KR910008315B1 - 개량된 수분 농축제 - Google Patents

개량된 수분 농축제 Download PDF

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KR910008315B1
KR910008315B1 KR1019830004269A KR830004269A KR910008315B1 KR 910008315 B1 KR910008315 B1 KR 910008315B1 KR 1019830004269 A KR1019830004269 A KR 1019830004269A KR 830004269 A KR830004269 A KR 830004269A KR 910008315 B1 KR910008315 B1 KR 910008315B1
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후앙 초르
칼 슐라체르 로버트
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더 비. 에프. 굿드리치 캄파니
존 디. 하니
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Abstract

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Description

개량된 수분 농축제
본 발명은 개량된 수분 농축제에 관한 것이다.
미국특허 제3,915,921호에는 60-95중량％의 카르복실산 단량체를 함유하고, 알킬기가 10-30개의 탄소원자를 가진 아크릴산의 알킬에스테르를 39.9-4중량％ 함유하며 0-6중량％의 교차결합된 단량체를 갖는 공중합체에 관해 기술되어 있다. 이러한 중합체들은 적어도 부분적으로 염기성 물질에 의해 중화되었을 경우 많은 양의 물을 흡수하여 효과적인 농축제가 되며 소금과 같은 염의 존재하에서는 미국특허 제2,798,053호에 기술된 종래의 농축제보다 점도 상실이 상당히 줄어든 물 점액질을 형성한다. 상기한 두 가지 특허에서의 물질들은 많은 용도를 가지고 있는 반면, 이러한 물질들이 다른 많은 용도에 대해서는 불만족스럽다. 예를 들면 이러한 물질이 직물 염색에서 염색제내의 농축제로 사용될 경우이다. 이러한 종래의 중합체들을 염색제의 제조에 사용할 경우, 염색제는 끈적거리게 되고, 그리고 또는 나쁜 유변학적 특성을 갖으며, 점성이 변하게 되어 염색이 좋지 않게 된다. 즉, 그러한 염색제를 사용하면 윅킹(wicking) 또는 플러싱(flushing)그리고 세탁시에 탈색등으로 인하여 선명한 염색과 좋은 색도를 얻을 수 없다. 그러므로 본 발명은 이러한 단점들과 다른 문제점들을 갖지 않는 계량된 농축제에 관한 것이다.
98.9-95.5중량％의 적어도 하나의 활성 이중 결합을 갖는 올레핀과 같은 불포화 카르복실산과 알킬기가 1-약 3.5중량％의 10-30개의 탄소 원자를 함유하는 아크릴산 또는 메타아크릴산의 알킬 아크릴레이트 에스테르와 0.1-1중량％ 이하의 교차 결합된 단량체로 된 중합체는 높은 이온성 조건하에서 많은 경우에 효과적인 농축제로서 사용되며, 낮은 농도에서 종래의 농축제보다 좋거나 또는 동등한 결과를 얻기 위해서도 사용 가능하다. 이러한 중합체들은 고이온, 가변성 이온을 함유하며, 반응성 염료, 직접 염료, 분산 염료등이 염색에 사용될 경우 특별히 효과적이다. 더우기, 스크리인 염색에서는 계량된 염색제는 본 발명의 새로운 중합체를 함유하고 있기 때문에 염색압의 반향이 적은 유변학적 특성을 가지고 있으며, 그렇게 완성된 직조 염색은 침투가 좋다. 염색의 결과는 선명도, 윅킹의 결핍, 침투도, 수평도, 색도의 우수한 조합이다.
본 발명에 사용된 중합체 생산에 유용한 카르복실 단량체는 적어도 하나의 활성화된 탄소-탄소의 이중결합과 적어도 하나의 카르복실기를 함유하는 올레핀과 같은 불포화된 카르복실산이다. 즉 단량체 내에서 카르복실기에 대해 α-β위치,
Figure kpo00001
, 또는 메틸렌기 CH₂=＜의 일 부분으로 올레핀 이중 결합이 존재하기 때문에 중합 반응에 역할을 한다. 이러한 부류의 올레핀과 같은 불포화 산은 아크릴산 자체, 메타아크릴산, 에타아크릴산, α-클로로-암크릴산, α-시아노-아크릴산, β-아크릴록시 프로피온산, 소르브산, α-클로로소르브산, 안젤산, 신남산, ρ-클로르 신남산, β-스티릴, 아크릴산, 이타콘산, 시트라콘산, 메사콘산, 글루타콘산, 아코니트산, 말레인산, 퓨마산등과 같은 아크릴산과 트리카르복실에틸렌과 같은 물질을 함유하고 있다. 본 명세서에 사용된 카르복실산이라는 단어는 폴리카르복실산 뿐만 아니라 동일한 폴리카르복실산 분자에 위치한 두개의 카르복실기로 부터 한개의 물분자를 제거시킴으로써 형성되는 무수기를 함유하는 말레인산 무수물과 같은 이러한 산의 무수물을 포함한다. 본 발명에 사용되는 말레인산의 무수물과 다른 산의 무수물은 다음과 같은 일반적인 구조를 가지고 있다 :
Figure kpo00002
상기 구조식에서 R과 R°는 수소, 할로겐, 시아노겐(-C≡N)기, 알킬기, 아릴기, 알카릴기, 아랄킬기와 메틸, 에틸, 프로필, 옥틸, 데실, 페닐, 톨릴, 크실릴, 벤질, 사이클로헥실등과 같은 사이클로 알킬기로 구성된 그룹으로 부터 선택된다.
바람직한 카르복실 단량체는 다음의 구조식을 갖는 아크릴산이다 :
Figure kpo00003
상기구조식에서 R²는 수소, 할로겐, 시아노겐(-C≡N)기 1가의 알킬기, 1가의 아릴기, 1가의 아랄킬기,1가의 알카릴기와 1가의 사이클로알리파틱기로 구성된 그룹으로 부터 선택된 치환기이다. 이러한 그룹중에서 아크릴산, 메타아크릴산, 에타아크릴산이 가장 바람직하다. 다른 유용한 카르복실 단량체는 말레인 무수물 또는 말레인산이다. 사용된 산의 양은 전체 사용된 단량체의 약 95.5-약 98.9중량％이다. 좀 더 바람직한 범위는 약 96-약 97.9중량％이다.
아크릴 에스테르 단량체는 다음의 구조식으로 대표되는 아크릴산의 유도체를 포함한다 :
Figure kpo00004
상기구조식에서 R³는 10-30개의 탄소원자, 바람직하기로는 12-22개의 탄소원자를 함유하는 알킬기이며 R²는 약 1-약 3.5중량％로 공중합체 내에 존재하는 수소, 메틸 또는 에틸기이다.
대표적인 아크릴레이트는 데실 아크릴레이드. 이소데실 아크릴레이트, 로릴 아크릴레이트, 도데실아크릴레이트, 스트레아릴아크릴레이트, 대응되는 메타아크릴레이트들, 즉 데실메타아크릴레이트, 이소데실메타아크릴레이트, 로릴 메타아크릴레이트, 도데실 메타아크릴레이트, 스테아릴 메타아크릴레이트 등을 포함한다. 둘 또는 셋 또는 그 이상 긴 체인을 가진 아크릴 에스테르의 혼합물은 카르복실 단량체들중 하나와 매우 잘 중합된다.
중합체들은 적어도 두개의 단말기 CH₂＜, 예를 들면 부타디엔, 이소프렌, 디비닐 벤젠, 다비닐 나프탈렌, 알릴 아크릴레이트 등을 함유하는 다기능 비닐리덴 단량체와 교차결힙된다. 공중합체 제조에 특별히 유용한 교차 결합된 단량체는 분자 하나에 하나 이상의 알케닐 에테르를 가진 폴리알케닐 폴리에테르이다. 올레핀이중 결합이 단말 메틸렌기, CH₂=C＜에 붙어서 존재하는 알케닐기가 가장 좋다. 그것들은 적어도 4개의 탄소원자와 적어도 2개의 하이드록시기를 함유하는 폴리하이드릭 알콜의 에테르화에 의해 제조된다. 이러한 부류의 화합물은 알릴 클로라이드 또는 알릴 브로마이드 등과 같은 알케닐 할라이드를 하나 또는 그 이상의 폴리하이드릭 알콜의 강한 알칼리성 수용액과 반응시킴으로써 제조할 수 있다. 생성물은 에테르기의 숫자가 변하는 폴리에테르의 착화합 혼합물이다. 분석 결과로 각기 분자에 대하여 에테르기의 평균 숫자를 알 수 있다. 폴리에테르 교차결합제의 효율은 분자에서 잠재적으로 중합될 수 있는 기의 숫자를 증가시킨다. 분자당 평균적으로 둘 이상의 알케닐 에테르 기를 함유하는 폴리에테르를 이용하는 것이 바람직하다. 다른 교차결합 단량체는 예를 들면 디알릴 에스테르, 디메탈릴 에테르, 알릴 또는 메탈릴 아크릴레이트와 아크릴아미드, 테트라알릴주석, 테트라 비닐 실레인, 폴리알케닐 메탄, 디아크릴레이트, 디메타크릴레이트, 디비닐벤젠과 같은 디비닐 화합물, 폴리알릴 포스페이트, 디알릴록시 화합물, 포스파이트 에스테르 등을 포함한다.
대표적인 교차 결합제로는 알릴 펜타에리트리톨, 알릴 수크로즈, 트리메틸올 프로판 트리아크릴레이트, 1,6-헥산디올 디아크릴레이트, 트리메틸올 프로판 디알릴에테르, 펜타에리트리톨 트리아크릴레이트, 테트라메틸렌 디메타아크릴레이트, 에틸렌 디아크릴레이트, 에틸렌 디메타크릴레이트, 트리에틸렌 글리콜 디메타크릴레이트 등이 있다. 알릴 펜타에리트리톨, 트리메틸올 프로판 디알릴에테르와 알릴 수크로즈가 좋은 중합제로 제공된다. 중합체 혼합물은 항상 카르복실산 단량체와 다른 단량체 전체에 기준하여 0.1-1중량％이하의 교차 결합된 단량체를 함유하며 바람직하기로는 0.1-0.6중량％이다.
다른 비닐리덴 단량체는 농축제의 염기성 특성이 역으로 작용하지 않는 소량의 범위내에서 산 대신에 쓰일 수 있다. 그 예로는 아르릴로니트릴, 메타크릴로니트릴, 아크릴아미드, 메타크릴아미드,스티렌, 비닐톨루엔, 비닐 메틸에테르, 비닐에틸케톤, 부타디엔, 비닐 아세테이트, 메틸 아크릴레이트, 부틸 아크릴레이트, 시아노 프로필, 아크릴레이트, 메톡시 에틸, 아크릴레이트, 클로로에틸, 아크릴레이트,염화비닐, 비닐리덴 클로라이드, 말레인산과 퓨마산의 에스테르, 비스(β-클로로에틸)비닐 포스포네이트등이며 상기 내용은 본기술에 숙련된 사람들에게는 잘 알려져 있다.
중합체를 포함하는 카르복실은 그 분자량이 약 500이상에서 수 백만 까지로 크며, 보통 약 10,000-900,000 이상이다.
단량체의 중합은 보통 폐 용기내에서 자생압력 또는 인위적으로 유도된 압력하에서 불활성 기체내에 자유기 촉매의 존재하에 수행되거나 또는 개방용기 내의 대기압하에서 환류조건으로 수행하고나, 적당한 교반과 함께 회분식 또는 연속식으로도 가능하다. 중합온도는 약 0°-125℃ 또는 그 이하, 그 이상으로 변화시킬 수 있다. 25°-90℃에서 자유기 촉매를 이용하여 중합하는 것이 중합체 생성율을 75％-100％로 하는데 일반적으로 효과적이다. 촉매를 구성하는 전형적인 자유기는 나트륨, 칼륨의 괴산화물과 암모니움 퍼설페이트, 카프릴릴 과산화물, 벤조일 과산화물, 과산화수소, 페라르고닐 과산화물, 큐멘하이드로퍼록사이드, tert-부틸디퍼프탈레이트, tert-부틸 퍼벤조에이트, 나트륨 퍼아세테이트, 디(2-에틸헥실)퍼옥시디카르보네이트 등과 아조디이소부티릴 니트릴과 같은 아조 촉매들이다. 사용되는 다른 촉매들은 "레독스"형 촉매와 활성화된 중금속 촉매이다. 자외선도 자유기의 원천으로서 사용될 수 있다. 어떤 경우에도 촉매없이 단지 열에 의해서만 중합되며 제어하기도 편하다. 단량체들은 중합과정중에 회분식 또는 연속식으로 부가될 수 있으며, 또는 통상적으로 중합 기술에서 사용되는 다른 방식도 가능하다.
중합 반응은 하나 이상의 단량체 성분에 대해 용해 효과를 가지고 있으며 생성된 중합체에는 실질적으로 그런 효과가 없는 불활성 액체내에서 수행된다. 즉, 중합에 사용되는 액체 매체는 바람직하기로는 그 속에서 단량체가 용해되고 중합체는 용해되지 않는 것이다. 그러한 물질들은 일반적으로 단량체에 대해 용매가되고 중합체에 대해서는 용매가 아닌 유기액이며, 또는 중합체 생성물이 바람직하게 매우 미세한 부스러지기 쉽고 솜털 같은 침전물로 얻어질 수 있도록 그러한 용매의 혼합물일 수도 있다. 일반적으로 이러한 용매들은 용해도가 약 5-약 10(cal/㎤)이며 유전도가 약 1.7-9.5이다. 대표적인 용매로는 6-8개의 탄소원자를 함유하는 탄화수소, 벤젠, 테트랄린, 헥산, 헵탄, 사이클로헥산, 사염화탄소, 클로로포름, 트리클로로에틸렌, 염화 메틸, 염화 에틸, 메틸렌 크롤라이드 : 적어도 4개의 할로겐 원자를 함유하는 클로로푸로로메탄과 클로로푸로로에탄과 같은 클로로푸로로알칸 : 메탈 아세테이트와 에틸 아세테이트와 같은 에스테르 : 메탄올, 에탄올, 부탄올 등을 포함하는 알콜등이 있다. 일반적으로 사용되는 유기용매의 양은 중합될 단량체에 대해 과잉량이며 비율은 적어도 1중량％의 단량체와 99중량％의 유기 용매로부터 약 50중량％ 단량체와 50중량％의 용매까지이다.
본 발명에 포함된 단량체로 제조된 중합체는 직물 염색, 특히 높은 이온 함량을 가진 반응염료, 직접염료, 분산염료를 포함하는 염색제와 같은 높은 이온 함량의 염료가 사용될 경우 효율적인 농축제 임이 알려졌다. 이러한 이온 조건하에서 본 발명의 중합체는 염료 농축에 있어서 기존의 중합체보다 더욱 효율적임이 알려졌다. 더우기, 본 발명의 중합체를 함유하는 염색제는 기존의 중합체에 비교하여 상당히 낮은 점도에서 더 좋은 염색도, 선명도, 색도를 나타낸다. 결과적으로, 본 발명의 중합체의 최저 수준이 기존의 중합체와 비슷한 염색도를 얻을 수 있다.
미국특허 제3,915,921호에 기술된 중합체와 비교할때, 본 발명의중합체로 덜 끈적거리고, 더 윤택한 염색제 생산이 가능한 것이 알려졌다. 이러한 형태의 염색제는 스크리인-염색에 더욱 효과적인데, 그 이윤는 염색봉에 의해 전달된 압력이 줄어들 때 염색제의 탄력을 감소시키기 때문이다. 본 발명의 중합체를 이용한 직물 염색은 좀 더 좋은 침투효과와 좀 더 좋은 수평도를 준다. 중합체 내에 교차 결합된 단량체의 양을 증가시킴으로써 끈적거리는 성질을 줄인 중합체는 본 발명의 중합체보다 더 큰 윅크(도는 플러쉬) 현상을 나타낸다. 본 발명의 중합체는 선명도(즉, 윅킹이 없음), 침투도, 수평도, 색도의 훌륭한 조합으로 염색을 하게된다.
그러한 중합체 물질은 바람직하기로는 약 2.5-3.5중량％의 긴 체인을 가진 알킬 메타크릴레이트, 또 바람직하기로는 체인이 약 12-22개의 탄소원자를 함유하는 단량체 혼합물로부터 쉽게 얻어지며, 그러한 중합체는 바람직하기로는 약 0.1-0.6중량％의 알릴 펜타에리트리톨, 트리 메틸올프로판 디알릴에테르 또는 알릴 수크로즈와 같은 교차 결합체, 아크릴 산에 남아 있는 단량체들과 같이 사용된다.
이러한 중합체들이 5중량％ 정도로 알킬 메타 아크릴레이트의 양을 많이 함유할 경우, 이러한 농축제를 함유하는 염색제는 유변학적 성질이 좋지 않게 되어 직물의 스크리인 염색에 사용될 경우, 상기 바람직한 유변학적 특성을 가진 중합체를 함유하는 염색제보다 색도가 나쁘게 되는 반면 상기 바람직한 특성을 가진 중합체를 함유하는 염색제는 훌륭한 색도, 즉 염색후의 직물을 세척한 후에 좋은 색도를 나타내게 된다.
교착 결합된, 단량체의 양 역시 여러가지 경우에 이러한 중합체내에서 중요하게 된다. 그 범위는 약 0.1-약 0.6이며 바람직하기로는 0.3이다. 염색제에 많은 양의 교차결합 물질이 사용될 경우, 즉 1중량％가 사용될 경우, 이온 농도에 관한 감도가 증가하게 되어 변색, 색의 재현성 결핍등이 나타나게 되고 염료는 내부에 어느정도의 염을 가지고 있고 외부에서 조절하지 않고 이러한 변화에 대응하기 위하여 교차 결합 물질의 많은 양을 함유하는 중합체 내에서 유연성이 결핍되어 한 성분에서 다른 성분으로 변하게 된다. 본 발명의 중합체의 단량체의 필요한 부분과 어느 임계농도를 넘어선 교차 결합물질의 과다한 양을 함유하는 염색제를 사용할 경우 염색물의 윅킹 현상이 나타난다.
본 발명의 잇점과 실제를 설명하기 위한 다음의 실시예에서의 중합체는 다음의 일반적인 방법으로 제조되었다 : 아크릴산, 아크릴레이트 에스테르, 교차결합 단량체는 불활성 기체하의 교반 반응조내에서 벤젠을 중합 매개체로 하여 중합되었다. 중합은 약 86℃에서 벤젠내에서 개시제로서 로릴과산화물과 17％ 단량체를 반응시켜 수행되었다. 반응 종료시에, 중합체는 100℃의 로터증발기내에서 건조되었다. 무개를 잰 중합체를 500ml의 증류수에 첨가하고 1％와 2％중합체를 함유하는 점액질을 제조하기 위해 수산화나트륨 수용액으로 중화시켰다. 이런 점액질의 점도는 20rpm에서 Brookfield 점도계로 측정했다. 물 용액에 소금을 부가하여 1％,2％,3％ 염을 함유하는 점액질을 생성하고 각 간격마다 점도를 측정했다.
[실시예]
중합체를 제조하기 위하여 벤젠 1100gm을 잠수형 교반기를 갖춘 교반 반응조에 채웠다. 250.28gm의 아크릴 산, 5.72gm의 스테아릴 메타크릴레이트, 0.858gm의 알릴펜타에리트리톨을 반응기에 부가하고, 반응기에 부가된 200g의 벤젠으로 용기를 세척했다. 반응기는 78℃로 가열되고 30분동안 2ft³/hr의 질소로 정화시켰다. 50gm의 벤젠에 0.4gm의 로릴 퍼옥사이드를 반응기에 부가하고 반응기에 부가된 50gm의 벤젠으로 반응용기를 세척했다. 중합반응은 5시간동안 온도를 80°-81℃로 제어하면서 진행시켰다. 반응의 최종 단계에서 중합체는 로터 증발기에서 100℃로 건조되고 다시 중합체는 500ml의 증류수에 부가되어 18％ NaOH용액으로 pH 7로 중화되었다.
일련의 중합체들이 표 1에 나타난 비율대로 상기 방법에 의해 제조되었다. 1％,2％ 중합체 용액의 점도가 점액질에 부가된 0, 1％2％,3％ NaCl 용액과 함께 결정되었다. 20rpm에서 Brookfield 점도계로 측정된 점도가 표 1에 나타나 있다.
[표 1]
Figure kpo00005
(a)phm=100개의 단량체에 대한 갯수
본 발명의 새로운 중합체의 용도와 이점을 설명하기 위하여 염색제의 유변학적 특성과 점도를 시험하기 위해 중합체로 염색제를 제조하고 기질에 염색을 했을때 윅킹과 색도가 측정되었다. 첫째, 중합체의 맑은 농축액을 중합체의 20중량％를 광물성물질(이소파라핀 혼합물, 비점은 207-254℃)의 65중량％에 부가시키서 얻고 20분간 교반시켰다. 나트륨카보네이트의 15중량％가 혼합물내에 교반주입되고 원하는 정도로 중화된 중합체염의 용액을 만들기 위해 20분간 교반되었다. 하나는 검은색의 염료이고 다른 하나는 적색 염료인 두개의 염기성 염색제가 제조되었다. 일반 제법은 다음과 같다.
Figure kpo00006
(1) 100％를 만들 수 있는 양
(2) 0.7-1.5％ 중합체가 되는 양
(3) 1.2-2.0％ 중합체가 되기 위한 양
(a) 모노클로로트리아진 염료(Ciba-Geigy사제품)
잠수형 교반기를 갖춘 용기에서 냉수에 실리콘 소포제와 계면활성제인 노닐페녹시폴리(에틸페녹시)에탄올을 용해시키기 위해 일반적인 방법으로 교반한다. 이 용액에 염료를 부가하고, 요소를 온수에 녹인다. 중합체 농축물은 혼합물내의 원하는 ％중합체를 얻기 위해, 즉, 혼합물내에 1.2％ 중합체를 얻기 위해 20％ 농축물 6％를 부가한다. 그리고 20분동안 교반시키고 KHCO₃및/또는 Na2CO3를 혼합물에 부가시키고 20분간 교반시킨다.
상기한 염색제 혼합물을 이용하여 (1) 반응성 흑색 8과 (2) 반응성 적색 24 염료 염색제를 3중량％의 스테아릴 메타크릴레이트와 97중량％의 아크릴산, 상기 두개의 단량체의 0.4％에 해당하는 알릴펜타에리트리톨과 함께 제조되었다. 염색제의 점도는 20rpm에서 Brookfield 점도계로 측정되었다. 그리고 염색제는 면직물의 스크린 염색에 사용되었다. 염색후에, 염색된 직물은 100℃에서 5분간 건조되었고 100％ 포화된 스팀으로 105℃에서 10분간 스팀을 쬐었고, 찬 물로 세척하고, 5분 동안 100℃의 Igepal CO-630 수용액에서 교반되어 찬 물로 세척하고 100℃에서 10분동안 건조되었다. 윅킹이 있을 경우 그 정도는 mm로 측정되었고 색가(Color value)(K/S)는 염색된 표본의 ％반사를 측정하는데 사용되는 Photovolt Reflection Meter에 의해 측정되었다. 이러한 반사 수치(R)은 다음과 같은 Kubelka-Munk식의 개량된 형태로 치환된다 :
Figure kpo00007
(E.R.Trotman, "Dyeing and Chemical Technology of Textile Fibers" 643페이지, 4판, 1970, Charles Griffin Company Ltd., 런던, 영국) 사용된 중합체의 농도와 얻어진 시험결과는 표 2에 나타나 있다.
[표 2]
Figure kpo00008
5％의 스테아릴 메타크릴레이트, 0.1％ 알릴 펜타에리트리톨과 94.9％ 아크릴 산을 함유하는 중합체 1.0％를 포함하는 8％의 반응성 흑색 8로 된 염색제가 좋은 염 또는 이온 저항성을 보이며, 즉 염색제의 고점도와 유변학적 특성은 불만족스럽고 염색제가 너무 끈적거려 스크린 염색이 거의 불가능하며 염색결과는 아주 불량한 색도를 나타낸다. 이 염료가 3중량％의 스테아릴 메타크릴레이트, 0.3중량％의 알릴 펜타에리트리톨을 함유하는 중합체를 포함하도록 제조된 경우, 염색제는 스크린 염색이 윅킹이 없이 좋은 색도를 나타낼 수 있도록 하는 개량된 유변학적 특성을 준다. 3중량％의 스테아릴 메타크릴레이트, 0.8중량％의 알릴펜타에리트리톨을 함유하는 중합체를 염색제에 사용할 경우 최소의 염 저항성을 나타냈다. 즉, 염색제의 점도가 매우 낮고 색도가 만족스러운 반면 매우 나쁜 윅킹이 나타나고 염색이 얼룩지게 나타났다.

Claims (9)

  1. 95.9-98.9중량％의 올레핀성 불포화된 카르복실 단량체, 약 1-3.5중량％인 다음 구조식(Ⅰ)의 아크릴레이트 에스테르와 불포화 이중결합이 각기 비공액인 CH₂=C＜기를 함유하는 0.1-1중량％ 이하의 중합가능한 교차결합된 단량체를 함유하는 단량체 혼합물로 된 중합체 조성물 :
    Figure kpo00009
    (Ⅰ)
    상기 구조식에서 R은 탄소원자수가 10-30인 알킬기이며 R1은 수소, 메틸 또는 에틸을 나타낸다.
  2. 제 1항에 있어서, 상기 카르복실산 단량체가 아크릴산, 메타크릴산, 말레인산으로 구성된 그룹으로부터 선택된 것을 특징으로 하는 중합체 조성물.
  3. 제 2항에 있어서, 상기 교차결합된 단량체가 분자하나에 하나 이상의 알케닐 에테르기를 함유하는 폴리하이드릭알콜의 폴리알케닐 폴리에테르이며, 상기 폴리하이드릭 알콜이 적어도 3개의 탄소원자와 적어도 3개의 하이드록시 기를 갖는 것을 특징으로 하는 중합체 조성물.
  4. 제 3항에 있어서, 약 96-97.9중량％의 아크릴산, 알킬기가 12-22개의 탄소원자를 함유하고 R₁이 메틸인 약 2.5-3.5중량％의 아크릴레이트 에스테르, 그리고 교차 결합된 단량체의 양이 약 0.2-0.6중량％로 구성된 것을 특징으로 하는 중합체 조성물.
  5. 제 4항에 있어서, 교차결합된 단량체가 알릴 펜타에리트리톨, 트리메틸올프로판 디알릴에테르 또는 알릴 수크로즈인 것을 특징으로 하는 중합체 조성물.
  6. 제 5항에 있어서, 아크릴레이트 에스테르가 약 3-3.5중량％의 스테아릴 메타크릴레이트이고 약 0.2-0.4중량％의 알릴 펜타에리트리톨이 존재하는 것을 특징으로 하는 중합체 조성물.
  7. 약 2.5-3.5중량％의 구조식(Ⅰ)의 아크릴레이트 에스테르와 불포화 이중결합이 각기 비공액인 CH₂=C＜기를 함유하는 약 0.2-0.6중량％의 중합 가능한 교차결합된 단량체와 약 95.9-97.3중량％의 아크릴산의 중합체의 염저항성 물 농축염과 액체 매체, 염료로 구성된 염색제 조성물 :
    Figure kpo00010
    (Ⅰ)
    상기 구조식에서 R은 탄소원자 10-30인 알킬기이며 R₁은 수소 또는 메틸기를 나타낸다.
  8. 제 7항에 있어서, 아크릴레이트 에스테르에서 R이 메틸기이고 약 0.2-0.4중량％의 알릴 펜타에리트리톨, 트리메틸올프로판 디알릴 에테르 또는 알릴 수크로즈 교차결합제가 존재하는 것을 특징으로 하는 염색제 조성물.
  9. 제 8항에 있어서, 아크릴레이트 에스테르가 약 3중량％로 존재하는 스테아릴 메타크릴레이트이며 교차결합제가 알릴 펜타에리트리톨인 것을 특징으로 하는 염색제 조성물.
KR1019830004269A 1983-06-13 1983-09-12 개량된 수분 농축제 KR910008315B1 (ko)

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FR3145688A1 (fr) 2023-02-15 2024-08-16 L'oreal Composition comprenant une émulsion de silicone particulière, un polymère vinylique amphotère ou cationique, des tensioactifs et un copolymère acrylique
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FR3147099A1 (fr) 2023-03-27 2024-10-04 L'oreal Composition à deux phases
FR3147098A1 (fr) 2023-03-28 2024-10-04 L'oreal Composition à deux phases

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EP0128237A1 (en) 1984-12-19
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ZA836734B (en) 1984-07-25
GR79062B (ko) 1984-10-02
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US4509949A (en) 1985-04-09
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FI833317A (fi) 1984-12-14
JPH0653857B2 (ja) 1994-07-20
JPS59232107A (ja) 1984-12-26
PT77563A (en) 1983-11-01
ES525822A0 (es) 1985-03-01
ES8503693A1 (es) 1985-03-01
AU1912183A (en) 1984-12-20
DK457883A (da) 1984-12-14
FI833317A0 (fi) 1983-09-16
PT77563B (en) 1986-05-05
DE3380063D1 (en) 1989-07-20
MX165410B (es) 1992-11-10
IN159148B (ko) 1987-03-28

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