에 비해 도막이 강인하고 치핑성, 슬리핑성 및 스크래치성이 우수하며, 내후성, 내열성 및 내산성이 우수하다.In addition, the paint of the present invention has a stronger coating film, excellent chipping, sleeping and scratching properties, and excellent weather resistance, heat resistance and acid resistance.

이하, 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, the present invention is not limited by the Examples.

<긴 사슬 하이드록시기를 갖는 모노머의 제조><Production of Monomer Having Long Chain Hydroxy Group>

제조예 1(C-1)Preparation Example 1 (C-1)

아크릴산 360g, 카두라(CADURA) E-10(쉘사 제품) 1250g, 하이드로퀴논 3.2g을 플라스크에 넣고 100℃의 반응온도로 15시간 유지하여 산가가 1mgKOH/g 이하에서 반응을 종결한다.360 g of acrylic acid, 1250 g of CADURA E-10 (manufactured by Shell Company), and 3.2 g of hydroquinone were placed in a flask and maintained at a reaction temperature of 100 ° C. for 15 hours to terminate the reaction at an acid value of 1 mgKOH / g or less.

제조예 2(C-2)Preparation Example 2 (C-2)

메르캅토프로피온산 480g, 글리시딜메타아크릴레이트 568g, 하이드로퀴논 2.1g을 플라스크에 넣고 100℃의 반응온도로 15시간 유지하여 산가가 1mgKOH/g 이하에서 반응을 종결한다.480 g of mercaptopropionic acid, 568 g of glycidyl methacrylate, and 2.1 g of hydroquinone were placed in a flask and maintained at a reaction temperature of 100 ° C. for 15 hours to terminate the reaction at an acid value of 1 mgKOH / g or less.

제조예 3(C-3)Preparation Example 3 (C-3)

디메틸올프로피온산 366g, 글리시딜메타아크릴레이트 426g, 하이드로퀴논 0.2g과 n-부탄올 528g을 플라스크에 넣고 100℃의 반응온도로 15시간 유지하여 산가가 1mgKOH/g 이하에서 반응을 종결한다.366 g of dimethylol propionic acid, 426 g of glycidyl methacrylate, 0.2 g of hydroquinone and 528 g of n-butanol were placed in a flask and maintained at a reaction temperature of 100 ° C. for 15 hours to terminate the reaction at an acid value of 1 mgKOH / g or less.

<아크릴 수지의 제조><Production of Acrylic Resin>

제조예 1(A-1)Preparation Example 1 (A-1)

메틸메타아크릴레이트 240g, n-부틸메타아크릴레이트 150g, 스타이렌 90g, 하이드록시에틸메타아크릴레이트 60g, 아크릴산 60g, 벤조일퍼옥사이드 12g을 혼합하여 톨루엔 580g에 3시간에 걸쳐 첨가하고 2시간 동안 환류 반응시킨 다음, 톨루엔 20g에 벤조일퍼옥사이드 0.3g을 용해시켜 10분간 첨가하고 3시간 동안 환류 반응시켜 1차 반응물을 제조한다. 상기 1차 반응물을 상온으로 냉각시킨 후 카두라 E-10 145.8g을 첨가하여 100℃의 반응온도에서 15시간 동안 유지(2차 반응)시킨 후 산가 24mgKOH/g 이하에서 반응을 종결시킨다. 이의 수평균 분자량은 10000이다.240 g of methyl methacrylate, 150 g of n-butyl methacrylate, 90 g of styrene, 60 g of hydroxyethyl methacrylate, 60 g of acrylic acid, 12 g of benzoyl peroxide were mixed and added to 580 g of toluene over 3 hours and refluxed for 2 hours. After dissolving 0.3 g of benzoyl peroxide in 20 g of toluene, the mixture was added for 10 minutes and refluxed for 3 hours to prepare a primary reactant. After cooling the first reactant to room temperature, 145.8 g of Kadura E-10 was added thereto, maintained at a reaction temperature of 100 ° C. for 15 hours (secondary reaction), and the reaction was terminated at an acid value of 24 mgKOH / g or less. Its number average molecular weight is 10000.

제조예 2(A-2)Preparation Example 2 (A-2)

메틸메타아크릴레이트 180g, n-부틸메타아크릴레이트 180g, 스타이렌 90g, 하이드록시에틸메타아크릴레이트 30g, 아크릴산 18g, 중간체 제조예(C-1)에서 제조한 것 102g을 혼합하고, 여기에 개시제로 아조비스이소부티로니트릴 6g을 혼합하여 톨루엔 580g에 3시간에 걸쳐 첨가하고 2시간 동안 환류 반응시킨 다음, 톨루엔 20g에 아조비스이소부티로니트릴 0.3g을 용해시켜 첨가하고 3시간 동안 유지하여 아크릴 수지를 제조한다. 이의 수평균 분자량은 12000이다.180 g of methyl methacrylate, 180 g of n-butyl methacrylate, 90 g of styrene, 30 g of hydroxyethyl methacrylate, 18 g of acrylic acid, 102 g of the product prepared in Intermediate Preparation Example (C-1) are mixed, and as an initiator 6 g of azobisisobutyronitrile was mixed and added to 580 g of toluene over 3 hours, and refluxed for 2 hours. Then, 0.3 g of azobisisobutyronitrile was added to 20 g of toluene, and maintained for 3 hours. To prepare. Its number average molecular weight is 12000.

제조예 3(A-3)Preparation Example 3 (A-3)

에틸아크릴레이트 120g, n-부틸아크릴레이트 240g, 스타이렌 90g, 하이드록시에틸메타아크릴레이트 60g, 메타아크릴산 24g, 중간체 제조예(C-2)에서 제조한 것 78g, 디메틸아미노에틸메타아크릴레이트 18g, 아조비스이소부티로니트릴 12g을혼합하여 톨루엔 580g에 3시간에 걸쳐 첨가하고 2시간 동안 환류 반응시킨 다음, 톨루엔 20g에 아조비스이소부티로니트릴 0.3g을 용해시켜 첨가하고 3시간 동안 유지하여 아크릴 수지를 제조한다. 이의 수평균 분자량은 10000이다.120 g of ethyl acrylate, 240 g of n-butyl acrylate, 90 g of styrene, 60 g of hydroxyethyl methacrylate, 24 g of methacrylic acid, 78 g prepared in Intermediate Preparation Example (C-2), dimethylaminoethyl methacrylate 18 g, 12 g of azobisisobutyronitrile was mixed and added to 580 g of toluene over 3 hours, and refluxed for 2 hours. Then, 0.3 g of azobisisobutyronitrile was added to 20 g of toluene, and maintained for 3 hours. To prepare. Its number average molecular weight is 10000.

제조예 4(A-4)Preparation Example 4 (A-4)

메틸메타아크릴레이트 240g, n-부틸아크릴레이트 180g, 하이드록시에틸메타아크릴레이트 90g, 중간체 제조예(C-3)에서 제조한 것 120g, 메타아크릴레이트 12g, 디에틸아미노에틸메타아크릴레이트 12g, n-옥틸메르캅탄 0.4g, 벤조일퍼옥사이드 14g을 혼합하여 톨루엔 454g에 3시간에 걸쳐 첨가하고 2시간 동안 환류 반응시킨 다음, 톨루엔 20g에 벤조일퍼옥사이드 0.3g을 용해시켜 첨가하고 3시간 동안 유지하여 아크릴 수지를 제조한다. 이의 수평균 분자량은 9000이다.240 g of methyl methacrylate, 180 g of n-butyl acrylate, 90 g of hydroxyethyl methacrylate, 120 g of the one prepared in Intermediate Preparation Example (C-3), 12 g of methacrylate, 12 g of diethylaminoethyl methacrylate, n 0.4 g of octyl mercaptan and 14 g of benzoyl peroxide were mixed and added to 454 g of toluene over 3 hours and refluxed for 2 hours. Then, 0.3 g of benzoyl peroxide was added to 20 g of toluene, and maintained for 3 hours. Prepare a resin. Its number average molecular weight is 9000.

제조예 5(A-5)Preparation Example 5 (A-5)

스타이렌 90g, 이소부틸메타아크릴레이트 210g, 하이드록시에틸메타아크릴레이트 60g, 중간체 제조예(C-1)에서 제조한 것 60g, n-부틸메타아크릴레이트 150g, 바이소머(BISOMER) 이엠피(EMP)(International Speciality Chemical사 제품) 30g, 벤조일퍼옥사이드 9g을 혼합하여 톨루엔 580g에 3시간에 걸쳐 첨가하고 2시간 동안 환류 반응시킨 다음, 톨루엔 20g에 벤조일퍼옥사이드 0.3g을 용해시켜 첨가하고 3시간 동안 유지하여 아크릴 수지를 제조한다. 이의 수평균 분자량은 14000이다.90 g of styrene, 210 g of isobutyl methacrylate, 60 g of hydroxyethyl methacrylate, 60 g of the product prepared in Intermediate Preparation Example (C-1), 150 g of n-butyl methacrylate, BISOMER EMMP (EMP ) (Manufactured by International Specialty Chemical) 30g, 9g of benzoyl peroxide were added to 580g of toluene over 3 hours, refluxed for 2 hours, 0.3g of benzoyl peroxide was added to 20g of toluene, and added for 3 hours. To prepare an acrylic resin. Its number average molecular weight is 14000.

비교예 1(B-1)Comparative Example 1 (B-1)

메틸메타아크릴레이트 180g, n-부틸메타아크릴레이트 240g, 스타이렌 90g, 하이드록시에틸메타아크릴레이트 72g, 메타아크릴레이트 18g을 혼합하고, 벤조일퍼옥사이드 12g을 혼합하여 톨루엔 580g에 3시간에 걸쳐 첨가하고 2시간 동안 환류 반응시킨 다음, 톨루엔 20g에 벤조일퍼옥사이드 0.3g을 용해시켜 첨가하고 3시간 동안 유지하여 아크릴 수지를 제조한다.180 g of methyl methacrylate, 240 g of n-butyl methacrylate, 90 g of styrene, 72 g of hydroxyethyl methacrylate, 18 g of methacrylate were mixed, 12 g of benzoyl peroxide was mixed and added to 580 g of toluene over 3 hours. After refluxing for 2 hours, 0.3 g of benzoyl peroxide was added to 20 g of toluene, and then maintained for 3 hours to prepare an acrylic resin.

비교예 2(B-2)Comparative Example 2 (B-2)

메틸메타아크릴레이트 240g, n-부틸아크릴레이트 90g, 스타이렌 120g, 하이드록시에틸아크릴레이트 90g, 아크릴산 18g을 혼합하고, 아조비스이소부티로니트릴 12g을 혼합하여 톨루엔 580g에 3시간에 걸쳐 첨가하고 2시간 동안 환류 반응시킨 다음, 톨루엔 20g에 아조비스이소부티로니트릴 0.3g을 용해시켜 첨가하고 3시간 동안 유지하여 아크릴 수지를 제조한다.240 g of methyl methacrylate, 90 g of n-butyl acrylate, 120 g of styrene, 90 g of hydroxyethyl acrylate, 18 g of acrylic acid were mixed, 12 g of azobisisobutyronitrile were mixed and added to 580 g of toluene over 3 hours. After refluxing for an hour, 0.3 g of azobisisobutyronitrile was added to 20 g of toluene and dissolved for 3 hours to prepare an acrylic resin.

<밀베이스(millbase) 제조>Millbase manufacturing

제조예 1(M-1)Preparation Example 1 (M-1)

카본블랙 안료 150g, 멜라민 수지(1) 500g, 용제 400g, 레올로지 조절제 150g을 10시간 동안 볼밀하여 밀베이스를 제조한다.A mill base is prepared by ball milling 150 g of carbon black pigment, 500 g of melamine resin (1), 400 g of solvent, and 150 g of rheology control agent for 10 hours.

제조예 2(M-2)Preparation Example 2 (M-2)

카본블랙 안료 150g, 멜라민 수지(1) 500g, 용제 400g을 10시간 동안 볼밀하여 밀베이스를 제조한다.A mill base is prepared by ball milling 150 g of carbon black pigment, 500 g of melamine resin (1), and 400 g of a solvent for 10 hours.

제조예 3(M-3)Preparation Example 3 (M-3)

프탈로시아닌블루 150g, 멜라민 수지(2) 500g, 용제 400g을 10시간 동안 볼밀하여 밀베이스를 제조한다.Millbase is prepared by ball milling 150 g of phthalocyanine blue, 500 g of melamine resin (2), and 400 g of a solvent for 10 hours.

실시예 1~5Examples 1-5

다음 표 1은 본원발명의 조성비로 자동차 상도용 도료를 제조한 실시예이다.Table 1 is an example of manufacturing a coating for automotive top coat with a composition ratio of the present invention.

이들 실시예 및 비교예에서 제조한 도료를 사용하여 전착과 중도를 도장한 시편 위에 상도 도료를 도장한 후 클리어 도료를 도장하고, 상기의 상도 도료를 포드-컵(Ford-Cup)으로 25℃에서 15sec로 맞춘 후 분무하여 150℃에서 20분간 걸쳐 경화시켜 도막두께 17±3㎛인 도편을 제조하였다. 이때 클리어 도료로는 고려화학의 도료를 사용하였으며, 이에 대한 물성 시험 데이터는 표 2와 같다.Using the paints prepared in these Examples and Comparative Examples, the top coat was coated on the specimens coated with electrodeposition and the intermediate, and then the clear coat was applied. The top coat was coated at 25 ° C. with a pod-cup. After adjusting to 15 sec and sprayed to harden at 150 ℃ for 20 minutes to prepare a coating having a film thickness of 17 ± 3㎛. In this case, a clear paint was used as a paint of Korea Chemical, and the physical property test data thereof is shown in Table 2.

외관 시험: 텐션메타(Tension Meter)로써 사진 육안 확인 방법으로 시험함.Appearance Test: Tested by visual inspection method with tension meter.

광택 시험: 비.와이.케이.(BYK)사에서 제작한 마이크로-트리-글라스메타(Micro-Tri-Glassmeter)를 사용하여 시험 각도를 60˚로 하여 시험함.Gloss test: Tested at 60 ° using a Micro-Tri-Glassmeter manufactured by BYK.

내산성 시험: 26% 및 36% 황산 0.5㎖를 시편 위에 떨어뜨린 후 70℃ 온도에서 1시간 방치 후 흔적을 확인함(1: 양호, 2: 미세 흔적, 3: 칼라 리텐션(Colour Retention), 4: 부식).Acid Resistance Test: After dropping 0.5 ml of 26% and 36% sulfuric acid on the specimen, and left for 1 hour at 70 ° C, the traces were checked (1: good, 2: fine trace, 3: color retention, 4 : corrosion).

내수성 시험: 40℃의 물에 10일간 침적 후 도막의 외관 상태를 확인함.Water resistance test: After immersion in water at 40 ℃ for 10 days to confirm the appearance of the coating film.

내한 치핑성 시험: -40℃에서 3시간 방치 후 치핑 테스트를 실시하고 지엠(GM) 스펙(Spec)과 비교함.Cold resistance chipping test: After chipping at -40 ° C for 3 hours, chipping test is performed and compared with GM specification.

저장성 시험: 도료를 원액 점도로 제조한 후 60℃에서 3일 저장 후 도료의외관 상태를 확인함.Storage test: After the paint was prepared with the viscosity of the stock solution and stored for 3 days at 60 ℃ to check the appearance of the paint.

내후성 시험: 큐-패널(Q-Pannel)사의 큐.유.브이.(Q.U.V.)기기를 사용하여 측정함.Weatherability Test: Measured using Q-Pannel's Q.U.V.

상기 표 2의 물성 시험 결과에서 알 수 있듯이, 본 발명에 의한 도료는 외관, 광택, 내산성, 내수성, 저장성, 내한치핑성, 내후성 면 모두에서 종래의 도료에 비해 우수함을 알 수 있다.As can be seen from the physical property test results of Table 2, it can be seen that the paint according to the present invention is superior to the conventional paint in terms of appearance, gloss, acid resistance, water resistance, storage resistance, cold resistance, weather resistance.

Claims (9)

구조식(1)로 표시되는 화합물;A compound represented by formula (1); 구조식(2)로 표시되는 화합물; 및,A compound represented by formula (2); And, 관능성 모노머로서 활성수소 화합물로 글리시딜 에스테르의 에폭시 링을 개환시키는 방법으로 얻어진 모노머 및 메르캅탄류 산 또는 폴리에스테르 모노머로 글리시딜 에스테르의 에폭시 링을 개환시키는 방법으로 얻어진 모노머 중에서 선택된 1종 이상의 긴사슬 하이드록시기를 갖는 모노머, 하이드록시 모노머 및 산기 또는 아미노기를 갖는 모노머의 혼합물을 50~85 : 5~20 : 10 ~ 30중량부의 비율로 용액중합시킴을 특징으로 하는 아크릴 수지의 제조 방법.1 type selected from monomers obtained by ring-opening an epoxy ring of glycidyl ester with an active hydrogen compound as a functional monomer and monomers obtained by ring-opening an epoxy ring of glycidyl ester with a mercaptanic acid or polyester monomer A method of producing an acrylic resin, characterized by solution polymerization of a mixture of a monomer having a long chain hydroxyl group, a hydroxy monomer and a monomer having an acid group or an amino group in a proportion of 50 to 85: 5 to 20: 10 to 30 parts by weight. 여기서, R1은 수소원자 또는 메틸기이고,Here, R 1 is a hydrogen atom or a methyl group, R2는 탄소수가 1~14인 알킬기이다.R <2> is a C1-C14 alkyl group. 여기서, R은 방향족 비닐 화합물이다.Wherein R is an aromatic vinyl compound. 제 1 항의 제조방법에 따라 제조되며, 수평균 분자량 5000~30000, 하이드록시가 30~100mgKOH/g, 산가 5~30mgKOH/g, 유리 전이온도 20~70℃인 것을 특징으로하는 아크릴 수지.The acrylic resin is prepared according to the production method of claim 1, the number average molecular weight 5000 ~ 30000, the hydroxy is 30 ~ 100mgKOH / g, the acid value 5 ~ 30mgKOH / g, the glass transition temperature 20 ~ 70 ℃. 주재로 제 1 항의 아크릴 수지를 사용하고, 경화제로 멜라민 수지와 무기 및 유기 안료, 레벨링제, 자외선 흡수제 및 용제를 혼합하여 160℃ 이하의 온도에서 50분 이하로 경화 반응시켜서 됨을 특징으로 하는 자동차 상도용 도료.An automobile phase characterized in that the acrylic resin of claim 1 is used as a main material, and a melamine resin, an inorganic and organic pigment, a leveling agent, an ultraviolet absorber, and a solvent are mixed and cured at a temperature of 160 ° C. or less for 50 minutes or less as a curing agent. Pottery paints. 제 1 항에 있어서,The method of claim 1, 산기를 갖는 모노머는 다음 구조식(3)의 이중결합을 갖는 화합물이며, 아미노기를 갖는 모노머는 디메틸아미노에틸메타아크릴레이트, 디에틸아미노에틸메타아크릴레이트, n-부톡시메틸아크릴아미드 및 아크릴아미드 중에서 선택된 1종 이상의 것을 사용하는 것을 특징으로 하는 아크릴 수지의 제조 방법.The monomer having an acid group is a compound having a double bond of the following structural formula (3), and the monomer having an amino group is selected from dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, n-butoxymethylacrylamide and acrylamide. The manufacturing method of the acrylic resin characterized by using 1 or more types. 여기서, R1은 수소 또는 메틸기이고,Wherein R 1 is hydrogen or a methyl group, R2는 아로메틱 링 또는 탄소수가 1~8인 알킬기이며,R 2 is an aromatic ring or an alkyl group having 1 to 8 carbon atoms, n은 1~4인 정수이다.n is an integer of 1-4. 구조식(1)로 표시되는 화합물; 구조식(2)로 표시되는 화합물; 및, 관능성 모노머로서 하이드록시 모노머 및 산기 또는 아미노기를 갖는 모노머의 혼합물을50~85 : 5~20 : 10 ~ 30중량부의 비율로 용액중합시켜 산 코폴리머 수지를 제조한 다음, 여기에 글리시딜 부틸레이트, 글리시딜팔미테이트, 글리시딜 라우레이트 및 글리시딜 스테아레이트 중에서 선택된 1종 이상의 글리시딜 에스테르를 첨가하여 에폭시 링을 개환시켜 브랜치 또는 그래프트 중합하는 것을 특징으로 하는 아크릴 수지의 제조 방법.A compound represented by formula (1); A compound represented by formula (2); And a solution copolymer of a mixture of a hydroxy monomer and an monomer having an acid group or an amino group as a functional monomer in a ratio of 50 to 85: 5 to 20: 10 to 30 parts by weight to prepare an acid copolymer resin, The branched or graft polymerization of an acrylic resin by ring-opening an epoxy ring by adding at least one glycidyl ester selected from dibutyl butyrate, glycidyl palmitate, glycidyl laurate and glycidyl stearate Manufacturing method. 여기서, R1은 수소원자 또는 메틸기이고,Here, R 1 is a hydrogen atom or a methyl group, R2는 탄소수가 1~14인 알킬기이다.R <2> is a C1-C14 alkyl group. 여기서, R은 방향족 비닐 화합물이다.Wherein R is an aromatic vinyl compound. 제 5 항에 있어서, 산과 글리시딜 에스테르의 에폭시간의 당량비가 1:0.8∼1.2가 되도록 수행하는 것을 특징으로 하는 아크릴 수지의 제조 방법.The process for producing an acrylic resin according to claim 5, wherein the equivalent ratio between the acid and the epoxy of the glycidyl ester is 1: 0.8 to 1.2. 제 5 항에 있어서,The method of claim 5, wherein 산기를 갖는 모노머는 다음 구조식(3)의 이중결합을 갖는 화합물이며, 아미노기를 갖는 모노머는 디메틸아미노에틸메타아크릴레이트, 디에틸아미노에틸메타아크릴레이트, n-부톡시메틸아크릴아미드 및 아크릴아미드 중에서 선택된 1종 이상의것을 사용하는 것을 특징으로 하는 아크릴 수지의 제조 방법.The monomer having an acid group is a compound having a double bond of the following structural formula (3), and the monomer having an amino group is selected from dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, n-butoxymethylacrylamide and acrylamide. The manufacturing method of the acrylic resin characterized by using 1 or more types. 여기서, R1은 수소 또는 메틸기이고,Wherein R 1 is hydrogen or a methyl group, R2는 아로메틱 링 또는 탄소수가 1~8인 알킬기이며,R 2 is an aromatic ring or an alkyl group having 1 to 8 carbon atoms, n은 1~4인 정수이다.n is an integer of 1-4. 제 5 항의 제조방법에 따라 제조되며, 수평균 분자량 5000~30000, 하이드록시가 30~100mgKOH/g, 산가 5~30mgKOH/g, 유리 전이온도 20~70℃인 것을 특징으로 하는 아크릴 수지.The acrylic resin is prepared according to the production method of claim 5, the number average molecular weight 5000 ~ 30000, the hydroxy is 30 ~ 100mgKOH / g, the acid value 5 ~ 30mgKOH / g, the glass transition temperature 20 ~ 70 ℃. 주재로 제 8 항의 아크릴 수지를 사용하고, 경화제로 멜라민 수지와 무기 및 유기 안료, 레벨링제, 자외선 흡수제 및 용제를 혼합하여 160℃ 이하의 온도에서 50분 이하로 경화 반응시켜서 됨을 특징으로 하는 자동차 상도용 도료.An automobile phase characterized in that the acrylic resin of claim 8 is used as a main material, and the melamine resin and the inorganic and organic pigments, the leveling agent, the ultraviolet absorber and the solvent are mixed and cured at a temperature of 160 ° C. or less for 50 minutes or less as a curing agent. Pottery paints.
KR1019950068608A 1995-12-30 1995-12-30 Method for producing acrylic resin for use in top coating for cars having excellent pigment dispersibility, clearness, heat resistance, chemical resistance and weather resistance, acrylic resin obtained therefrom and top coating for cars based on the same resin KR100427706B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5876410A (en) * 1981-11-02 1983-05-09 Tokuyama Soda Co Ltd Manufacture of high-refractive index resin
KR830002811A (en) * 1979-05-18 1983-05-30 칼 에취. 크루코우 Resin manufacturing method
JPS62225501A (en) * 1986-03-28 1987-10-03 Mitsui Toatsu Chem Inc Aqueous emulsion resin composition
KR880014038A (en) * 1987-05-21 1988-12-22 요꼬야마 료지 Resin Compositions and Electrical Laminates Obtained therefrom
US4855369A (en) * 1985-12-11 1989-08-08 Exxon Chemical Patents Inc. High solids acrylic-based coatings
US4985517A (en) * 1985-12-11 1991-01-15 Exxon Chemical Patents, Inc. High solids acrylic-based coatings
JPH044270A (en) * 1990-04-20 1992-01-08 Honny Chem Ind Co Ltd Emulsion composition for electrodepositing paint

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR830002811A (en) * 1979-05-18 1983-05-30 칼 에취. 크루코우 Resin manufacturing method
JPS5876410A (en) * 1981-11-02 1983-05-09 Tokuyama Soda Co Ltd Manufacture of high-refractive index resin
US4855369A (en) * 1985-12-11 1989-08-08 Exxon Chemical Patents Inc. High solids acrylic-based coatings
US4985517A (en) * 1985-12-11 1991-01-15 Exxon Chemical Patents, Inc. High solids acrylic-based coatings
JPS62225501A (en) * 1986-03-28 1987-10-03 Mitsui Toatsu Chem Inc Aqueous emulsion resin composition
KR880014038A (en) * 1987-05-21 1988-12-22 요꼬야마 료지 Resin Compositions and Electrical Laminates Obtained therefrom
JPH044270A (en) * 1990-04-20 1992-01-08 Honny Chem Ind Co Ltd Emulsion composition for electrodepositing paint

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