KR970011245B1 - Fluorine-containing copolymer for textiles treatment - Google Patents
Fluorine-containing copolymer for textiles treatment Download PDFInfo
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- KR970011245B1 KR970011245B1 KR1019950006685A KR19950006685A KR970011245B1 KR 970011245 B1 KR970011245 B1 KR 970011245B1 KR 1019950006685 A KR1019950006685 A KR 1019950006685A KR 19950006685 A KR19950006685 A KR 19950006685A KR 970011245 B1 KR970011245 B1 KR 970011245B1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
Abstract
Description
본 발명은 섬유처리용 공중합체에 관한 것으로서, 더욱 상세하게는 퍼플루오르알킬 함유 화합물, 페녹시폴리옥시알킬글리콜(메타)아크릴레이트, 하이드록시알킬(메타)아크릴레이트 및 염화비닐리덴을 공중합시킨 공중합물로서 이를 의류나 섬유와 같은 직물표면에 처리하여 발수 발유성의 향상은 물론 직물 또는 비직물의 표면으로부터 오염물의 이탈을 용이하게 하여 세탁성을 증진시킬 수 있는 섬유처리용 공중합체에 관한 것이다.The present invention relates to a copolymer for fiber treatment, and more particularly, copolymerization of a perfluoroalkyl-containing compound, a phenoxypolyoxyalkylglycol (meth) acrylate, hydroxyalkyl (meth) acrylate, and vinylidene chloride. The present invention relates to a fiber treatment copolymer capable of improving water repellency and water-repellency as well as water and oil repellency by facilitating the removal of contaminants from the surface of a fabric or a non-woven fabric by treating it as a water or a textile surface such as clothing or textiles.
섬유제품 처리제로서 유용한 다수의 폴로오르공중합체 조성물이 제시되어 있으나 [미국 특허 제3,574,791호 ; 미국 특허 제3728,151호 ; Senshoku Kogyo 29(12), pp. 599-609(1981)], 이 플루오르공중합체들은 일반적으로 섬유표면에 발수성 및 발유성을 부여할 수 있는 퍼플루오르알킬기를 포함하고 있어 이를 직물의 표면에 코팅할 경우 단순히 발수성과 발유성은 부여하지만 세탁시 오염물질의 이탈을 용이하게 하는 SR(soil release)성은 기대할 수 없었다.There are a number of poloorcopolymer compositions that are useful as textile processing agents, but are described in US Pat. No. 3,574,791; US Patent No. 3728,151; Senshoku Kogyo 29 (12), pp. 599-609 (1981)], these fluorocopolymers generally contain perfluoroalkyl groups that can impart water and oil repellency to the fiber surface, which, when coated on the surface of the fabric, simply gives water and oil repellency. Soil release (SR), which facilitates the removal of contaminants during washing, could not be expected.
따라서, 발수성과 발유성이 우수하면서도 SR성이 우수한 방오가공제를 제조하고자 하는 노력은 지속적으로 진행되어 왔는 바, 미국 특허 제2,642,416호 ; 미국 특허 제3,923,715호 ; 제3,574,791호 ; 일본 특허공보 제52-35033호에서는 퍼플루오르알킬기를 함유하는 아크릴레이트 또는 메타아크릴레이트와 특정의 에틸렌 옥사이드기가 포함된 친수성 단량체 또는 아크릴로니트릴, 무수 말레인산, 부타디엔, 클로로프렌 등의 모노머 중의 한 성분을 공중합시켜 제조하였다. 그러나, 이와 같은 방오가공제를 섬유 직물에 처리할 경우 동식물유나 점도가 낮은 석유류 등에 대해서는 반발성(발유성)이 비교적 양호하나, 건성 오염물이나 점도가 높은 엔진오일류에 대해서는 반발성이 불충분하다. 따라서 이러한 방오가공제로 처리된 섬유직물은 건성 오염물이나 고점도의 오일류에 대해서 때가 타기 쉬우며 세탁시에도 부착된 오염물이 잘 이탈되지 않는 문제점이 있다.Therefore, efforts to produce an antifouling agent having excellent water repellency and oil repellency, but also excellent SR property have been continuously progressed, US Patent No. 2,642,416; US Patent No. 3,923,715; 3,574,791; 3,574,791; Japanese Patent Application Laid-Open No. 52-35033 copolymerizes a component of an acrylate or methacrylate containing perfluoroalkyl group with a hydrophilic monomer or monomer such as acrylonitrile, maleic anhydride, butadiene, chloroprene containing a specific ethylene oxide group It was prepared by. However, when the antifouling agent is treated to textile fabrics, the repellency (oil repellency) is relatively good for animal and vegetable oils and petroleum with low viscosity, but the repellency is insufficient for dry contaminants and high engine oils. Therefore, the textile fabric treated with the antifouling agent has a problem in that it is easy to burn with respect to dry contaminants or oils of high viscosity, and the attached contaminants are not easily separated even during washing.
이에 본 발명에서는 발수 발유성 향상을 위한 퍼플루오르알킬기 함유 화합물과 SR성 향상을 위한 페녹시 폴리옥시알킬글리콜(메타)아크릴레이트, 하이드록시알킬메타아크릴레이트 및 염화비닐리덴 단량체를 적정 함량 비율로 공중합하므로써 본 발명을 완성하였다.Therefore, in the present invention, a perfluoroalkyl group-containing compound for improving water and oil repellency and a phenoxy polyoxyalkyl glycol (meth) acrylate, hydroxyalkyl methacrylate and vinylidene chloride monomer for improving SR properties are copolymerized in an appropriate content ratio. Thus, the present invention has been completed.
본 발명은 발수성, 발유성 및 SR성이 우수한 섬유처리용 공중합체를 제공하는데 그 목적이 있다.It is an object of the present invention to provide a fiber treatment copolymer having excellent water repellency, oil repellency and SR properties.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 다음 구조식(I)로 표시되는 퍼플루오르알킬기 함유 화합물 30~70중량%, 다음 구조식(II)로 표시되는 페녹시폴리옥시에틸렌글리콜(메타)아크릴레이트 5~40중량%, 다음 구조식(III)으로 표시되는 하이드록시알킬(메타)아크릴레이트 5~20중량% 염화비닐리덴 1~30중량%로 이루어진 섬유처리용 공중합체를 특징으로 한다.The present invention is 30 to 70% by weight of a perfluoroalkyl group-containing compound represented by the following structural formula (I), 5 to 40% by weight of phenoxypolyoxyethylene glycol (meth) acrylate represented by the following structural formula (II), the following structural formula ( It is characterized by the fiber treatment copolymer which consists of 1-30 weight% of 5-20 weight% vinylidene chloride of the hydroxyalkyl (meth) acrylate represented by III).
상기 식에서, Rf는 CKF2K+1이고 R1, R2및 R3은 각각 같거나 다른 것으로서 수소원자 또는 메틸기이고, R4는 수소원자, 메틸기 또는 에틸기이고, k는 8 내지 16의 정수이고, n은 1 내지 6의 정수이고, m은 1 내지 6의 정수이다.Wherein R f is C K F 2K + 1 and R 1 , R 2 and R 3 are the same or different and each is a hydrogen atom or a methyl group, R 4 is a hydrogen atom, a methyl group or an ethyl group, k is 8 to 16 It is an integer, n is an integer of 1-6, m is an integer of 1-6.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 퍼플루오르알킬기 함유 화합물, 친수성기 함유 단량체 및 염화비닐리덴을 공중합한 공중합체에 관한 것으로서, 이를 섬유에 처리하면 섬유의 발수성, 발유성, 반발성, 내구성 및 내세탁성을 향상시키게 되며 이러한 성질은 공중합 반응 원료의 종류와 함량에 따라 달라질 수 있다.The present invention relates to a copolymer obtained by copolymerizing a perfluoroalkyl group-containing compound, a hydrophilic group-containing monomer and vinylidene chloride, and treating the fiber improves the water repellency, oil repellency, repellency, durability and washing resistance of the fiber. Properties may vary depending on the type and content of the copolymerization reaction raw materials.
상기 구조식(I)로 표시되는 퍼플루오르알킬기 함유 화합물은 발수성과 발유성을 향상시킬 목적으로 사용되며, 이들 화합물을 구체적으로 예시하면 ;The perfluoroalkyl group-containing compound represented by the above structural formula (I) is used for the purpose of improving water repellency and oil repellency, and exemplifying these compounds specifically;
CF3(CF2)9(CH2)2OCOCH=CH2,CF 3 (CF 2 ) 9 (CH 2 ) 2 OCOCH = CH 2 ,
CF3(CF2)9CH2OCOC(CH3)=CH2,CF 3 (CF 2 ) 9 CH 2 OCOC (CH 3 ) = CH 2 ,
CF3(CF2)11(CH2)2OCOCH=CH2,CF 3 (CF 2 ) 11 (CH 2 ) 2 OCOCH = CH 2 ,
CF3(CF2)11(CH2)2OCOC(CH3)=CH2,CF 3 (CF 2 ) 11 (CH 2 ) 2 OCOC (CH 3 ) = CH 2 ,
(CF3)2CF(CF2)7(CH2)2OCOCH=CH2,(CF 3 ) 2 CF (CF 2 ) 7 (CH 2 ) 2 OCOCH = CH 2 ,
(CF3)2CF(CF2)7(CH2)2OCOC(CH3)=CH2,(CF 3 ) 2 CF (CF 2 ) 7 (CH 2 ) 2 OCOC (CH 3 ) = CH 2 ,
(CF3)2CF(CF2)9(CH2)3OCOCH=CH2, (CF 3 ) 2 CF (CF 2 ) 9 (CH 2 ) 3 OCOCH = CH 2,
또는or
(CF3)2CF(CF2)10(CH2)3OCOCH=CH2 (CF 3 ) 2 CF (CF 2 ) 10 (CH 2 ) 3 OCOCH = CH 2
등이다.And so on.
상기 퍼플루오르알킬기 함유 화합물은 공중합체 내에 30~80중량% 함유되며, 만약 퍼플루오르알킬기 함유 화합물의 함량이 30중량% 미만이면 발수성과 발유성이 저하되는 문제가 있고, 또 80중량% 초과하면 과량으로 함유되어 경제성이 없으며 SR성도 저하될 수 있다.The perfluoroalkyl group-containing compound is contained in the copolymer 30 to 80% by weight, if the content of the perfluoroalkyl group-containing compound is less than 30% by weight, there is a problem that the water repellency and oil repellency is lowered, and if the content exceeds 80% by weight It is contained, and it is not economical and SR property may be reduced.
또한, 본 발명에서는 상기 퍼플루오르알킬기 함유 화합물 이외에도 친수성기 함유 단량체들을 첨가하여 공중합하므로써 SR성을 향상시키게 되는데 친수성기 함유 단량체로는 상기 구조식(II)로 표시되는 페녹시 폴리옥시에틸렌글리콜(메타)아크릴레이트 및 상기 구조식(III)으로 표시되는 하이드록시알킬(메타)아크릴레이트를 사용한다.In addition, in the present invention, SR property is improved by copolymerizing by adding hydrophilic group-containing monomers in addition to the perfluoroalkyl group-containing compound. As the hydrophilic group-containing monomer, phenoxy polyoxyethylene glycol (meth) acrylate represented by the above formula (II) And hydroxyalkyl (meth) acrylates represented by the above structural formula (III).
상기 구조식(II)로 표시되는 페녹시폴리옥시에틸렌글리콜(메타)아크릴레이트를 구체적으로 예시하면 ;Specific examples of the phenoxypolyoxyethylene glycol (meth) acrylate represented by the above structural formula (II);
C6H5O(CH2CH2O)1COCH=CH2,C 6 H 5 O (CH 2 CH 2 O) 1 COCH = CH 2 ,
C6H5O(CH2CH2O)2COCH=CH2,C 6 H 5 O (CH 2 CH 2 O) 2 COCH = CH 2 ,
C6H5O(CH2CH2O)2COC(CH3)=CH2,C 6 H 5 O (CH 2 CH 2 O) 2 COC (CH 3 ) = CH 2 ,
C6H5O(CH2CH2O)4COCH=CH2,C 6 H 5 O (CH 2 CH 2 O) 4 COCH = CH 2 ,
C6H5O(CH2CH2O)4COC(CH3)=CH2,C 6 H 5 O (CH 2 CH 2 O) 4 COC (CH 3 ) = CH 2 ,
C6H5O(CH2CH2O)6COC(CH3)=CH2,C 6 H 5 O (CH 2 CH 2 O) 6 COC (CH 3 ) = CH 2 ,
또는or
C6H5O(CH2CH2O)6COCH=CH2,C 6 H 5 O (CH 2 CH 2 O) 6 COCH = CH 2 ,
등이다.And so on.
상기 친수성기 함유 단량체는 공중합체 내에 5~40중량% 함유되는데, 만약 이들의 사용량이 5중량% 미만이면 SR성이 저하되는 문제가 있고, 40중량% 초과하면 반발성이 떨어지는 문제가 있다.The hydrophilic group-containing monomer is contained 5 to 40% by weight in the copolymer, if the amount of these used is less than 5% by weight, there is a problem that the SR property is lowered, if it exceeds 40% by weight there is a problem of poor resilience.
그리고, 또 다른 친수성기 함유 단량체로서 상기 구조식(III)으로 표시되는 하이드록시알킬(메타)아크릴레이트를 구체적으로 예시하면 ;And when hydroxyalkyl (meth) acrylate represented by the said structural formula (III) is specifically illustrated as another hydrophilic group containing monomer;
CH2=CHCOOCH2CH2OH,CH 2 = CHCOOCH 2 CH 2 OH,
CH2=C(CH3)COOCH2CH2OH,CH 2 = C (CH 3 ) COOCH 2 CH 2 OH,
CH2=C(CH3)COOCH2CH(OH)CH3,CH 2 = C (CH 3 ) COOCH 2 CH (OH) CH 3 ,
또는or
CH2=CHCOOCH2CH(OH)CH3 CH 2 = CHCOOCH 2 CH (OH) CH 3
등이다.And so on.
상기 하이드록시알킬(메타)아크릴레이트는 공중합체 내에 5~20중량% 함유되는데, 만약 이들의 사용량이 5중량% 미만이면 SR성이 저하되는 문제가 있고, 20중량% 초과하면 발수성과 발유성이 저하되는 문제가 있다.The hydroxyalkyl (meth) acrylate is contained in the copolymer 5 to 20% by weight, if their amount is less than 5% by weight, there is a problem that the SR property is lowered, if it exceeds 20% by weight water and oil repellency There is a problem of deterioration.
그리고, 본 발명의 공중합체 내에 염화비닐리덴이 1~30중량% 함유되는데 만약 그 사용량이 1중량% 미만이면 반발성과 내구성이 저하되는 문제가 있고, 30중량% 초과하면 반응성이 떨어지는 문제가 있다.And, 1 to 30% by weight of vinylidene chloride is contained in the copolymer of the present invention, if the amount is less than 1% by weight, there is a problem that the resilience and durability is lowered, if it exceeds 30% by weight there is a problem of poor reactivity.
상기와 같은 단량체는 공지된 여러가지의 중합방법 예를 들면 유화중합, 용액중합, 현탁중합 또는 벌크중합에 의해 공중합체를 제조하며, 이 공중합체는 공중합 반응용매 또는 서로 섞일 수 있는 다른 용매 즉, 물 또는 극성용매에 희석하여 사용할 수 있고 필요하다면 용매를 제거하여 공중합체를 분리해내어 사용할 수도 있다.Such monomers are prepared by a variety of known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization or bulk polymerization, which copolymers are copolymerization reaction solvents or other solvents that can be mixed with each other, namely water. Alternatively, the solvent may be diluted with a polar solvent and, if necessary, the solvent may be removed to separate the copolymer.
상기 중합방법에 의해 제조된 수성중합체 분산액은 공지된 가공방법으로 폴리에스테르, 나이론, 모직, 비단, 면과 같은 합성섬유 또는 자연섬유에 처리할 수 있다.The aqueous polymer dispersion prepared by the polymerization method can be treated to synthetic fibers such as polyester, nylon, wool, silk, cotton or natural fibers by known processing methods.
특히 폴리에스테르와 같은 합성섬유직물 제품의 표면에 처리할 때 효과적이다.It is particularly effective when treating the surface of synthetic textile products such as polyester.
또한, 본 발명의 공중합체는 단독으로 사용하거나, 또는 희석한 비플루오르중합체(예를 들면 멜라민 또는 우레탄과 같은 가교성 수지) 또는 다른 섬유제품 처리제(예를 들면 대전방지제)와 함께 혼합물로 사용할 수 있다. 본 발명의 중합체는 일반적으로 분무, 담금, 패딩(pedding) 또는 잘 알려진 다른 방법에 의해 수성 분산액으로서 섬유직물 제품에 사용되며, 과량의 액체는 압축로울러로 제거한 후 직물을 건조시킨다. 건조된 직물은 보통 60~180초 동안 140~180℃로 가열시켜 경화시키는데, 이와 같은 경화는 반발성과 내구성을 증진시키게 된다.The copolymers of the invention can also be used alone or in mixtures with diluted nonfluoropolymers (eg crosslinking resins such as melamine or urethane) or other textile product treatment agents (eg antistatic agents). have. The polymers of the present invention are generally used in textile fabric products as aqueous dispersions by spraying, soaking, padding or other well known methods, and excess liquid is removed by compression rollers and then the fabric is dried. The dried fabric is usually cured by heating to 140-180 ° C. for 60-180 seconds, which enhances resilience and durability.
상기와 같은 본 발명의 공중합체는 적은 사용량 수준에서 섬유표면을 처리하여도 종래의 섬유 가공제보다 우수한 발수성, 발유성 및 SR성을 갖는다.The copolymer of the present invention as described above has excellent water repellency, oil repellency and SR properties even when the fiber surface is treated at a small amount of use level, compared to conventional fiber processing agents.
이와 같은 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 한정되는 것은 아니다.If the present invention will be described in detail based on the embodiment as follows, the present invention is not limited to the embodiment.
본 발명의 섬유처리용 공중합체로 처리된 직물은 다음과 같은 시험방법에 의하여 발수성, 발유성 및 SR성을 평가하였다.Fabrics treated with the fiber treatment copolymer of the present invention were evaluated for water repellency, oil repellency and SR properties by the following test method.
1. 섬유처리용 공중합체의 직물처리1. Textile Treatment of Copolymer for Textile Treatment
섬유처리용 공중합체의 성능을 평가하기 위해서는 우선 제조된 공중합체를 폴리에스테르나 면과 같은 직물표면을 처리해야 한다. 폴리에스테르는 0.5중량% 고형분 농도의 수성분산액 중에서 1분간 담그어 적시고, 적셔진 폴리에스테르는 압축로울러로 과량의 액체를 제거한다. 이때 수성 분산액의 픽업(pick-up)은 약75%이다. 처리된 직물은 105℃에서 3분 동안 건조시킨 후 160℃에서 3분 동안 경화시킨다.In order to evaluate the performance of the fiber treatment copolymer, first, the prepared copolymer must be treated with a fabric surface such as polyester or cotton. The polyester is immersed for 1 minute in an aqueous acidic solution having a concentration of 0.5% by weight of solid content, and the wetted polyester removes excess liquid by a compression roller. At this time, the pick-up of the aqueous dispersion is about 75%. The treated fabric is dried at 105 ° C. for 3 minutes and then cured at 160 ° C. for 3 minutes.
2. 발수성 및 발유성 측정2. Water repellency and oil repellency measurement
처리된 섬유제품은 일본공업규격 JIS L 1092(1977)의 시험법을 이용하여 발수성을 측정하였다. 그리고 발유도는 미국직물화학자 및 염색화 연합회 규격 AATCCTM-118(1983)법을 이용하여 측정하였다.The treated textile product was measured for water repellency using the test method of Japanese Industrial Standard JIS L 1092 (1977). Oil repellency was measured using the American Textile Chemists and Dyeing Association Standard AATCCTM-118 (1983) method.
3. SR성 측정3. SR property measurement
SR성은 때가 묻은 섬유표면에서 세탁할 때 때가 얼마나 잘 빠지는가를 나타내는 척도이다. SR성의 수치가 높을수록 섬유표면으로부터 때의 이탈이 쉽다는 것을 나타내고 세탁하면 섬유의 표면이 깨끗해진다는 것을 의미한다. SR성의 측정은 우선 섬유처리용 공중합체가 처리된 시험직물(폴리에스테르 100%, 6×7cm)을 준비하여 수평한 평면에 있는 텍스타일 블로팅 종이(또는 여과 종이) 위에 둔다. 여기에 스포이드를 이용하여 자동차용 엔지오일(7.5W/30) 1방울을 시험직물 위의 중앙에 떨어뜨린다. 이 오일 위에 폴리에틸렌 필름(10cm W×15cm L×0.05cm)을 덮는다.SR is a measure of how well the soil falls out when laundered from the stained fiber surface. The higher the SR value, the easier the delamination from the fiber surface, and the more clear the surface of the fiber. The measurement of SR property is made by first preparing a test fabric (100% polyester, 6 × 7 cm) treated with a fiber treatment copolymer and placing it on a textile blotting paper (or filter paper) in a horizontal plane. Drop a drop of automotive engine oil (7.5 W / 30) into the center on the test fabric. Cover this oil with a polyethylene film (10 cm W x 15 cm L x 0.05 cm).
그 위에 무게 추(직경 6.4cm, 500g)을 올려 놓고 60초 동안 유지한다. 그리고나서 무게 추와 폴리에틸렌 필름을 제거하고 실온에서 30분 정도 방치한다. 그리고 1.5ι 비이커에 2g의 세제(태평양화학(주) 제품)가 포함된 1ι의 수용액을 준비한다. 이 수용액에 오일 처리된 시험직물과 미처리된 직물 3장을 함께 넣고 15분동안 실온에서 교반한다. 세탁이 완료된 시험직물은 건조기에서 75℃로 30분동안 건조한 후에 오염된 섬유 표면 상태를 관찰하여 다음 표 1의 판정표로부터 등급을 평가하였다.Place the weight (6.4cm in diameter, 500g) on it and hold for 60 seconds. Then remove the weight and polyethylene film and leave for 30 minutes at room temperature. And a 1ι aqueous solution containing 2 g of detergent (Pacific Chemical Co., Ltd.) in a 1.5ι beaker is prepared. Add the oiled test fabric and three untreated fabrics to this aqueous solution and stir at room temperature for 15 minutes. The test fabric after washing was dried for 30 minutes at 75 ° C. in a drier, and the grade was evaluated from the determination table of Table 1 by observing the contaminated fiber surface condition.
표 1. 오염저항 등급Table 1. Pollution Resistance Rating
4. 5회 세탁처리4. 5 times washing
초기 SR성을 측정할 때 세탁하는 경우와 같은 방법으로 2g의 세제가 포함된 1ι의 수용액을 준비한다. 이 수용액에 섬유처리용 공중합체가 처리된 폴리에스테르를 넣고 15분 동안 실온에서 교반한다. 세탁이 완료된 시험직물은 건조기에서 75℃에서 30분 동안 건조한다. 이와 같은 방법으로 4회 더 반복하여 세탁처리한다.When measuring the initial SR properties, prepare an aqueous solution of 1ι containing 2 g of detergent in the same manner as washing. The polyester treated with the fiber treatment copolymer was added to this aqueous solution and stirred at room temperature for 15 minutes. The washed test fabric is dried in a dryer at 75 ° C. for 30 minutes. Repeat this procedure four more times in this manner.
실시예 1Example 1
온도조절장치와 교반기가 부착된 유리압력 반응기(1ι)에 퍼플루오르데실에틸메티아크릴레이트(이하 FA)[C10F21CH2CH2OCOC(CH3)=CH2] 75g, 페녹시폴리옥시에틸렌 글리콜아크릴레이트(에틸렌 옥사이드 부가몰수 6몰) 25g, 2-하이드록시프로필메타아크릴레이트 12.5g을 첨가하고, 부틸셀로솔브와 물이 82:18비율로 혼합된 혼합용매 355g을 투입한다.75 g of perfluorodecylethyl methacrylate (hereinafter FA) [C 10 F 21 CH 2 CH 2 OCOC (CH 3 ) = CH 2 ] in a glass pressure reactor (1ι) equipped with a temperature controller and a stirrer. 25 g of ethylene glycol acrylate (6 mol of ethylene oxide added mole number) and 12.5 g of 2-hydroxypropyl methacrylate are added, and 355 g of a mixed solvent in which butyl cellosolve and water are mixed in an 82:18 ratio is added.
실온에서 약 20~30분 동안 질소치환을 행한 다음, 여기에 개시제로서 아조비스아미디노프로판 디하이드록시클로라이드 2.8g을 투입하고 반응온도를 70℃로 유지하면서 60시간 동안 중합반응을 진행시킨다.After nitrogen replacement at room temperature for about 20 to 30 minutes, 2.8 g of azobisamidinopropane dihydroxy chloride was added thereto as an initiator, and polymerization was performed for 60 hours while maintaining the reaction temperature at 70 ° C.
반응물을 실온으로 냉각하여 고형분 농도 26%의 용액형 중합체를 얻었으며, 섬유처리용 공중합체의 공중합 반응의 전환율은 가스크로마토그라피로 분석한 결과 98%(FA) 이상이었다.The reaction product was cooled to room temperature to obtain a solution type polymer having a solid concentration of 26%, and the conversion rate of the copolymerization reaction of the copolymer for fiber treatment was 98% (FA) or more when analyzed by gas chromatography.
실시예 2~7, 비교예 1~3Examples 2-7, Comparative Examples 1-3
상기 실시예 1과 동일한 중합방법으로 중합체를 제조하되, 다만 다음 표 2에 제시한 바와 같이 단량체의 종류 및 사용량을 달리하였다.The polymer was prepared by the same polymerization method as in Example 1, except that the type and amount of the monomer were changed as shown in the following Table 2.
표 2TABLE 2
FA : 퍼플루오르알킬에틸아크릴레이트FA: perfluoroalkylethyl acrylate
FA-1 : CF3(CF2)9CH2CH2OCOC(CH3)=CH2 FA-1: CF 3 (CF 2 ) 9 CH 2 CH 2 OCOC (CH 3 ) = CH 2
FA-2 : CF3(CF2)11(CH2)2OCOCH=CH2 FA-2: CF 3 (CF 2 ) 11 (CH 2 ) 2 OCOCH = CH 2
PG : 페녹시폴리옥시에틸렌글리콜(메타)아크릴레이트PG: Phenoxypolyoxyethylene glycol (meth) acrylate
PG-1 : C6H5O(CH2CH2O)6COCH=CH2 PG-1: C 6 H 5 O (CH 2 CH 2 O) 6 COCH = CH 2
PG-2 : C6H5O(CH2CH2O)4COC(CH3)=CH2 PG-2: C 6 H 5 O (CH 2 CH 2 O) 4 COC (CH 3 ) = CH 2
HA : 하이드록시알킬(메타)아크릴레이트HA: hydroxyalkyl (meth) acrylate
HA-1 : CH2=C(CH3)COOCH2CH(OH)CH3 HA-1: CH 2 = C (CH 3 ) COOCH 2 CH (OH) CH 3
HA-2 : CH2=C(CH3)COOCH(OH)CH3 HA-2: CH 2 = C (CH 3 ) COOCH (OH) CH 3
VDC : 염화비닐리덴VDC: vinylidene chloride
AN : 아크릴로니트릴AN: Acrylonitrile
N-MAN : N-메틸올아크릴아미드N-MAN: N-methylol acrylamide
상기 표 2에 의하면, 본 발명에 따른 실시예에 의해 제조된 공중합체는 폴리에스테르의 직물표면에 처리하는 경우에 발수성과 발유성 및 SR성이 우수한데 반하여, 비교예에 의해 제조된 공중합체는 반발성이 약하고 SR성이 저조하였으며 특히 5회 세탁후의 반발성과 SR성은 아주 낮아 처리효과가 거의 없었다. 따라서, 본 발명의 섬유처리용 공중합체는 반발성과 SR성이 양호하고 특히 우수한 내구성을 갖고 있어 의류나 섬유와 같은 직물표면처리에 유용하다.According to Table 2, the copolymer prepared according to the embodiment of the present invention is excellent in water repellency and oil repellency and SR properties when treated on the fabric surface of the polyester, the copolymer prepared by the comparative example The repulsion property was weak and the SR property was low. In particular, the repulsion property and the SR property after 5 washings were very low and there was almost no treatment effect. Therefore, the copolymer for fiber treatment of the present invention has good resilience and SR properties and particularly excellent durability, and thus is useful for textile surface treatments such as clothing and textiles.
Claims (3)
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