KR960015813B1 - Process for having a prepellent on surface - Google Patents
Process for having a prepellent on surface Download PDFInfo
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- KR960015813B1 KR960015813B1 KR1019930005596A KR930005596A KR960015813B1 KR 960015813 B1 KR960015813 B1 KR 960015813B1 KR 1019930005596 A KR1019930005596 A KR 1019930005596A KR 930005596 A KR930005596 A KR 930005596A KR 960015813 B1 KR960015813 B1 KR 960015813B1
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- water
- group
- oil
- repellent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/185—Processes for applying liquids or other fluent materials performed by dipping applying monomolecular layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain 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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/005—Applying monomolecular films on textile products like fibres, threads or fabrics
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
내용없음.None.
Description
제1도는 본 발명의 제1 및 제3실시예인 기재의 발수발유처리방법을 설명하기 위하여 사용한 공정단면도.1 is a cross-sectional view of the process used to explain the water and oil repellent treatment method of the substrate of the first and third embodiments of the present invention.
제2도는 본 발명의 제2 및 제4실시예인 기재의 발수발유처리방법을 설명하기 위하여 사용한 공정단면도.Figure 2 is a cross-sectional view of the process used to explain the water and oil repellent treatment method of the substrate of the second and fourth embodiments of the present invention.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
1 : 유리기재(목면섬유) 2, 12 : 도포막1: Glass base material (cotton fiber) 2, 12: Coating film
3 : 수산기 4 : 실록산결합3: hydroxyl group 4: siloxane bond
5, 15 : 발수발유성초막 11 : 나일론-ABS 수지기재5, 15: water and oil repellent cottage 11: nylon-ABS resin substrate
13 : 이미노기 14 : SiN-결합13: imino group 14: SiN-bond
본 발명은, 기재표면을 발수발유성화시키는 방법에 관한 것이다. 더욱 상세하게는 금속이나 세라믹, 유리, 플라스틱, 섬유, 종이등의 표면에 발수발유성의 초박막을 형성해서 기재표면을 발수발유화시키는 방법에 관한 것이다.The present invention relates to a method for water- and oil-repellent substrate surface. More specifically, the present invention relates to a method for forming a water / oil repellent ultra-thin film on the surface of a metal, ceramic, glass, plastic, fiber, paper, or the like to make the surface of the substrate water / oil repellent.
또한, 본 발명은, 발수발유성 어패럴용부재에 관한 것이다. 더욱 상세하게는, 우비, 코트, 스포츠웨어(스키 웨어를 포함), 장갑용옷감, 혹은 모피나 피혁등으로 대표되는 고성능 발수발유방오성어패럴용부재에 관한 것이다.The present invention also relates to a water / oil repellent apparel member. More specifically, the present invention relates to a member for high-performance water-repellent oil-repellent oil-resistant apparel represented by raincoats, coats, sportswear (including skiwear), glove cloths, or fur or leather.
종래, 금속, 세라믹, 유리, 플라스틱, 섬유 종이, 목재등의 표면을 발수발유화시키는 방법으로서, 각종수지나 도료를 합침 또는 코팅하거나 폴리테트라플루오로에틸렌등의 불소수지의 에멀션을 도포하거나, 베이킹하는 방법이 사용되고 있었다.Conventionally, as a method for water- and oil-repellent surface of metal, ceramic, glass, plastic, fiber paper, wood, etc., various resins or paints are combined or coated, or an emulsion of fluororesin such as polytetrafluoroethylene is applied or baked. How to use was used.
또, 우비, 코트, 스포츠웨어(스키웨어를 포함), 장갑용옷감, 혹은 모피나 피혁을 발수발유처리하는 것은 더러움방지나 우천대책상 중요한 과제이다.In addition, water- and oil-repellent treatment of raincoats, coats, sportswear (including skiwear), glove cloths, or furs or leathers is an important task in preventing dirt and rain.
종래, 섬유제품등의 어패럴용부재에 대해서는, 통기성을 어느정도 보유한채, 발수성을 부여하기 위해서는, 플로로카본계의 에멀션(불소수지)을 스프레이법등에 의해서 코팅하고, 미세한 구멍을 가진 다공질성코팅막을 형성하는 방법이 제안되고 있다. 다른 수단으로서는, 우레탄수지등의 수지를 얇게 코팅하고, 미세한 구멍을 가진 다공질성코팅막을 형성하는 방법도 제안되고 있다. 또 다른 수단으로서는, 수축률이 비교적 높은 가는 섬유를 고밀도로 짜고, 직물의 상태에서 고온 처리해서 수축시키는 것도 알려져 있다.Conventionally, for apparel members such as textile products, in order to impart water repellency while retaining air permeability to some extent, a fluorocarbon emulsion (fluorine resin) is coated by a spray method or the like, and a porous coating film having fine pores is applied. A method of forming is proposed. As another means, a method of thinly coating a resin such as urethane resin and forming a porous coating film having fine pores has also been proposed. As another means, it is also known to squeeze a thin fiber having a relatively high shrinkage ratio to a high density and to shrink it by high temperature treatment in the state of a woven fabric.
또, 잉크등의 천연모피에 대해서는, 실리콘화합물이나 불소화합물을 포함한 도포액을 사용해서 폴리싱가공등이 행해지고 있다.Moreover, about natural fur, such as ink, polishing processing etc. are performed using the coating liquid containing a silicon compound and a fluorine compound.
그러나 종래의 방법에서는, 도포막은 기재표면에 화학결합하고 있지 않아 내구성이 나쁘다는 큰 결점이 있었다. 또 기재자체가 가진 표면의 미관을 손상한다는 문제점도 있었다. 또 종래의 발수제를 코팅하는 방법으로는 효과가 적고, 내구성도 거의 없는 것이었다. 또 부재표면에 수지를 코팅하는 방법으로는, 착용시 무덥다는 등의 결점이 있었다. 섬유의 광택이나 감촉 또는 통기성을 손상하는 일없이 섬유표면만 발수발유처리하는 것은, 어패럴용부재의 개량에서 중요한 과제이다.However, in the conventional method, the coating film does not chemically bond to the surface of the base material, and thus has a large disadvantage of poor durability. In addition, there is a problem that damages the appearance of the surface of the substrate itself. In addition, the conventional method of coating the water repellent agent has little effect and almost no durability. In addition, the method of coating the resin on the surface of the member has the drawback of being hot when worn. It is important to improve water repellent treatment for the apparel member without water damage to the gloss, texture or breathability of the fiber.
본 발명은, 상기 종래기술의 과제를 해결하기 위하여, 금속이나 세라믹, 유리, 플라스틱, 섬유, 종이, 목재등의 기재 표면을 내구성이 높은 초박막으로 덮고 발수발유화시키는 방법을 제공한다. 또 어패럴용부재에서 착용시의 무더움이 없고, 또한 내구성이 뛰어난 발수발유성 어패럴용부재를 제공하는 것을 목적으로 한다.The present invention provides a method of covering the surface of a substrate such as metal, ceramic, glass, plastic, fiber, paper, wood, etc. with a highly durable ultra-thin film and water / oil repellent in order to solve the problems of the prior art. Another object of the present invention is to provide a water / oil-repellent apparel member that is free from swelling when worn and has excellent durability.
상기 목적을 달성하기 위하여, 본 발명의 기재표면의 발수발유처리방법은, 불화 탄소기와 클로로실릴기를 복수개 함유한 물질을 비수계의 용매에 용해한 용액에, 표면에 수산기, 아미노기 및 카르복실기로부터 선택되는 적어도 1개의 관능기를 함유한 기재를 침지하는 공정과, 상기 용액중으로부터 기재를 꺼내서 수분을 전혀 함유하지 않거나 실질적으로 함유되지 않은 분위기속에서 건조하고, 상기 비수계 용매를 제거하는 공정과, 상기 처리물을 수분을 함유한 분위기속으로 꺼내는 공정을 포함하는 것을 특징으로 한다.In order to achieve the above object, the water- and oil-repellent treatment method of the substrate surface of the present invention is selected from hydroxyl, amino and carboxyl groups on the surface in a solution in which a substance containing a plurality of fluorocarbon groups and chlorosilyl groups is dissolved in a non-aqueous solvent. Immersing the substrate containing at least one functional group, removing the substrate from the solution, drying in an atmosphere containing no or substantially no moisture, and removing the non-aqueous solvent; and the treatment And removing the water into the atmosphere containing water.
상기 구성에 있어서는, 불화탄소기와 클로로실릴기를 복수개 함유한 물질로서, CF3-(CF2)n-R-SiXpCl3-p(단, n은 정수, R은 알킬기 또는 실리콘 혹은 산소원자를 함유한 치환기 또는 화학결합, X는 H 또는 알킬기, 알콕시기로부터 선택되는 치환기, P는 0 또는 1)을 사용하는 것이 바람직하다.In the above structure, a substance containing a plurality of fluorocarbon groups and chlorosilyl groups is CF 3- (CF 2 ) n -R-SiX p Cl 3-p (wherein n is an integer and R is an alkyl group or a silicon or oxygen atom). It is preferable to use a substituent or a chemical bond, X is a substituent selected from H or an alkyl group, an alkoxy group, and P is 0 or 1).
또 상기 구성에 있어서는, 비수계의 용매로서 탄화수소계 또는 불화탄소계의 용매를 사용하는 것이 바람직하다.Moreover, in the said structure, it is preferable to use a hydrocarbon type or a fluorocarbon solvent as a non-aqueous solvent.
본 발명에 있어서는, 매우 발수발유성이 높은 불소를 다수 함유한 초박막을 화학결합을 개재해서 기재표면에 형성할 수 있으므로, 내구성이 높은 발수발유처리를 행할 수 있는 작용이 있다. 즉, 불화탄소기와 클로로실릴기를 복수개 함유한 물질을 비수계의 용매에 용해한 용액에, 표면에 수산기나 아미노기 혹은 카르복실기를 함유한 기재를 침지한 후 상기 용액중에서 기재를 꺼내서 수분을 거의 함유하지 않는 분위기속에서 건조하여 비수계 용매를 제거하면, 상기 단분자막 표면에 상기 클로로실릴기를 복수개 함유한 물질의 도포막이 형성된다. 그리고 다시 수분을 함유한 분위기속, 예를 들면 공기중으로 꺼내면, 이 도포막은 공기중의 수분과 탈염산반응해서 폴리머화된다. 이때, 도포막은 상기 기재표면과도 탈염산반응해서 공유결합을 발생하고 있으므로, 화학결합을 개재해서 기재표면에 결합한 매우 발수발유성이 높은 초박막을 형성할 수 있다.In the present invention, an ultra-thin film containing a large amount of fluorine having a very high water and oil repellency can be formed on the surface of the substrate via a chemical bond, so that a highly durable water and oil repellent treatment can be performed. That is, in a solution in which a substance containing a plurality of fluorocarbon and chlorosilyl groups is dissolved in a non-aqueous solvent, the substrate is immersed in a surface containing a hydroxyl group, an amino group or a carboxyl group, and then the substrate is taken out of the solution to contain little moisture. When the solvent is dried to remove the non-aqueous solvent, a coating film of a substance containing a plurality of chlorosilyl groups is formed on the surface of the monomolecular film. Then, when taken out again in an atmosphere containing water, for example, in the air, the coating film is polymerized by dehydrochlorination reaction with water in the air. At this time, since the coating film is dehydrochlorinated with the substrate surface to generate covalent bonds, it is possible to form a very high water / oil repellent ultra thin film bonded to the substrate surface via a chemical bond.
또한, 불화탄소기와 클로로실릴기를 복수개 함유한 물질로서, CF3(CF2)7(CH2)2SiCl3, CF3(CF2)5(CH2)2SiCl3, CF3CH2O(CH2)15SiCl3, CF(CH2)2Si(CH3)2(CH2)15SiCl3, F(CF2)4(CH2)2Si(CH3)2(CH2)5SiCl3, CF3COO(CH2)15SiCl3을 사용할 수 있다.In addition, as a substance containing a plurality of fluorocarbon groups and chlorosilyl groups, CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3 , CF 3 CH 2 O ( CH 2 ) 15 SiCl 3 , CF (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 15 SiCl 3 , F (CF 2 ) 4 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 5 SiCl 3 , CF 3 COO (CH 2 ) 15 SiCl 3 can be used.
또, 비수계의 용매로서 탄화수소계 혹은 불화탄소계의 용매를 사용하면 독성이 없으므로 형편이 좋다.In addition, use of a hydrocarbon-based or fluorocarbon-based solvent as the non-aqueous solvent has no toxicity, which is advantageous.
또한, 본 발명의 발수발유성 어패럴용부재는, 발수발유성의 관능기를 다수 함유한 초박막의 -Si-를 함유한 공유결합을 개재해서 부재표면에 형성되어 있는 것을 특징으로 한다.In addition, the water / oil-repellent apparel member of the present invention is characterized in that it is formed on the member surface via a covalent bond containing —Si— of an ultra-thin film containing a large number of water- and oil-repellent functional groups.
상기 구성에 있어서는, 발수발유성의 관능기가 불화탄소기이고, 또한 공유결합이 실록산결합인 것이 바람직하다.In the above structure, it is preferable that the water / oil repellent functional group is a fluorocarbon group, and the covalent bond is a siloxane bond.
상기 본 발명의 구성에 의하면, 발수발유성의 관능기를 다수 함유한 초박막이 -Si-를 함유한 공유결합을 개재해서 부재표면에 형성되어 있으므로, 내구성이 높은 발수발유처리한 어패럴용부재로 할 수 있다. 또 부재의 표면에는, 나노미터 레벨의 초박막이 형성되어 있으므로, 직물이나 편물의 통기성을 방해하는 일이 없고, 착용시의 찌는 느낌은 매우 적다.According to the configuration of the present invention, since the ultra-thin film containing a large number of water- and oil-repellent functional groups is formed on the surface of the member via the covalent bond containing -Si-, the durable water- and oil-repellent treated apparel can be used. Can be. Moreover, since the nanometer level ultra-thin film is formed in the surface of a member, the air permeability of a fabric or a knitted fabric is not disturbed, and the steaming feeling at the time of wearing is very few.
또, 발수발유성의 관능기가 불소이고, 또한 공유결합이 실록산결합이라는 본 발명의 바람직한 구성에 의하면, 매우 발수발유성이 높은 불소를 다수 함유한 초박막을 화학결합을 개재해서 어패럴용부재표면에 형성할 수 있으므로, 내구성이 높은 발수발유처리한 어패럴용부재를 공급할 수 있다.Further, according to the preferred configuration of the present invention in which the water and oil repellent functional group is fluorine and the covalent bond is a siloxane bond, an ultra thin film containing a large number of fluorine having high water and oil repellency is formed on the surface of the apparel through a chemical bond. Since it is possible to provide high durability, the water-repellent oil-repellent apparel member can be supplied.
이하 실시예를 사용해서 본 발명 방법을 더욱 구체적으로 설명한다. 이하의 실시예는, 본 발명에 관한 대표적인 발수발유처리방법이다.The present invention is explained in more detail using the following examples. The following examples are representative water and oil repellent treatment methods according to the present invention.
[실시예 1]Example 1
먼저, 가공이 종료한 유리기재(금속이나 세라믹, 플라스틱, 섬유등 표면에 수산기나 아미노기, 카르복실기등 클로로실릴기와 탈염산반응을 발생하는 관능기를 표면에 함유한 것이면 무엇이든 좋다)(1)를 준비하고 (제1도(a)), 세정한후 불화탄소기와 클로로시릴기를 복수개 가진 화합물, 예를 들면First, a glass substrate (finished with metal, ceramics, plastics, fibers, etc.) (1) may be prepared if the surface contains functional groups that cause dehydrochlorination with chlorosilyl groups such as hydroxyl groups, amino groups, and carboxyl groups. (FIG. 1 (a)), after washing, a compound having a plurality of fluorocarbon groups and chlorosilyl groups, for example,
CF3(CF2)n-R-SiXpCl3-p CF 3 (CF 2 ) n -R-SiX p Cl 3-p
(단, n은 정수, R은 알킬기 또는 실리콘이나 산소원자를 함유한 치환기 또는 화학결합, X는 H 또는 알킬기, 알콕시기등의 치환기, P는 0 또는 1)로 표시되는 물질, 예를 들면, CF3(CF2)7(CH2)2SiCl3를 불화탄소계 용매(예를 들면 일본국, 아시히유리회사제 ; 아푸루드)에 1wt% 용해한 용액에 10분정도 침지하고, 그후 유기용제에 의해서 세정하는 일없이, 그대로 수분을 거의 함유하지 않는(바람직한 상대습도 5% 이하)분위기 속에서 용매를 증발시키고 건조시키면, 표면에 남은 불화탄소기와 클로로실릴기를 복수개 가진 물질에 의해서 200Å 정도의 막두께로 도포막(2)이 형성된다. 이때, 일부의 불화탄소기와 클로로실릴기를 함유한 물질은, 기재표면의 수산기(3)와 탈염산반응해서 실록산결합(-SiO-)(4)을 발생하고, 기재표면에 고정된다(제1도(b)). 그리고, 다시 기재를 수분을 함유한(상대습도 30% 정도이상) 분위기속, 예를 들면 공기중으로 옮기면, 이 도포막 및 고정된 불화탄소기와 클로로실릴기를 함유한 물질이 남은 클로로실릴기는 공기중의 수분과 탈염산반응해서 폴리머화된다. 이와 같이 해서 작성된 도포막은 불소를 다수 함유하고 실록산결합(4)에 의해서 기재표면에 결합되기 때문에, 매우 발수발유성이 높은 초박막(5)이 기재표면에 형성된다(제1도(C)).Where n is an integer, R is an alkyl group or a substituent or chemical bond containing a silicon or oxygen atom, X is H or an substituent such as an alkyl group or an alkoxy group, P is 0 or 1, for example, CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 is immersed in a solution of 1 wt% dissolved in a fluorocarbon solvent (e.g., Japan, Ashhi Glass Co .; Afurud) for about 10 minutes, then organic solvent If the solvent is evaporated and dried in an atmosphere that contains almost no moisture (preferably relative humidity of 5% or less) without being cleaned by water, the surface of the film is about 200 Pa by the material having a plurality of fluorocarbon and chlorosilyl groups remaining on the surface. The coating film 2 is formed in thickness. At this time, the substance containing some fluorocarbon group and chlorosilyl group is subjected to dehydrochlorination reaction with the hydroxyl group 3 on the surface of the base to generate a siloxane bond (-SiO-) 4 and fixed to the surface of the base (FIG. 1). (b)). Then, when the substrate is transferred to an atmosphere containing water (at least about 30% relative humidity), for example, in air, the chlorosilyl group remaining with the coating film and the substance containing a fixed fluorocarbon group and chlorosilyl group is removed from the air. It is polymerized by dehydrochlorination with water. Since the coating film thus produced contains a large amount of fluorine and is bonded to the substrate surface by the siloxane bond 4, an ultra thin film 5 having high water and oil repellency is formed on the substrate surface (FIG. 1C).
또한, 이 초박막은 기재와 실록산결합을 개재해서 공유결합되어 있고, 문질러도 세정해도 벗겨지는 일이 없었다. 또 물에 대한 젖음각도를 예측하면 대략 150˚였다.In addition, this ultra-thin film was covalently bonded through a base material and a siloxane bond, and even if it rubs and washes, it was not peeled off. The wet angle was estimated to be 150 °.
[실시예 2]Example 2
가공이 종료한 나일론 -ABS 수지(폴리머알로이)기재(11)를 준비하고(제2도(a)), 세정한 후 불화탄소기와 클로로실릴기를 복수개 가진 물질, 예를 들면 CF3(CF2)5(CH2)2SiCl3을 탄화수소계 용매(노멀헥산)에 1wt%용해한 용액에 20분정도 침지하고, 그후 유기용재에 의해서 세정하는 일없이, 그대로 수분을 거의 함유하지 않는(바람직하게는 상대습도 5%이하) 분위기속에서 용매를 증발시키고 건조시키면, 표면에 남은 불화탄소기와 클로로실릴기를 복수개가진 물질에 의해서 100Å 정도의 막두께로 도포막(12)이 형성된다. 이때, 일부의 불화탄소기와 클로로실릴기를 함유한 물질은, 기재표면의 이미노기(13)와 탈염산 반응해서 실록산결합(-SiO-)(14)을 발생하고, 기재표면에 고정된다.(제2도(b)).A material having a plurality of carbon fluoride groups and chlorosilyl groups after preparing the nylon-ABS resin (polymer alloy) substrate 11 having finished processing (FIG. 2 (a)) and washed, for example, CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3 is immersed in a solution of 1 wt% dissolved in a hydrocarbon solvent (normal hexane) for about 20 minutes, and then contains little moisture as it is without washing with an organic solvent (preferably relative Humidity 5% or less) When the solvent is evaporated and dried in an atmosphere, the coating film 12 is formed to a film thickness of about 100 kPa by a substance having a plurality of fluorocarbon groups and chlorosilyl groups remaining on the surface. At this time, the substance containing some fluorocarbon group and chlorosilyl group is subjected to dechlorination reaction with the imino group 13 on the surface of the base to generate a siloxane bond (-SiO-) 14, and is fixed to the surface of the base. 2 degrees (b)).
그리고 다시 기재를 수분을 함유한(상대습도 30% 정도 이상) 분위기속, 예를 들면 공기중으로 옮기면, 이 도포막 및 고정된 불화탄소기와 클로로실릴기를 함유한 물질이 남은 클로로실릴기를 공기중의 수분과 탈염산반응해서 폴리머화된다.Then, when the substrate is transferred to an atmosphere containing water (at least about 30% relative humidity), for example, in air, the chlorosilyl group in which the coating film and the substance containing a fixed fluorocarbon group and chlorosilyl group are left It is polymerized by dehydrochlorination.
이와같이 해서 작성된 도포막은 불소를 다수 함유하고 -SiN=결합(14)에 의해서 기재표면에 결합되기 때문에 매우 발수발유성이 높은 초박막(15)이 기재표면에 형성된다(제2도(C)).Since the coating film thus produced contains a large amount of fluorine and is bonded to the substrate surface by -SiN = bonding 14, an ultra-thin film 15 having very high water and oil repellency is formed on the substrate surface (FIG. 2C).
또한, 이 초박막은 기재와 -SiN=결합을 개재해서 공유결합되어 있고, 문질러도 세정해도 벗겨지는 일이 없었다. 또 물에 대한 젖음각도도 대략 130˚로서 매우 높았다.In addition, this ultra-thin film was covalently bonded via a base material and -SiN = bond, and it did not peel off even if it rubs and washes. In addition, the wet angle with respect to water was also very high, approximately 130 degrees.
또한, 상기 실시예에서는 불화탄소기와 클로로실릴기를 함유한 물질로서, CF3(CF2)7(CH2)2SiCl3, CF3(CF2)5(CH2)2SiCl3을 사용했으나, 이외에, CF3CH2O(CH2)15SiCL3, CF3(CH2)2Si(CH3)2(CH2)15SiCl3, F(CF2)4(CH2)2Si(CH3)2(CH2)3SiCl3, CF3COO(CH2)15SiCl3등을 이용할 수 있었다.In addition, in the above examples, CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3 was used as a material containing a fluorocarbon group and a chlorosilyl group. In addition, CF 3 CH 2 O (CH 2 ) 15 SiCL 3 , CF 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 15 SiCl 3 , F (CF 2 ) 4 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 3 SiCl 3 , CF 3 COO (CH 2 ) 15 SiCl 3 and the like could be used.
또, 미리 표면을 10∼0.1μm 정도 조면처리해둔 기재를 사용하면, 실시예 1 및 2에서 있어서 발수각도는 각각 대략 160˚ 및 150˚의 것이 얻어졌다.Moreover, when the base material which roughened the surface about 10-0.1 micrometer previously was used, the water repelling angle of about 160 degrees and 150 degrees was obtained in Examples 1 and 2, respectively.
또, 어패럴용부재를 발수발유처리하는 경우의 본 발명의 실시예를 더욱 구체적으로 설명한다. 불화탄소기와 클로로실릴기를 복수개 함유한 물질을 비수계의 용매에 용해한 용액에, 표면에 수산기나 아미노기 혹은 카르복실기를 함유한 어패럴용부재를 침지한 후 상기 용액중에서 어패럴용부재를 꺼내서 수분을 거의 함유하지 않는 분위기속에서 건조하여 비수계용매를 제거하면, 상기 단분자막 표면에 상기 클로로실릴기를 복수개 함유한 물질의 도포막이 형성된다. 그리고 다시 공기중으로 꺼내면, 이 도포막은 공기중의 수분과 탈염산 반응해서 폴리머화된다.In addition, the embodiment of the present invention in the case of water-repellent oil repellent treatment for the apparel member will be described in more detail. After immersing an apparel member containing a hydroxyl group, an amino group, or a carboxyl group on the surface of a solution containing a plurality of fluorocarbon and chlorosilyl groups in a non-aqueous solvent, the apparel member is removed from the solution and contains little moisture. When the non-aqueous solvent is removed by drying in a non-ambient atmosphere, a coating film of a substance containing a plurality of chlorosilyl groups is formed on the surface of the monomolecular film. Then, when taken out into the air again, the coating film is polymerized by dehydrochloric acid reaction with water in the air.
이때, 도포막은 상기 어패럴용부재 표면과도 탈염산 반응해서 공유결합을 발생하므로, 화학결합을 개재해서 어패럴용부재 표면에 결합한 불소를 다수 함유한 매우 발수발유이 높은 초박막을 형성할 수 있다.At this time, since the coating film is dehydrochloric acid also reacts with the surface of the apparel member to generate a covalent bond, it is possible to form a very high water / oil repellent ultra-thin film containing a large amount of fluorine bonded to the surface of the apparel member via a chemical bond.
[실시예 3]Example 3
먼저, 가공이 종료한 레인코트용 목면재 옷감(섬유등 표면에 수산기나 아미노기, 카르복실기등 클로로실릴기와 탈염산반응을 발생하는 관능기를 표면에 함유한 것이면 모피나 피혁등 무엇이든 좋다)을 준비하고(제1도(a)), 세정한 후 불화탄소기와 클로로실릴기를 복수개 가진 하기 일반식First, prepare the finished cotton for raincoat cloth (fur, leather, etc., if the surface contains functional groups such as hydroxyl group, amino group, carboxyl group, chlorosilyl group and dehydrochlorination reaction on the surface). (A) of the following general formula which has two or more fluorocarbon group and chlorosilyl group after washing | cleaning
CF3-(CF2)n-R-SiXpCl3-p CF 3- (CF 2 ) n -R-SiX p Cl 3-p
(단, n은 정수, R은 알킬기 또는 실리콘이나 산소원자를 함유한 치환기 또는 화학결합, X는 H 또는 알킬기, 알콕시기 등의 치환기, P는 0 또는 1)로, 표시되는 물질에 의해서 처리한다. 처리에 있어서는 비수계용매에 희석해서 사용한다.Where n is an integer, R is an alkyl group or a substituent containing a silicon or oxygen atom or a chemical bond, X is H or an substituent such as an alkyl group or an alkoxy group, and P is 0 or 1). . In the treatment, dilution with a non-aqueous solvent is used.
상기 일반식으로 표시되는 물질의 구체적 화합물로서는, 예를 들면 CF3(CF2)7(CH2)2SiCl3이 있다. 이 화합물을 불화탄소계용매(예를 들면 일본국 아사히유리회사제 : 하푸루드)에 1wt% 용해한 용액에 10분정도 침지하고, 그후 유기용제에 의해서 세정하는 일없이, 그대로 수분을 거의 함유하지 않는(바람직하게는 상대습도 5% 이하)분위기속에서 용매를 증발시키고 건조시키면 목면섬유(1)표면에 남은 불화탄소기와 클로로실릴기를 복수개 가진 물질에 의해서 약 2000Å 정도의 막두께로 도포막(2)이 형성된다. 이때, 일부의 불화탄소기와 클로로실릴기를 함유한 물질은, 면섬유표면의 수산기(3)의 탈염반응해서 실록산결합(-SiO-)(4)을 발생하고, 섬유표면에 고정된다(제1도(b)). 그리고, 다시 면제옷감을 수분을 함유한(상대습도 30% 정도 이상) 분위기속, 예를 들면 공기중으로 옮기면, 이 섬유표면에 도포막 및 고정된 불화탄소기와 클로로실릴기를 함유한 물질이 남은 클로로실릴기는 공기중의 수분과 탈염산 반응해서 폴리머화된다. 이와 같이 해서 작성된 도포막은 불소를 다수 함유하고 실록산결합(4)에 의해서 면섬유표면에 결합되기 때문에, 매우 발수발유성이 높은 초박막(5)이 목면섬유 표면에 형성된다(제1도(c)).Examples of specific compounds of the substance represented by the general formula, for example, a CF 3 (CF 2) 7 ( CH 2) 2 SiCl 3. This compound is immersed in a solution of 1 wt% dissolved in a carbon fluoride solvent (e.g., Asahi Glass Co., Ltd .: Hafurud) for about 10 minutes, and thereafter contains almost no moisture without being washed with an organic solvent. When the solvent is evaporated and dried in an atmosphere, preferably, the coating film has a film thickness of about 2000Å by a material having a plurality of carbon fluoride groups and chlorosilyl groups remaining on the surface of the cotton fiber (2). Is formed. At this time, the substance containing some fluorocarbon group and chlorosilyl group is desalted by the hydroxyl group 3 on the surface of the cotton fiber to generate a siloxane bond (-SiO-) 4, and is fixed to the surface of the fiber (FIG. b)). Then, when the exemption cloth is transferred to an atmosphere containing water (at least about 30% relative humidity), for example, in the air, chlorosilyl in which the coating film and the substance containing fluorocarbon group and chlorosilyl group remain on the fiber surface. The group is polymerized by dehydrochloric acid reaction with water in the air. Since the coating film produced in this way contains many fluorine and is bonded to the surface fiber surface by the siloxane bond 4, the ultra-thin water-repellent ultra-thin film 5 is formed in the surface fiber surface (FIG. 1 (c)). .
또한, CF3(CF2)7(CH2)2SiCL3을 아푸루드에 용해한 용액에 등 mol 농도로 피리딘(클로로실릴기와 반응하지 않고, 수분을 함유하지 않은 알칼리이면 무엇이든 좋다)을 첨가해두면, 목면재 옷감을 열화시키지 않고 처리를 행할 수 있었다.In addition, pyridine (anything that does not react with chlorosilyl groups and does not contain moisture) may be added to a solution of CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCL 3 dissolved in Afurud at an equimolar concentration. If it was, it could process without degrading cotton fabric.
이 이유는 목면섬유의 수산기(-OH기) 또는 카르복실기와, 상기 CF3(CF2)7(CH2)2SiCl3의 클로로실릴기(-Cl기)와의 화학흡착에 의해서 생성된 염산은 목면을 열화시키는 것으로 생각된다. 그러나, 피리딘을 상당량 첨가해두면, 탈염산은 피리딘에 의해서 증화하고, 목면섬유를 손상하지 않기 때문이라고 생각된다.This is because the hydrochloric acid produced by chemical adsorption of hydroxyl group (-OH group) or carboxyl group of cotton fiber with chlorosilyl group (-Cl group) of CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 It is thought to deteriorate. However, if pyridine is added in a considerable amount, it is considered that dehydrochloric acid increases with pyridine and does not damage cotton fibers.
이와 같이 해서 얻어진 불화탄소기를 함유한 초박막은 면섬유와 실록산결합을 개재해서 공유결합되어 있고, 문질러도 세정해도 벗겨지는 일이 없었다. 또 이와 같이 해서 발수발유처리된 면제옷감의 물에 대한 젖음각도를 계측하면 대략 170˚였다.The ultra-thin film containing the fluorocarbon group thus obtained was covalently bonded via cotton fibers and siloxane bonds, and did not peel off even if rubbed or washed. Moreover, it was about 170 degrees when the wet angle with respect to the water of the water- and oil-repellent exempt cloth treated in this way was measured.
[실시예 4]Example 4
가공이 종료한 나일론섬유(11)을 준비하고(제2도(a)), 세정한 후 불화탄소기와 클로로실릴기를 복수개 가진 물질, 예를 들면 CF3(CF2)5(CH2)2SiCl3을 탄화수소계 용매(노멀헥산)에 1wt% 용해한 용액에 20분정도 침지하고, 그후 유기용제에 의해서 세정하는 일없이, 그대로 수분을 거의 함유하지 않는(바람직하게는 상대습도 5% 이하)분위기속에서 용매를 증발시키고 건조시키면, 표면에 남은 불화탄소기와 클로로실릴기를 복수개 가진 물질에 의해서 100Å 정도의 막두께로 도포막(12)이 형성된다. 이때, 일부의 불화탄소기의 클로로실릴기를 함유한 물질은, 섬유표면의 이미노기(13)와 탈염산반응해서 실록산 결합(-SiO-)(14)을 발생하고, 섬유기재표면에 고정된다(제2도(b)). 그리고, 다시 기재의 수분을 함유한(상대습도 30% 정도이상) 분위기속, 예를 들면 공기중으로 옮기면, 이 도포막 및 고정된 불화탄소기와 클로로실릴기를 함유한 물질이 남은 클로로실릴기는 공기중의 수분과 탈염산 반응해서 폴리머화된다. 이와 같이 해서 작성된 도포막은 불소를 다수 함유하고 -SiN- 결합(14)에 의해서 섬유표면에 결합되기 때문에, 매우 발수발유성이 높은 초박막(15)이 섬유표면에 형성된다(제2도(C)).The nylon fiber 11 after processing is prepared (FIG. 2 (a)), and after cleaning, a substance having a plurality of fluorocarbon groups and chlorosilyl groups, for example, CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3 is immersed in a solution of 1 wt% dissolved in a hydrocarbon solvent (normal hexane) for about 20 minutes, and then washed almost with an organic solvent, containing almost no moisture (preferably relative humidity of 5% or less). When the solvent is evaporated and dried, the coating film 12 is formed to a film thickness of about 100 GPa by a material having a plurality of fluorocarbon groups and chlorosilyl groups remaining on the surface. At this time, the substance containing the chlorosilyl group of some fluorocarbon group dehydrochloric acid reacts with the imino group 13 of a fiber surface, and produces | generates a siloxane bond (-SiO-) 14, and is fixed to the fiber base surface ( 2 (b)). Then, when transferred to an atmosphere containing moisture of the base material (about 30% or higher relative humidity), for example, in air, the chlorosilyl group in which the coating film and the substance containing the fixed fluorocarbon group and chlorosilyl group remain is present in the air. Dehydrochloric acid reacts with water to polymerize. Since the coating film thus produced contains a large amount of fluorine and is bonded to the fiber surface by the -SiN-bond 14, an ultra-thin film 15 having a very high water and oil repellency is formed on the fiber surface (FIG. 2C). ).
또한, 이 초박막은 섬유와 -SiN- 결합을 개재해서 공유결합되어 있고, 문질러도 세정해도 벗겨지는 일이 없다. 이와 같이 해서 발수발유처리된 나일론 섬유를 옷감으로 찐후, 물에 대한 젖음강도를 측정하면, 대략 170˚로서 매우 높았다.In addition, this ultra-thin film is covalently bonded via fiber and -SiN- bond, and it does not peel off even if it rubs and washes. In this way, after the water- and oil-repellent treated nylon fibers were steamed with a cloth, the wet strength with respect to water was measured, which was very high as approximately 170 degrees.
또한, 상기 실시예에서는 불화탄소기와 클로로실릴기를 함유한 물질로서, CF3(CF2)7(CH2)2SiCl3, CF3(CF2)5(CH2)2SiCl3를 사용했으나, 이 이외에 하기의 물질등도 이용할 수 있었다.In addition, in the above examples, CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 SiCl 3 was used as a material containing a fluorocarbon group and a chlorosilyl group. In addition, the following substances were also available.
CF3CH2O(CH2)15SiCl3, CF3(CH2)2Si(CH3)2(CH2)15SiCl3, F(CF2)4(CH2)2Si(CH3)2(CH2)9SiCl3, CF3COO(CH2)15SiCl3 CF 3 CH 2 O (CH 2 ) 15 SiCl 3 , CF 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 15 SiCl 3 , F (CF 2 ) 4 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 9 SiCl 3 , CF 3 COO (CH 2 ) 15 SiCl 3
이상 설명한 바와 같이, 본원 발명의 방법을 사용하면, 매우 발수발유효과가 높은 초박막을 화학결합을 개재해서 기재표면에 형성할 수 있으므로, 내구성이 높은 발수발유화처리를 매우 간단히 행할 수 있는 효과가 있었다.As described above, when the method of the present invention is used, an ultra-thin film having a very high water and oil repelling effect can be formed on the surface of the substrate via a chemical bond, so that the highly durable water and oil repellent treatment can be easily performed. .
또한 이상 설명한 대로, 본원 발명을 사용하면, 매우 발수발유효과가 높은 초박막을 공유결합을 개재해서 기재표면에 형성할 수 있으므로, 내구성이 높은 발수발유처리한 어패럴용부재를 저코스트로 제공할 수 있는 효과가 있다.As described above, according to the present invention, an ultra-thin film having a very high water / oil repelling effect can be formed on the surface of the substrate via a covalent bond, so that the durable water / oil repellent treated apparel member can be provided at a low cost. It has an effect.
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4194266A JP2500178B2 (en) | 1991-07-26 | 1992-07-21 | Water and oil repellent treatment method for substrate surface |
| JP92-194266 | 1992-07-21 |
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| Publication Number | Publication Date |
|---|---|
| KR940005779A KR940005779A (en) | 1994-03-22 |
| KR960015813B1 true KR960015813B1 (en) | 1996-11-21 |
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| KR1019930005596A KR960015813B1 (en) | 1992-07-21 | 1993-04-02 | Process for having a prepellent on surface |
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