KR0167539B1 - The preparation of anti-soluble thermoplastic acrylic resin - Google Patents
The preparation of anti-soluble thermoplastic acrylic resin Download PDFInfo
- Publication number
- KR0167539B1 KR0167539B1 KR1019950011873A KR19950011873A KR0167539B1 KR 0167539 B1 KR0167539 B1 KR 0167539B1 KR 1019950011873 A KR1019950011873 A KR 1019950011873A KR 19950011873 A KR19950011873 A KR 19950011873A KR 0167539 B1 KR0167539 B1 KR 0167539B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- resistance
- resin
- methacrylic acid
- acrylic resin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Abstract
본 발명은 메타 아크릴산 알킬 에스테르류, 아크릴산 알킬 아세테르류,메타 아크릴산류, 아크릴산류, 메타 아크릴산 히드록시 알킬 에스테르류, 알키드 중간체류 등을 용액중합하여 공중합된 화합물이 내용제성, 내가솔린성이 양호하고 도막의 깨짐현상, 박리현상이 발생하지 않는 열가소성 아크릴수지의 제조방법에 관한 것으로According to the present invention, a compound copolymerized by solution polymerization of alkyl methacrylates, alkyl acrylates, methacrylates, acrylic acids, hydroxy hydroxy alkyl esters, alkyd intermediates, and the like has good solvent resistance and resistance to gasoline. To a method for producing a thermoplastic acrylic resin which does not cause cracking or peeling of the coating film.
본 발명은 메타 아크릴산 알킬 에스테르 80∼90 중량%, 아크릴산 알킬 에스테르 3∼15 중량%, 메타 아크릴산 혹은 아크릴산이 0.1∼5 중량%, 메타 아크릴산 히드록시 알킬 에스테르 5∼10 중량%, 알키드 중간체수지 2∼10 중량%를 주성분으로 하는 단량체 조성물과 용액중합에 사용되는 용제를 교반장치, 온도계, 질소투입관, 적하장치 및 환류 냉각기가 부착된 반응기에서 라디칼 중합이 가능한 개시제를 사용하여 미반응 단량체가 잔존하지 않도록 완전히 반응시켜 공중합된 화합물로 내용제성, 내가솔린성이 우수하고 도막상태가 좋은 열가소성 아크릴수지를 제조함을 특징으로 한 것이며,The present invention is 80 to 90% by weight of methacrylic acid alkyl ester, 3 to 15% by weight of acrylic acid alkyl ester, 0.1 to 5% by weight of methacrylic acid or acrylic acid, 5 to 10% by weight of methacrylic acid hydroxy alkyl ester, 2 to alkyd intermediate resin 10% by weight of monomer composition and the solvent used in the polymerization of the solution are used in the reactor equipped with a stirring device, a thermometer, a nitrogen injection tube, a dropping device and a reflux condenser. It is characterized in that the thermoplastic acrylic resin which is excellent in solvent resistance and gasoline resistance and has good coating state as a copolymer copolymerized by fully reacting
이와 같은 제조된 본 발명의 열가소성 아크릴수지는 내용제성, 내가솔린성이 양호하고 도막의 깨짐현상, 박리현상이 발생하지 않는 효과가 있어 건축용 수지와 건축도료용수지로 널리 사용할 수가 있는 매우 획기적인 제품인 것이다.The thermoplastic acrylic resin of the present invention prepared as described above is a very breakthrough product that can be widely used as a building resin and a building paint resin because it has a good solvent resistance and resistance to gasoline, and does not cause cracking or peeling of the coating film.
Description
본 발명은 내용제성 및 내가솔린성이 양호하면서 도막 형성시 깨짐현상(Crack)이 발생하지 않고 도막 상태가 좋은 열가소성 아크릴수지를 제공하기 위한 것으로,The present invention is to provide a thermoplastic acrylic resin having a good solvent resistance and good resistance to gasoline, and does not cause cracks when forming a coating film, and has a good coating state.
본 발명은 메타아크릴산 알킬에스테르 혹은 아크릴산 알킬에스테르류에서 측쇄의 탄소수가 1-4인 단량체로 메틸메타아크릴레이트, 부틸아크릴레리트, 에틸아크릴레이트, 2-하이드록시에틸메타아크릴레이트, 메타아크릴산, 아크릴산을 측쇄의 탄소수가 5-14인 단량체로 2-에틸헥실아크릴레이트. 라우릴메타아크릴레이트. 스테아릴메타아크릴레이트와 불포화기를 함유한 중유 알키드중간체수지(유형:홍화유, 탈수피마자유, 유장:55%, 무수프탈산 함량:35%, Mn:1500, Tg:256K)를 열분해 개시제에 의한 라디칼 반응으로 용액중합하여 공중합된 화합물이 내용제성, 내가솔린성이 양호하고 도막의 깨짐현상이 발생하지 않는 열가소성 아크릴수지의 제조방법에 관한 것이다.The present invention is a methyl methacrylate, butyl acrylate, ethyl acrylate, 2-hydroxyethyl methacrylate, methacrylic acid, acrylic acid as a monomer having 1 to 4 carbon atoms in the side chain of alkyl methacrylate or alkyl acrylate esters. 2-ethylhexyl acrylate as a monomer having 5-14 carbon atoms in the side chain. Lauryl methacrylate. Radical reaction of heavy oil alkyd intermediate resin (type: safflower oil, dehydrated castor oil, whey: 55%, phthalic anhydride content: 35%, Mn: 1500, Tg: 256K) containing stearyl methacrylate and unsaturated group by pyrolysis initiator The present invention relates to a method for producing a thermoplastic acrylic resin in which the copolymerized by solution polymerization is good in solvent resistance and solin resistance and does not cause cracking of the coating film.
본 발명은 메타아크릴산 알킬에스테르 혹은 아크릴산 알킬에스테르류에서 측쇄의 탄소수가 1-4인 단량체로 메틸메타아크릴레이트를 주종으로 측쇄의 탄소수가 5-14인 단량체로 2-에틸헥실아크릴레이트의 불포화기를 함유한 중유 알키드 중간체수지(유형:홍화유, 탈수피마자유, 유장:55%, 무수프탈산 함량:35%, Mn:1500, Tg:256K)를 용액중합법으로 공중합체를 생성한 것으로 본 발명에 사용되는 비닐계 단량체의 일반식은 다음과 같다.The present invention is a monomer having 1 to 4 carbon atoms in the methacrylic acid alkyl esters or alkyl acrylates, mainly containing methyl methacrylate, and containing monomers having 2-ethylhexyl acrylate as monomers having 5 to 14 carbon atoms in the side chain. A heavy oil alkyd intermediate resin (type: safflower oil, dehydrated castor oil, whey: 55%, phthalic anhydride content: 35%, Mn: 1500, Tg: 256K) was produced by copolymerization of the copolymer by solution polymerization. The general formula of the vinyl monomer is as follows.
또는 or
상기 일반식중의 알킬기(R₂, R₃)는 직쇄상 혹은 측쇄상일때도 차이는 없고 구체적으로 메틸, 에틸, n-부틸, iso-부틸, 2-에틸헥실, iso-옥틸 등이 있다.Alkyl groups (R 2, R 3) in the general formula are not different even when linear or branched, and specific examples include methyl, ethyl, n-butyl, iso-butyl, 2-ethylhexyl, and iso-octyl.
이러한 원료를 2종이상 단량체 전량의 80∼90 중량％ 사용하여 공중합시킨다.These raw materials are copolymerized using 80-90 weight% of 2 or more types of whole monomers.
이외에 사용되는 비닐계 단량체로서는 스티렌 모노머, 아크릴산 히이드록시에틸, 메타아크릴산 하이드록시 프로필 등과 같은 공중합이 가능한 불포화 단량체들이 불포화 결합에 치환되어 사용될 수 있다.In addition, as the vinyl monomer to be used, copolymerizable unsaturated monomers such as styrene monomer, hydroxyethyl acrylate, hydroxy methacrylate, and the like may be substituted with the unsaturated bond.
본 발명에 사용되는 단량체중 메타아크릴산 알킬에스테르 혹은 아크릴산 알킬에스테르류에서 측쇄의 탄소수 1-4인 단량체로 메틸메타아크릴레이트는 80∼90 중량%, 2-하이드록시에틸메타아크릴레이트는 5-10중량%, n-부틸아크릴레이트 혹은 에틸아크릴레이트 3-5중량%, 메타아크릴산 혹은 아크릴산 0.1-5 중량%을 측쇄의 탄소수가 5-14인 단량체로 2-에틸헥실아크릴레이트는 5-10 중량%와 불포화기를 함유한 중유알키드 중간체수지(유형:홍화유, 탈수피마자유, , 무수프탈산 함량:35%, 유장:55% Mn:1500, Tg:256K)는 2-10중량% 이내의 조성으로 적용한다.Of the monomers used in the present invention, alkyl methacrylates or alkyl acrylates are monomers having 1 to 4 carbon atoms in the side chain, and methyl methacrylate is 80 to 90 wt% and 2-hydroxyethyl methacrylate is 5 to 10 wt%. %, 3-5% by weight of n-butyl acrylate or ethyl acrylate, 0.1-5% by weight of methacrylic acid or acrylic acid, monomers having 5-14 carbon atoms in the side chain, and 5-10% by weight of 2-ethylhexyl acrylate. Heavy oil alkyd intermediate resins containing unsaturated groups (type: safflower oil, dehydrated castor oil,, phthalic anhydride content: 35%, whey: 55% Mn: 1500, Tg: 256K) are applied in a composition within 2-10% by weight.
메타아크릴산 알킬에스테르류에서 측쇄의 탄소수 1-4인 다량체로 메틸메타아크릴레이트는 중합될시 도막의 내용제성, 내화학성의 특성을 갖는 중요한 인자로 90중량% 이상 사용하면 내용제성은 양호하지만 도막의 경질화로 도막의 박리, 깨짐현상등이 발생하고 80 중량% 이하로 적용하면 도막이 연질화되어 부착성 및 도면상태는 양호하지만 내용제성 및 내가솔린성의 도막 요구성능에 맞지않음으로 80∼90 중량%가 적절하다.Methyl methacrylate as a multimer having 1 to 4 carbon atoms in the side chain of methacrylic acid alkyl esters is an important factor having solvent resistance and chemical resistance characteristics of the coating film when polymerized. When hardening occurs, peeling and cracking of the coating film occurs, and when applied at 80 wt% or less, the coating film is softened and the adhesion and drawing state are good, but 80 ~ 90 wt% is not satisfied due to the solvent resistance and the resistance to the paint resistance. proper.
불포화기를 함유하고 있는 알키드 중간체수지는 비닐계단량체의 불포화기와 라디칼 반응에 의한 중합을 하여 점착성, 도막박리 방지, 내가솔린성 향상 등의 효과가 있는데 10중량% 이상 적용시 도막의 색변화가 발생할 수 있어 10중량% 이내로 적용하고, 2-하이드록시에틸메타아크릴레리트는 작업성, 내가솔린성을 향상시키는 것으로 하이드록시기를 함유하고 있어 10중량%이상 적용시 내수성, 내약품성, 내구성 등의 문제가 발생되므로 사용용도, 목적에 따라 적절히 조절하고 측쇄의 탄소수가 5-14인 단량체로 2-에틸헥실아크릴레이트는 도막박리, 부착성, 작업성을 향상시키는 것으로 10중량%이상 적용시 내약품성 , 내구성 등의 문제가 발생되므로 10중량%이내가 적절하다.Alkyd intermediate resins containing unsaturated groups can be polymerized by radical reactions with unsaturated groups of vinyl monomers, which improves adhesiveness, prevents film peeling, and improves resistance to oil. It is applied within 10% by weight, and 2-hydroxyethyl methacrylate improves workability and resistance to gasoline, and it contains hydroxy group.When applying more than 10% by weight, problems such as water resistance, chemical resistance, and durability occur. Therefore, 2-ethylhexyl acrylate is a monomer having 5-14 carbon atoms in the side chain, which is appropriately adjusted according to the purpose of use and purpose, and improves film peeling, adhesion, and workability. Since a problem occurs, less than 10% by weight is appropriate.
상기의 비닐계 단량체를 이용하여 상압, 중합개시제의 존재하에서 용액중합으로 공중합시킬 수 있는데 중합촉매는 BPO, TBPO, TBPB, DTBPO, AIBN 등과 같은 라디칼 중합이 가능한 과산화물을 사용할 수 있다.The vinyl-based monomer may be copolymerized by solution polymerization in the presence of atmospheric pressure and a polymerization initiator. The polymerization catalyst may be a peroxide capable of radical polymerization such as BPO, TBPO, TBPB, DTBPO, AIBN, and the like.
중합개시제의 선택을 반응온도에 맞게 적절하게 선정하고 중합개시제의 사용량은 분자량에 큰 영향이 있음으로 적정량을 사용한다Select the polymerization initiator appropriately according to the reaction temperature and use the appropriate amount because the amount of the polymerization initiator has a large influence on the molecular weight.
보통 용액중합에서 중합개시제의 사용량은 비닐계 단량체에 대하여 1∼2 중량% 정도 사용한다.Usually, the amount of polymerization initiator used in solution polymerization is about 1 to 2% by weight based on the vinyl monomer.
용액중합에서 사용되는 용재는 탄화수소계, 알콜계, 에스테르계, 케톤계, 에틸렌 글리콜 유도체계 등이 사용 가능하고 용재의 선택은 건조성 , 반응온도, 분자량을 고려하여 사용한다..Hydrocarbons, alcohols, esters, ketones, ethylene glycol derivatives, etc. may be used for the solution polymerization, and the choice of the solvent should be used considering drying, reaction temperature and molecular weight.
본 발명에서 사용된 용제는 작업성이 양호한 방향족 계통의 탄화수소계를 주로 사용하였다.The solvent used in the present invention mainly used an aromatic hydrocarbon system having good workability.
용액중합의 반응온도는 분자량에 관계가 있음으로 분자량에 맞게 선정하고 보통 80℃에서 120℃로 반응을 실시한다The reaction temperature of the solution polymerization is related to the molecular weight, so it is selected according to the molecular weight.
상기의 비닐계 단량체에 중합개시체, 용제 등을 적절하게 선정하여 용액중합 방법으로 미반응 단량체가 존재하지 않도록 반응을 조절하여 내용제성 및 내가솔린성이 양호한 공중합체의 열가소성 아크릴 수지를 제조한다.A polymerization initiator, a solvent, and the like are appropriately selected for the vinyl monomer, and the reaction is controlled so that an unreacted monomer does not exist by a solution polymerization method, thereby preparing a thermoplastic acrylic resin having a good solvent resistance and resistance to gasoline resistance.
만약 미반응 단량체가 존재하면 도막 형성시 내가솔린성, 내용제성, 옥외내구성 , 부착성 등 제반물성이 떨어짐으로 용액중합시 주의를 요한다.If unreacted monomer is present, it is necessary to use caution when polymerizing the solution because it has poor physical properties such as gasoline resistance, solvent resistance, outdoor durability, and adhesion.
이렇게 하여 제조된 공중합체는 분자량 10,000∼50,000 정도로 현재 사용되고 있는ROLLER,SPRAY 도장방법으로 건축용도의 수지로서 사용될 수 있다.The copolymer prepared in this way can be used as a resin for building use by the ROLLER, SPRAY coating method currently used in molecular weight 10,000 ~ 50,000.
종래 건축용도의 아크릴수지는 도막이 단단하면 내용제성, 내가솔린성, 내화학성 등은 양호하지만 도막이 깨지는 현상이 발생하여 도막의 제기능을 상실하고 수지와의 부착성이 떨어지며 도막이 연질화되면 부착성 및 도막상태는 양호하지만 내용제성 및 내가솔린성 등이 불량하여 그 사용폭이 좁아 범용화가 어려웠으나 양자의 결점을 보완한 본 발명의 아크릴수지로 인하여 건축도료용수지로서 널리 사용할 수가 있는 것이다.Acrylic resins for conventional building use have good solvent resistance, resistance to gasoline, and chemical resistance when the coating is hard, but the coating film is broken, resulting in loss of the function of the coating and poor adhesion to the resin. The condition is good, but the solvent resistance and the resistance to gasoline resistance is poor, its use range is narrow, it is difficult to use the general purpose, but it can be widely used as a building paint resin due to the acrylic resin of the present invention which compensates for the shortcomings of both.
이하 본 발명을 실시예에 의하여 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples.
[실시예 1]Example 1
교반장치, 온도계, 질소투입관, 적하장치(단량체 혼합조, 촉매 혼합조), 환류 냉각기가 부착된 반응기에 개시제 0.9 중량%, 메틸 메타 아크릴레이트 85 중량%, N-부틸 아크릴레이트 5 중량%, 2-하이드록시 에틸 메타 아크릴레이트 5 중량%, 알키드 중간체(OL : 55, Tg :265K, Mn : 1500)4.7 중량%, 메타 아크릴산 0.3 중량%를 톨루엔을 이용하여 반응 고형분이 50%가 되게 하여 반응온도 90∼110℃로 용액 중합시킨다.Agitator, thermometer, nitrogen inlet tube, dropping device (monomer mixing tank, catalyst mixing tank), 0.9 wt% initiator, 85 wt% methyl methacrylate, 5 wt% N-butyl acrylate, 5% by weight of 2-hydroxyethyl methacrylate, an alkyd intermediate (OL: 55, Tg: 265K, Mn: 1500), and 0.3% by weight of methacrylic acid were made to react with 50% solids using toluene. Solution polymerization is carried out at a temperature of 90 to 110 ° C.
반응이 완료되면 불휘발분(NVM)50%, 가드너 점도 Z₃정도, 가드너 색수 1 이하인 점성용액의 중합체(T-1)가 생성된다.When the reaction was completed, a polymer (T-1) of a viscous solution having a nonvolatile content (NVM) of 50%, a Gardner viscosity of Z 3 and a Gardner color number of 1 or less was formed.
[실시예 2]Example 2
교반장치, 온도계, 질소투입관, 적하장치(단량체 혼합조, 촉매 혼합조), 환류 냉각기가 부착된 반응기에 개시제 0.9 중량%, 메틸 메타 아크릴레이트 88 중량%, N-부틸 아크릴레이트 3 중량%, 알키드 중간체( OL : 55%, Tg : 265K, Mn :1500)3.5 중량%, 2-하이드록시 에틸 메타아크릴레이트 5 중량%, 메타아크릴산 0.5 중량%를 톨루엔을 이용하여 반응 고형분이 50%가 되게 하여 반응온도 90∼110℃로 용액 중합시킨다.Stirring device, thermometer, nitrogen inlet tube, dropping device (monomer mixing tank, catalyst mixing tank), 0.9% by weight of initiator, 88% by weight of methyl methacrylate, 3% by weight of N-butyl acrylate, Alkyd intermediate (OL: 55%, Tg: 265K, Mn: 1500) 3.5% by weight, 2-hydroxyethyl methacrylate 5% by weight, methacrylic acid 0.5% by weight to 50% by using toluene Solution polymerization is carried out at a reaction temperature of 90 to 110 ° C.
반응이 완료되면 불휘발분(NVM) 50%, 가드너 점도 Z₃정도, 가드너 색수 1 이하인 점성용액의 중합체(T-2)가 생성된다.When the reaction was completed, a polymer (T-2) of viscous solution having a nonvolatile content (NVM) of 50%, a Gardner viscosity of Z 3 and a Gardner color number of 1 or less was formed.
[실시예 3]Example 3
교반장치, 온도계, 질소투입관, 적하장치(단량체 혼합조, 촉매 혼합조), 환류 냉각기가 부착된 반응기에 개시제 0.9 중량%, 메틸 메타 아크릴레이트 80 중량%, N-부틸 아크릴레이트 6.5 중량%, 2-하이드록시 에틸 메타 아크릴레이트 8 중량%, 메타 아크릴산 0.5 중량%, 알키드 중간체( OL : 55%, Tg : 265K, Mn :1500) 5 중량%를 톨루엔을 이용하여 반응 고형분이 50%가 되게 하여 반응온도 90∼110℃로 용액중합시킨다.Stirring device, thermometer, nitrogen inlet tube, dropping device (monomer mixing tank, catalyst mixing tank), 0.9 wt% of initiator, 80 wt% of methyl methacrylate, 6.5 wt% of N-butyl acrylate, 8% by weight of 2-hydroxyethyl methacrylate, 0.5% by weight of methacrylic acid, and 5% by weight of alkyd intermediates (OL: 55%, Tg: 265K, Mn: 1500) using toluene to make the reaction solid content 50% The solution is polymerized at a reaction temperature of 90 to 110 ° C.
반응이 완료되면 불휘발분(NVM) 50%, 가드너 점도 Z₂정도, 가드너 색수 1 이하인점성용액의 중합체(T-3)가 생성된다.When the reaction was completed, a polymer (T-3) of viscous solution having a nonvolatile content (NVM) of 50%, a Gardner viscosity of Z 2 and a Gardner color number of 1 or less was formed.
[비교예 1]Comparative Example 1
교반장치, 온도계, 질소투입관, 적하장치(단량체 혼합조, 촉매 혼합조), 환류 냉각기가 부착된 반응기에 개시제 0.9 중량%, 메틸 메타 아크릴레이트 95 중량%, 에틸 아크릴레이트 5 중량%를 톨루엔을 이용하여 반응 고형분이 50%가 되게 하여 반응온도 90∼110℃로 용액중합시킨다.0.9% by weight of initiator, 95% by weight of methyl methacrylate and 5% by weight of ethyl acrylate were added to a reactor equipped with a stirring device, a thermometer, a nitrogen input pipe, a dropping device (monomer mixing tank, a catalyst mixing tank), and a reflux condenser. The reaction solid content is 50%, and the solution is polymerized at a reaction temperature of 90 to 110 ° C.
반응이 완료되면 불휘발분(NVM) 50%, 가드너 점도 Z₃정도, 가드너 색수 1 이하인점성용액의 중합체(T-4)가 생성된다.When the reaction was completed, a polymer (T-4) of viscous solution having a nonvolatile content (NVM) of 50%, a Gardner viscosity of Z 3 and a Gardner color number of 1 or less was formed.
[비교예 2]Comparative Example 2
교반장치, 온도계, 질소투입관, 적하장치(단량체 혼합조, 촉매 혼합조), 환류 냉각기가 부착된 반응기에 개시제 0.9 중량%, 메틸 메타 아크릴레이트 76 중량%, N-부틸 아크릴레이트 22 중량%, 메타아크릴산 2 중량%를 톨루엔과 키실렌을 이용하여 반응 고형분이 50%가 되게 하여 반응온도 90∼110℃로 용액중합시킨다.Stirring device, thermometer, nitrogen inlet tube, dropping device (monomer mixing tank, catalyst mixing tank), 0.9 wt% initiator, 76 wt% methyl methacrylate, 22 wt% N-butyl acrylate, 2% by weight of methacrylic acid is solution-polymerized at a reaction temperature of 90 to 110 ° C. using toluene and xylene to make the reaction solid content 50%.
반응이 완료되면 불휘발분(NVM) 50%, 가드너 점도 Z₃정도, 가드너 색수 1 이하인점성용액의 중합체(T-5)가 생성된다.When the reaction was completed, a polymer (T-5) of viscous solution having a nonvolatile content (NVM) of 50%, a Gardner viscosity of Z 3 and a Gardner color number of 1 or less was formed.
[성능시험][Performance Test]
상기의 공중합된 수지 조성물의 성능 시험을 위하여 수지 70.0 중량%, R-902 18.85 중량%, XYLENE 11.15 중량%를 BALL MILL 에 넣고 교반속도 2000 rpm으로 1시간 동안 분산시켜 입도 7 이상의 도료를 만든 다음 탄화수소계와 에스테르계 혼합용제를 사용하여 Ford Cup#4 16∼19초로 spray 점도를 조절하였다.In order to test the performance of the copolymerized resin composition, 70.0% by weight of resin, 18.85% by weight of R-902, and 11.15% by weight of XYLENE were added to a ball mill, and dispersed at a stirring speed of 2000 rpm for 1 hour to prepare a paint having a particle size of 7 or more. Spray viscosity was adjusted to Ford Cup # 4 16-19 seconds using a mixed solvent based on esters.
이렇게 제조된 PWC 35%(TiO₂)백색도료를 slate 시편에 Air spray 로 도장하여 건조도막 30∼40μ 로 만든 후 5일 동안 건조하여 용제 및 시험시약을 침적하였다.The PWC 35% (TiO₂) white paint thus prepared was coated with air spray on the slate specimen to make a dry coating 30-40μ, then dried for 5 days to deposit a solvent and a test reagent.
실시예 (T-1)∼(T-3)과 비교예(T-4), (T-5)의 공중합된 수지 조성물을 도료화하여 상기와 같은 방법으로 시편을 작성 후 용제 및 시험시약에 72시간 침적시킨 후의 도막성능을 비교, 측정한 결과치는 아래와 같다.Paint the copolymerized resin compositions of Examples (T-1) to (T-3) with Comparative Examples (T-4) and (T-5) to prepare the specimens in the same manner as above, and then to the solvent and test reagent. The result of comparing and measuring the coating film performance after 72 hours immersion is as follows.
상기 실험의 결과와 같이 단량체가 적절하게 배합되면 내용제성 및 도막의 상태가 우수하지만 비교예와 같이 단량체의 선정이 경질 혹은 연질의 한쪽으로 편중되면 내용제성이 불량하거나 도막이 깨지는 결점이 있어 도막의 제반기능이 상실된다.As the result of the experiment, when the monomer is properly blended, the solvent resistance and the state of the coating film are excellent.However, as in the comparative example, when the monomer is selected to be hard or soft, the solvent is poor or the coating film is broken. The function is lost.
상술한 바와 같이 제조되는 본 발명의 열가소성 아크릴수지의 내용제성, 내가솔린성이 양호하고 도막의 깨짐현상, 박리현상이 발생하지 않는 효과가 있어 건축용 수지와 건축도료용수지로 널리 사용할 수가 있는 매우 획기적인 제품인 것이다.It is a very innovative product which can be widely used as a building resin and a building paint resin because it has good effect of solvent resistance and gasoline resistance of the thermoplastic acrylic resin of the present invention manufactured as described above and does not cause cracking or peeling of the coating film. will be.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950011873A KR0167539B1 (en) | 1995-05-11 | 1995-05-11 | The preparation of anti-soluble thermoplastic acrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950011873A KR0167539B1 (en) | 1995-05-11 | 1995-05-11 | The preparation of anti-soluble thermoplastic acrylic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR960041211A KR960041211A (en) | 1996-12-19 |
| KR0167539B1 true KR0167539B1 (en) | 1999-03-20 |
Family
ID=19414420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019950011873A KR0167539B1 (en) | 1995-05-11 | 1995-05-11 | The preparation of anti-soluble thermoplastic acrylic resin |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR0167539B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190089619A (en) | 2018-01-23 | 2019-07-31 | 주식회사 케이에스넷 | Method and apparatus for transit of financial service |
-
1995
- 1995-05-11 KR KR1019950011873A patent/KR0167539B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190089619A (en) | 2018-01-23 | 2019-07-31 | 주식회사 케이에스넷 | Method and apparatus for transit of financial service |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960041211A (en) | 1996-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110577614B (en) | Preparation of high-solid-content hydroxy acrylic acid dispersion | |
| US4740546A (en) | Aqueous dispersion of vinyl copolymer resin | |
| JP5156160B2 (en) | Leveling agent for surface coating | |
| KR0142411B1 (en) | Thermosetting resin composition | |
| US4312797A (en) | Aqueous coating composition | |
| US3551525A (en) | Surface coating copolymers containing etherified n-methylolamide | |
| FI83429B (en) | VATTENFRIA BESTRYKNINGSKOMPOSITIONER, VILKA INNEHAOLLER FILMBILDNINGSMATERIAL, KOLVAETEVAETSKA OCH POLYMERISK STABILISATOR. | |
| US4687822A (en) | Acrylic resin composition for use in high solids paints | |
| US4309321A (en) | Aqueous coating composition | |
| US4565839A (en) | Aqueous emulsion composition | |
| AU690284B2 (en) | Catalytic compositions and coatings made therefrom | |
| US4122052A (en) | Emulsion composition | |
| US5726249A (en) | Coating compositions with branched polymer | |
| US4245074A (en) | Method for the preparation of an acrylate copolymer and liquid coating composition having a high solids content based on an acrylate copolymer thus prepared | |
| KR0167539B1 (en) | The preparation of anti-soluble thermoplastic acrylic resin | |
| JPH08509768A (en) | Thermosetting coating composition | |
| US4098841A (en) | Thermoplastic copolymers and preparation thereof | |
| US3288736A (en) | Coating compositions comprising partial fatty acid esters of hydroxyl interpolymers | |
| CA1042582A (en) | Producing self-stabilizing polymer dispersions in hydrocarbon liquids | |
| CA2037581A1 (en) | Aqueous dispersions of hybrid polymers and coating compositions containing same | |
| JPH02115238A (en) | Resin composition for plastic coating material | |
| CN1228442A (en) | High solid low viscosity acrylic resin and its preparing method | |
| US3449277A (en) | Coating compositions comprising drying oil acid esters of styrene-acrolein copolymer-polymer reaction products | |
| JPS6223002B2 (en) | ||
| US2603611A (en) | Styrenated oil-tall oil vinyl esters coating compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20070723 Year of fee payment: 10 |
|
| LAPS | Lapse due to unpaid annual fee |