KR20180081052A - Polymer-modified organosilicon compounds containing fluoropolyether groups, surface treatment agents and articles - Google Patents
Polymer-modified organosilicon compounds containing fluoropolyether groups, surface treatment agents and articles Download PDFInfo
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- KR20180081052A KR20180081052A KR1020187011940A KR20187011940A KR20180081052A KR 20180081052 A KR20180081052 A KR 20180081052A KR 1020187011940 A KR1020187011940 A KR 1020187011940A KR 20187011940 A KR20187011940 A KR 20187011940A KR 20180081052 A KR20180081052 A KR 20180081052A
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- 150000003961 organosilicon compounds Chemical class 0.000 title claims abstract description 42
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 229920000642 polymer Polymers 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 2
- -1 silylene group Chemical group 0.000 abstract description 23
- 238000005299 abrasion Methods 0.000 abstract description 20
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- 125000005375 organosiloxane group Chemical group 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 22
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- 238000003786 synthesis reaction Methods 0.000 description 17
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- 229910052796 boron Inorganic materials 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 2
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- 125000001033 ether group Chemical group 0.000 description 2
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
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- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BABPEPRNSRIYFA-UHFFFAOYSA-N silyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)O[SiH3] BABPEPRNSRIYFA-UHFFFAOYSA-N 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 description 1
- LHJCZOXMCGQVDQ-UHFFFAOYSA-N tri(propan-2-yl)silyl trifluoromethanesulfonate Chemical compound CC(C)[Si](C(C)C)(C(C)C)OS(=O)(=O)C(F)(F)F LHJCZOXMCGQVDQ-UHFFFAOYSA-N 0.000 description 1
- STMPXDBGVJZCEX-UHFFFAOYSA-N triethylsilyl trifluoromethanesulfonate Chemical compound CC[Si](CC)(CC)OS(=O)(=O)C(F)(F)F STMPXDBGVJZCEX-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
온화한 조건하 단시간에 있어서도 내마모성이 우수한 발수발유층을 형성할 수 있는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물, 이 화합물을 포함하는 표면 처리제, 및 이 처리제로 표면 처리된 물품을 제공한다. 하기 일반식 (1)[Rf는 플루오로옥시알킬기 또는 플루오로옥시알킬렌기 함유 폴리머 잔기, Y는 2가 탄화수소기, Q는 2가 오가노실록세인 잔기, 실알킬렌기 또는 실아릴렌기, X는 수소 원자, 알킬기 또는 페닐기, Z는 수소 원자, 하식 -SiR3(R은 알킬기 또는 페닐기.)으로 표시되는 기, 또는 하식 -W-Q'-X(W는 단결합 또는 2가 탄화수소기, Q'는 실록세인 결합, 실알킬렌 구조 및 실아릴렌 구조로부터 선택되는 구조를 가지는 2가의 기.)으로 표시되는 기, α는 1 또는 2.]으로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.
Description
본 발명은 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물, 이 유기 규소 화합물을 포함하는 표면 처리제, 및 이 표면 처리제로 표면 처리된 물품에 관한 것이다.The present invention relates to a polymer-modified organosilicon compound containing a fluoropolyether group, a surface treatment agent containing the organosilicon compound, and an article surface-treated with the surface treatment agent.
최근, 휴대전화의 디스플레이를 비롯하여 화면의 터치패널화가 가속되고 있다. 그러나 터치패널은 화면이 노출된 상태이며, 손가락이나 뺨 등이 직접 부착되는 기회가 많아, 피지 등의 오염물이 부착되기 쉬운 것이 문제가 되고 있다. 그래서 외관이나 시인성을 좋게 하기 위해서 디스플레이의 표면에 지문이 묻기 어렵게 하는 기술이나, 오염물을 제거하기 쉽게 하는 기술의 요구가 해마다 높아지고 있으며, 이러한 요구에 부응할 수 있는 재료의 개발이 요망되고 있다. 특히 터치패널 디스플레이의 표면은 지문 얼룩이 부착되기 쉽기 때문에, 발수발유층을 설치하는 것이 요망되고 있다. 그러나 종래의 발수발유층은 발수발유성이 높고, 오염물을 닦아내는 성질이 우수하지만, 사용중에 방오 성능이 열화해버린다는 문제점이 있었다. 또 도공하는 방법에 의해 성능에 불균일이 생기거나, 도공하는 기재에 의해 밀착성이 떨어지거나 하는 경우가 있었다. 또한 지금까지의 표면 처리제는 유리에 대하여 양호한 표면 특성을 나타내는 것은 많이 있었지만, 수지 표면에 대하여 밀착성이나 발수발유성, 내마모성 등의 표면 특성을 충분히 나타내는 것이 없었다.BACKGROUND ART [0002] In recent years, a touch panel of a screen has been accelerated including a display of a mobile phone. However, the touch panel is in a state in which the screen is exposed, and there are many opportunities for the finger or cheek to be directly attached thereto, so that it is apt to attach contaminants such as sebum. Therefore, a technique for making fingerprints hard to get on the surface of the display to improve the appearance and visibility, and a technique for making it easier to remove contaminants are increasing every year, and development of a material capable of meeting such demands is desired. Particularly, since the surface of the touch panel display is prone to fingerprint unevenness, it is desired to provide a water-repellent layer. However, the conventional water- and oil-repellent layer has high water and oil repellency and is excellent in wiping off pollutants, but has a problem that the antifouling performance is deteriorated during use. In addition, there are cases where unevenness in performance is caused by the method of coating, or adhesiveness is deteriorated by a coating material. Although many of the surface treating agents so far exhibit good surface properties with respect to glass, there have been no satisfactory surface characteristics such as adhesiveness, water-repellency and oil repellency, and abrasion resistance to the resin surface.
일반적으로 플루오로폴리에터기 함유 화합물은 그 표면 자유 에너지가 매우 작기 때문에, 발수발유성, 내약품성, 윤활성, 이형성, 방오성 등을 가진다. 그 성질을 이용하여, 공업적으로는 종이·섬유 등의 발수발유 방오제, 자기 기록 매체의 활제, 정밀기기의 방유제, 이형제, 화장료, 보호막 등, 폭넓게 이용되고 있다. 그러나 그 성질은 동시에 다른 기재에 대한 비점착성, 비밀착성인 것을 의미하고 있어, 기재 표면에 도포할 수는 있어도, 그 피막을 밀착시키는 것은 곤란했다.Generally, the fluoropolyether group-containing compound has water and oil repellency, chemical resistance, lubricity, releasability and antifouling property because its surface free energy is very small. Utilizing such properties, it is industrially widely used as a water and oil repellent agent for paper and fiber, a lubricant for a magnetic recording medium, a lubricant for a precision instrument, a release agent, a cosmetic, and a protective film. However, this property means that it is non-tacky and non-tacky to other substrates at the same time, and it is difficult to adhere the film even if it can be applied to the surface of the substrate.
한편, 유리나 천 등의 기재 표면과 유기 화합물을 결합시키는 것으로서, 실레인커플링제가 잘 알려져 있고, 각종 기재 표면의 코팅제로서 폭넓게 이용되고 있다. 실레인커플링제는 1분자 중에 유기 관능기와 반응성 실릴기(일반적으로는 알콕시실릴기 등의 가수분해성 실릴기)를 가진다. 가수분해성 실릴기가 공기 중의 수분 등에 의해 자기 축합 반응을 일으켜 피막을 형성한다. 이 피막은 가수분해성 실릴기가 유리나 금속 등의 표면과 화학적·물리적으로 결합함으로써 내구성을 가지는 강고한 피막이 된다.On the other hand, a silane coupling agent is well known for bonding an organic compound to a substrate surface such as glass or cloth, and is widely used as a coating agent for various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silyl group (generally, a hydrolyzable silyl group such as an alkoxysilyl group) in a molecule. A hydrolyzable silyl group causes a self condensation reaction by moisture or the like in the air to form a film. This film is a strong film having durability by chemically and physically bonding the hydrolyzable silyl group to the surface of glass, metal, or the like.
그래서 플루오로폴리에터기 함유 화합물에 가수분해성 실릴기를 도입한 플루오로폴리에터기 함유 폴리머 변성 실레인을 사용함으로써, 기재 표면에 밀착하기 쉽고, 또한 기재 표면에 발수발유성, 내약품성, 윤활성, 이형성, 방오성 등을 가지는 피막을 형성할 수 있는 조성물이 개시되어 있다(특허문헌 1~8: 일본 특개 2003-238577호 공보, 일본 특허 제2860979호 공보, 일본 특허 제4672095호 공보, 일본 특표 2008-534696호 공보, 일본 특표 2008-537557호 공보, 일본 특개 2012-072272호 공보, 일본 특개 2012-157856호 공보, 일본 특개 2013-136833호 공보).Thus, by using a polymer-modified silane having a fluoropolyether group in which a hydrolyzable silyl group is introduced into a fluoropolyether group-containing compound, it is easy to adhere to the surface of the substrate, and the surface of the substrate is also excellent in water and oil repellency, chemical resistance, , Antifouling property, and the like (JP-A-2003-238577, JP-B-2860979, JP-A-4672095, JP-A-2008-534696 Japanese Patent Laid-Open Publication No. 2008-537557, Japanese Laid-Open Patent Publication No. 2012-072272, Japanese Laid-Open Patent Application No. 2012-157856, Japanese Laid-Open Patent Publication No. 2013-136833).
상기 플루오로폴리에터기 함유 폴리머 변성 실레인을 함유하는 조성물로 기재를 표면 처리할 때, 각종 도공 방법을 사용하여 기재에 대하여 피막 형성을 행하는데, 도공 후 가수분해성 실릴기를 가수분해하고, 피막을 경화하는 공정에 있어서, 80℃나 120℃ 등의 고온 조건이나, 가습하의 조건에 의해 가수분해 반응이 촉진된다. 또 실온하에서도 공기 중의 수분과 서서히 반응함으로써 경화 피막을 형성할 수 있다. 그러나 이 경화 공정은 고온 가습 조건을 필요로 하는 것이나, 실온하에서 경화하는 경우에 시간이 걸리는 등 제조상의 율속(지연 요인)이 될 수 있다는 문제가 있었다. 또한 실온 경화 등의 온화한 조건하에서 단시간에 경화한 피막(발수발유층)은 내마모성, 사용중에 방오 성능이 열화해버린다는 문제점이 있었다.When the substrate is surface-treated with the composition containing the fluoropolyether group-containing polymer-modified silane, the film is formed on the substrate by using various coating methods. After the coating, the hydrolyzable silyl group is hydrolyzed, In the curing step, the hydrolysis reaction is promoted by high temperature conditions such as 80 占 폚 or 120 占 폚 or under humidified conditions. Also, even at room temperature, a cured film can be formed by gradually reacting with moisture in the air. However, this curing process requires a high-temperature humidifying condition, and it may take time to cure under room temperature, which may lead to a rate-of-production (retarding factor). In addition, the coating (water-repellent oil layer) cured in a short time under mild conditions such as room temperature curing has a problem that abrasion resistance and antifouling performance are deteriorated during use.
특허문헌 9(일본 특개 2008-144144호 공보)에서는 코팅 조성물 내에 경화 촉매로서 함불소 카복실산을 첨가하여 경화를 촉진시킴으로써 온화한 조건하 단시간에 성막을 행하고 있다. 그러나 촉매량을 저감하면 내마모성이 떨어지고, 촉매량을 증가시키면 초기 성능이 저하된다. 또 극성기인 카복실기가 피막 최표면에 나와버릴 가능성도 높아, 그 때는 성능이 저하되어버린다.In Patent Document 9 (Japanese Unexamined Patent Application Publication No. 2008-144144), a fluorine-containing carboxylic acid is added as a curing catalyst in a coating composition to accelerate curing, thereby forming a film in a short time under mild conditions. However, when the amount of the catalyst is reduced, the abrasion resistance is lowered, and when the amount of the catalyst is increased, the initial performance is lowered. In addition, there is a high possibility that a carboxyl group, which is a polar group, comes out from the outermost surface of the coating film, and the performance is deteriorated at that time.
또 특허문헌 10(일본 특개 2004-145283호 공보)에서는 플루오로폴리알킬렌에터기 함유 실레인이 제안되어 있다. 이 플루오로폴리알킬렌에터기 함유 실레인으로 처리한 렌즈는 발유성, 지문을 닦아내는 성질이 우수하지만, 내마모성이 충분하지 않다.In addition, in Patent Document 10 (Japanese Unexamined Patent Application Publication No. 2004-145283), a silane having a fluoropolyalkylene ether group has been proposed. The lens treated with this fluoropolyalkylene ether group-containing silane has excellent properties of wiping off the oil repellency and fingerprints, but the abrasion resistance is not sufficient.
본 발명은 상기 사정을 감안하여 이루어진 것으로, 특히 수지 표면에 있어서, 실온 등의 온화한 조건하 단시간에 있어서도 내마모성이 우수한 발수발유층을 형성할 수 있는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물, 이 유기 규소 화합물을 포함하는 표면 처리제, 및 이 표면 처리제로 표면 처리된 물품을 제공하는 것을 목적으로 한다.The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polymer-modified organosilicon compound containing a fluoropolyether group capable of forming a water-repellent layer excellent in abrasion resistance even under a mild condition such as room temperature, A surface treatment agent containing an organosilicon compound, and an article surface-treated with the surface treatment agent.
본 발명자들은 상기 목적을 해결하기 위해 예의 검토한 결과, 후술하는 일반식 (1)로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 사용한 표면 처리제가, 말단 관능기를 가지지 않아도, 실온 등의 온화한 조건하 단시간에도 내마모성이 우수한 발수발유층을 수지 필름이나 플라스틱 렌즈 등의 수지 제품에 대하여 형성할 수 있는 것을 알아내어, 본 발명을 이루기에 이르렀다.DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to solve the above object, and as a result, they have found that a surface treating agent using a fluoropolyether group-containing polymer-modified organosilicon compound represented by the following general formula (1) The present inventors have found that a water-repellent oil-repellent layer having excellent abrasion resistance even under a mild condition for a short period of time can be formed on a resin product such as a resin film or a plastic lens.
따라서 본 발명은 하기 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물, 표면 처리제 및 물품을 제공한다.Accordingly, the present invention provides a fluorinated polyether group-containing polymer-modified organosilicon compound, a surface treatment agent and an article.
〔1〕〔One〕
하기 일반식 (1)(1)
[식 중, Rf는 1가의 플루오로옥시알킬기 또는 2가의 플루오로옥시알킬렌기 함유 폴리머 잔기이며, Y는 독립적으로 2가의 탄화수소기이며, Q는 독립적으로 2가의 직쇄상 혹은 환상 오가노실록세인 잔기, 실알킬렌기 또는 실아릴렌기이며, X는 독립적으로 수소 원자, 탄소수 1~4의 알킬기 또는 페닐기이며, Z는 독립적으로 수소 원자, 하기 식Wherein Rf is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, Q is independently a divalent linear or cyclic organosiloxane residue , X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, Z is independently a hydrogen atom, a group represented by the following formula
(식 중, R은 독립적으로 탄소수 1~4의 알킬기 또는 페닐기이다.)(Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group)
으로 표시되는 기, 또는 하기 식Or a group represented by the following formula
(식 중, X는 상기와 동일하며, W는 단결합 또는 2가의 탄화수소기이며, Q'는 실록세인 결합, 실알킬렌 구조 및 실아릴렌 구조로부터 선택되는 구조를 가지는 2가의 기이다.)(Wherein X is as defined above, W is a single bond or a divalent hydrocarbon group, and Q 'is a divalent group having a structure selected from siloxane bonds, alkylalkylene structures and silarylene structures.)
으로 표시되는 기이며, α는 1 또는 2이다.]And? Is 1 or 2.]
로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.And the fluoro polyether group-containing polymer modified organosilicon compound represented by the formula
〔2〕〔2〕
상기 식 (1)에 있어서, α가 1이며, Rf 기가 하기 일반식 (2)로 표시되는 기인 것을 특징으로 하는 〔1〕에 기재된 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.The fluoro polyether group-containing polymer-modified organosilicon compound according to [1], wherein? Is 1 and the Rf group is a group represented by the following general formula (2) in the above formula (1).
(식 중, p, q, r, s는 각각 0~200의 정수이며, p+q+r+s=3~200이며, 각 반복 단위는 직쇄상이어도 되고 분기상이어도 되며, 각 반복 단위끼리는 랜덤으로 결합되어 있어도 되고, d는 1~3의 정수이며, 이 단위는 직쇄상이어도 되고 분기상이어도 된다.)(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, D may be an integer of 1 to 3, and the unit may be linear or branched.
〔3〕[3]
상기 식 (1)에 있어서, α가 2이며, Rf 기가 하기 일반식 (3)으로 표시되는 기인 것을 특징으로 하는 〔1〕에 기재된 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.The fluoro polyether group-containing polymer-modified organosilicon compound according to [1], wherein? Is 2 in the above formula (1) and the Rf group is a group represented by the following formula (3).
(식 중, p, q, r, s는 각각 0~200의 정수이며, p+q+r+s=3~200이며, 각 반복 단위는 직쇄상이어도 되고 분기상이어도 되며, 각 반복 단위끼리는 랜덤으로 결합되어 있어도 되고, d는 1~3의 정수이며, 이 단위는 직쇄상이어도 되고 분기상이어도 된다.)(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, D may be an integer of 1 to 3, and the unit may be linear or branched.
〔4〕〔4〕
상기 식 (1)에 있어서, Y가 탄소수 3~10의 알킬렌기인 〔1〕 내지 〔3〕 중 어느 하나에 기재된 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.The polymer-modified organosilicon compound containing fluoropolyether group according to any one of [1] to [3], wherein Y is an alkylene group having 3 to 10 carbon atoms in the formula (1).
〔5〕[5]
상기 식 (1)에 있어서, Q가 하기 식으로 표시되는 기로부터 선택되는 기인 〔1〕 내지 〔4〕 중 어느 하나에 기재된 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.The fluoro polyether group-containing polymer-modified organosilicon compound according to any one of [1] to [4], wherein Q in the formula (1) is a group selected from groups represented by the following formulas.
(식 중, X는 상기와 동일하며, R1은 독립적으로 탄소수 1~4의 알킬기 또는 페닐기이며, R2는 탄소수 1~4의 알킬렌기 또는 탄소수 6~12의 아릴렌기이다. g는 1~20의 정수이며, j는 1~8의 정수이다.)(In the formula, X is the same as above, R 1 is independently an alkyl group or a phenyl group having from 1 to 4 carbon atoms, R 2 is an aryl group having from 1 to 4 carbon atoms, an alkylene group or carbon number of 6-12 in. G is 1 to 20, and j is an integer of 1 to 8.)
〔6〕[6]
상기 식 (1)에 있어서, Z가 수소 원자, 및 하기에 나타내는 기로부터 선택되는 기인 〔1〕 내지 〔5〕 중 어느 하나에 기재된 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.The fluoro polyether group-containing polymer-modified organosilicon compound according to any one of [1] to [5], wherein Z in the formula (1) is a hydrogen atom and a group selected from the following groups.
(식 중, g1은 2~20의 정수이며, e는 0~3의 정수이다.)(Wherein g1 is an integer of 2 to 20, and e is an integer of 0 to 3.)
〔7〕[7]
상기 식 (1)로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물이 하기 식 중 어느 하나로 표시되는 것인 〔1〕 내지 〔6〕 중 어느 하나에 기재된 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.The fluoro polyether group-containing polymer-modified organosilicon compound represented by the above-mentioned formula (1) is represented by any one of the following formulas (1) to (6) Silicon compounds.
(식 중, Z는 상기와 동일하며, p1은 5~100의 정수, q1은 5~100의 정수이며, p1+q1은 10~105의 정수이다. g1은 2~20의 정수이며, e는 0~3의 정수이다.)P1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1 + q1 is an integer of 10 to 105. g1 is an integer of 2 to 20, and e is It is an integer from 0 to 3.)
〔8〕〔8〕
〔1〕 내지 〔7〕 중 어느 하나에 기재된 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 포함하는 표면 처리제.A surface treatment agent comprising a polymer-modified organosilicon compound containing a fluoropolyether group according to any one of [1] to [7].
〔9〕[9]
표면 처리제가 추가로 하기 일반식 (4)The surface treating agent further comprises a compound represented by the general formula (4)
(식 중, A는 말단이 -CF3기인 1가의 불소 함유기이며, Rf'는 2가의 플루오로옥시알킬렌기 함유 폴리머 잔기이다.)(Wherein A is a monovalent fluorine-containing group whose terminal is a -CF 3 group and Rf 'is a divalent fluorooxyalkylene group-containing polymer residue).
로 표시되는 플루오로폴리에터기 함유 폴리머를 함유하는 것을 특징으로 하는 〔8〕에 기재된 표면 처리제.The surface treatment agent according to [8], which further comprises a fluoropolyether group-containing polymer represented by the formula
〔10〕[10]
〔9〕에 기재된 표면 처리제로 표면 처리된 물품.The article surface-treated with the surface-treating agent according to [9].
본 발명의 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 함유하는 표면 처리제로 형성되는 피막은 발수발유성이 높고, 특히 실온 등의 온화한 조건하 단시간에 형성되는 피막은 내마모성이 우수하다. 본 발명의 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 함유하는 표면 처리제는 특히 수지 표면에 대하여 특이적인 밀착성을 가지므로, 이 표면 처리제로 처리함으로써, 수지 필름이나 안경 렌즈와 같은 수지 제품에 우수한 발수발유성, 저동마찰성, 내마모성을 단시간에 용이하게 부여할 수 있다.The coating film formed from the surface treatment agent containing the fluoropolyether group-containing polymer modified organosilicon compound of the present invention has high water and oil repellency, and the coating film formed in a short time under mild conditions such as room temperature is excellent in abrasion resistance. The surface treatment agent containing the fluoropolyether group-containing polymer modified organosilicon compound of the present invention has a specific adhesion to the surface of the resin in particular, so that the surface treatment agent is excellent in resin products such as a resin film and a spectacle lens Water-repelling and oil-repellent, low-dynamic friction, and abrasion resistance in a short time.
본 발명의 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물은 하기 일반식 (1)로 표시되는 것이다.The polymer-modified organosilicon compound containing fluoropolyether group of the present invention is represented by the following general formula (1).
[식 중, Rf는 1가의 플루오로옥시알킬기 또는 2가의 플루오로옥시알킬렌기 함유 폴리머 잔기이며, Y는 독립적으로 2가의 탄화수소기이며, Q는 독립적으로 2가의 직쇄상 혹은 환상 오가노실록세인 잔기, 실알킬렌기 또는 실아릴렌기이며, X는 독립적으로 수소 원자, 탄소수 1~4의 알킬기 또는 페닐기이며, Z는 독립적으로 수소 원자, 하기 식Wherein Rf is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, Q is independently a divalent linear or cyclic organosiloxane residue , X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, Z is independently a hydrogen atom, a group represented by the following formula
(식 중, R은 독립적으로 탄소수 1~4의 알킬기 또는 페닐기이다.)(Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group)
으로 표시되는 기, 또는 하기 식Or a group represented by the following formula
(식 중, X는 상기와 동일하며, W는 단결합 또는 2가의 탄화수소기이며, Q'는 실록세인 결합, 실알킬렌 구조 및 실아릴렌 구조로부터 선택되는 구조를 가지는 2가의 기이다.)(Wherein X is as defined above, W is a single bond or a divalent hydrocarbon group, and Q 'is a divalent group having a structure selected from siloxane bonds, alkylalkylene structures and silarylene structures.)
으로 표시되는 기이며, α는 1 또는 2이다.]And? Is 1 or 2.]
상기 식 (1)에 있어서, α가 1인 경우, Rf로서는 하기 일반식 (2)로 표시되는 1가의 플루오로옥시알킬기가 바람직하다.In the formula (1), when? Is 1, Rf is preferably a monovalent fluorooxyalkyl group represented by the following formula (2).
(식 중, p, q, r, s는 각각 0~200의 정수이며, p+q+r+s=3~200이며, 각 반복 단위는 직쇄상이어도 되고 분기상이어도 되며, 각 반복 단위끼리는 랜덤으로 결합되어 있어도 되고, d는 1~3의 정수이며, 이 단위는 직쇄상이어도 되고 분기상이어도 된다.)(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, D may be an integer of 1 to 3, and the unit may be linear or branched.
상기 식(1)에 있어서, α가 2인 경우, Rf로서는 하기 일반식 (3)으로 표시되는 2가의 플루오로옥시알킬렌기가 바람직하다.In the formula (1), when? Is 2, Rf is preferably a divalent fluorooxyalkylene group represented by the following formula (3).
(식 중, p, q, r, s는 각각 0~200의 정수이며, p+q+r+s=3~200이며, 각 반복 단위는 직쇄상이어도 되고 분기상이어도 되며, 각 반복 단위끼리는 랜덤으로 결합되어 있어도 되고, d는 1~3의 정수이며, 이 단위는 직쇄상이어도 되고 분기상이어도 된다.)(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, D may be an integer of 1 to 3, and the unit may be linear or branched.
상기 식 (2), (3)에 있어서, p, q, r, s는 각각 0~200의 정수, 바람직하게는 p는 5~100의 정수, q는 5~100의 정수, r은 0~100의 정수, s는 0~100의 정수이며, p+q+r+s=3~200, 바람직하게는 10~100이며, 각 반복 단위는 직쇄상이어도 되고 분기상이어도 되며, 각 반복 단위끼리는 랜덤으로 결합되어 있어도 된다. 보다 바람직하게는 p+q는 10~105, 특히 15~60의 정수이며, r=s=0이다. p+q+r+s가 상기 상한값보다 작으면 밀착성이나 피막 형성성이 양호하며, 상기 하한값보다 크면 플루오로폴리에터기의 특징을 충분히 발휘할 수 있으므로 바람직하다.Each of p, q, r and s is an integer of 0 to 200, preferably p is an integer of 5 to 100, q is an integer of 5 to 100, and r is an integer of 0 to 100. In the above formulas (2) and (3) P + q + r + s = 3 to 200, preferably 10 to 100, and each repeating unit may be linear or branched, and each repeating unit may have a repeating unit Or they may be randomly combined. More preferably, p + q is an integer of 10 to 105, particularly 15 to 60, and r = s = 0. When p + q + r + s is smaller than the upper limit value, adhesion and film formability are good, and when it is larger than the lower limit value, the characteristics of the fluoropolyether can be sufficiently exhibited.
상기 식 (2), (3)에 있어서, d는 1~3의 정수이며, 바람직하게는 1 또는 2이며, 이 단위는 직쇄상이어도 되고 분기상이어도 된다.In the formulas (2) and (3), d is an integer of 1 to 3, preferably 1 or 2, and the unit may be linear or branched.
Rf로서 상기 식 (2) 또는 (3)으로 표시되는 주쇄 구조를 가짐으로써 동마찰계수가 낮은 피막을 형성할 수 있다.By having the main chain structure represented by the formula (2) or (3) as Rf, it is possible to form a film having a low coefficient of dynamic friction.
또 주쇄에 플루오로폴리에터 구조를 가지고, 분자쇄의 편말단에 실록세인 결합, 실페닐렌 결합 또는 실알킬렌 결합을 함유하는 직쇄상 폴리머(α가 1이며, Rf가 식 (2)로 표시되는 1가의 플루오로옥시알킬기)는 양 말단에 실록세인 결합, 실페닐렌 결합 또는 실알킬렌 결합을 함유하는 직쇄상 폴리머(α가 2이며, Rf가 식 (3)으로 표시되는 2가의 플루오로옥시알킬렌기)와 비교하여, 얻어지는 피막에 우수한 내마모성을 부여할 수 있다.A straight chain polymer having a fluoropolyether structure in its main chain and containing a siloxane bond, a silphenylene bond or a silylene linkage at one end of its molecular chain (a is 1 and Rf is a (A monovalent fluorooxyalkyl group to be represented) is a linear polymer containing a siloxane bond, a silphenylene bond or a silylene linkage at both terminals (a is 2 and Rf is a divalent fluorine represented by the formula (3) Oxyalkylene group), it is possible to impart excellent abrasion resistance to the obtained coating film.
Rf로서 구체적으로는 하기의 것을 예시할 수 있다.Specific examples of Rf include the following.
(식 중, p', q', r', s'는 각각 1 이상의 정수이며, 그 상한은 상기 p, q, r, s의 상한과 동일하다. u는 1~24, v는 1~24이며, u+v=r을 만족하는 수이다. 각 반복 단위는 랜덤으로 결합되어 있어도 된다.)Q, r 'and s' are each an integer of 1 or more, and the upper limit thereof is the same as the upper limit of p, q, r and s, u is 1 to 24, v is 1 to 24 And u + v = r. Each repeating unit may be bonded at random.)
상기 식 (1)에 있어서, Y는 독립적으로 2가의 탄화수소기이며, 탄소수 3~10, 특히 탄소수 3~8의 프로필렌기(트라이메틸렌기, 메틸에틸렌기), 뷰틸렌기(테트라메틸렌기, 메틸프로필렌기), 헥사메틸렌기, 옥타메틸렌기 등의 알킬렌기인 것이 바람직하고, 특히 바람직하게는 트라이메틸렌기이다.In the formula (1), Y is independently a divalent hydrocarbon group, and is a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene Group), a hexamethylene group, an octamethylene group and the like, and particularly preferably a trimethylene group.
상기 식(1)에 있어서, X는 독립적으로 수소 원자, 탄소수 1~4의 메틸기, 에틸기, 프로필기, 뷰틸기 등의 알킬기 또는 페닐기이며, 수소 원자, 메틸기가 바람직하다.In the above formula (1), X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, or a phenyl group, preferably a hydrogen atom or a methyl group.
상기 식 (1)에 있어서, Q는 독립적으로 2가의 직쇄상 혹은 환상 오가노실록세인 잔기, 실알킬렌기 또는 실아릴렌기이며, 하기 식으로 표시되는 기로부터 선택되는 기인 것이 바람직하다.In the above formula (1), Q is independently a divalent straight-chain or cyclic organosiloxane residue, an alkylene group or a silane group, and is preferably a group selected from the groups represented by the following formulas.
(식 중, X는 상기와 동일하며, R1은 독립적으로 탄소수 1~4의 메틸기, 에틸기, 프로필기, 뷰틸기 등의 알킬기 또는 페닐기이며, R2는 탄소수 1~4의 메틸렌기, 에틸렌기, 프로필렌기, 뷰틸렌기 등의 알킬렌기 또는 탄소수 6~12의 페닐렌기 등의 아릴렌기이다. g는 1~20, 바람직하게는 1~10의 정수이며, j는 1~8, 바람직하게는 1~3의 정수이다.)(Wherein X is as defined above, R 1 is independently an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, or a phenyl group, R 2 is a methylene group having 1 to 4 carbon atoms, , An alkylene group such as a propylene group or a butylene group or an arylene group such as a phenylene group having a carbon number of 6 to 12. g is an integer of 1 to 20, preferably 1 to 10, j is an integer of 1 to 8, preferably 1 It is an integer of ~ 3.)
Q의 구체예로서는 예를 들면 하기의 기를 들 수 있다.Specific examples of Q include, for example, the following groups.
(식 중, g1은 2~20, 바람직하게는 2~10의 정수이다.)(Wherein g1 is an integer of 2 to 20, preferably 2 to 10).
상기 식 (1)에 있어서, Z는 독립적으로 수소 원자, 하기 식In the above formula (1), Z is independently a hydrogen atom,
(식 중, R은 독립적으로 탄소수 1~4의 알킬기 또는 페닐기이다.)(Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group)
으로 표시되는 기, 또는 하기 식Or a group represented by the following formula
(식 중, X는 상기와 동일하며, W는 단결합 또는 2가의 탄화수소기이며, Q'는 실록세인 결합, 실알킬렌 구조 및 실아릴렌 구조로부터 선택되는 구조를 가지는 2가의 기이다.)(Wherein X is as defined above, W is a single bond or a divalent hydrocarbon group, and Q 'is a divalent group having a structure selected from siloxane bonds, alkylalkylene structures and silarylene structures.)
으로 표시되는 기이다.Lt; / RTI >
-SiR3에 있어서, R은 탄소수 1~4의 메틸기, 에틸기, 프로필기, 뷰틸기 등의 알킬기, 또는 페닐기이며, 그 중에서도 메틸기, 에틸기가 적합하다.In the case of -SiR 3 , R is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or a phenyl group, and among these, a methyl group and an ethyl group are suitable.
또 -W-Q'-X에 있어서, W는 단결합 또는 2가의 탄화수소기이며, 2가의 탄화수소기로서는 탄소수 2~10, 특히 탄소수 2~8의 에틸렌기, 프로필렌기(트라이메틸렌기, 메틸에틸렌기), 뷰틸렌기(테트라메틸렌기, 메틸프로필렌기), 헥사메틸렌기, 옥타메틸렌기 등의 알킬렌기를 들 수 있고, W로서는 단결합 또는 트라이메틸렌기인 것이 바람직하다.W represents a monovalent or divalent hydrocarbon group, and the divalent hydrocarbon group may be an ethylene group or a propylene group having 2 to 10 carbon atoms, particularly 2 to 8 carbon atoms, such as a trimethylene group, methylethylene (Tetramethylene group, methylpropylene group), hexamethylene group, and octamethylene group, and W is preferably a single bond or a trimethylene group.
X는 상기와 동일하며, 수소 원자, 메틸기가 바람직하다.X is the same as above, and a hydrogen atom and a methyl group are preferable.
또 Q'는 실록세인 결합, 실알킬렌 구조 및 실아릴렌 구조로부터 선택되는 구조를 가지는 2가의 기이며, 상기 Q에 있어서 예시한 2가의 직쇄상 혹은 환상 오가노실록세인 잔기, 실알킬렌 구조, 실아릴렌 구조를 가지는 것이 바람직하다.Q 'is a divalent group having a structure selected from a siloxane bond, a silylene structure and a silane structure, and is a divalent linear or cyclic organosiloxane residue as exemplified in Q above, , And a silylene structure.
Q'의 구체예로서는 예를 들면 하기의 기를 들 수 있다.Specific examples of Q 'include the following groups, for example.
(식 중, g1은 상기와 동일하다.)(Wherein g1 is as defined above).
Z로서 구체적으로는 수소 원자 및 하기에 나타내는 것을 예시할 수 있다.Specific examples of Z include a hydrogen atom and those shown below.
(식 중, g1은 상기와 동일하며, e는 0~3의 정수이다.)(Wherein g1 is as defined above, and e is an integer of 0 to 3.)
상기 식 (1)로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물로서는 하기 식으로 표시되는 것을 예시할 수 있다. 또한 각 식에 있어서, 플루오로옥시알킬기 또는 플루오로옥시알킬렌기를 구성하는 각 반복 단위의 반복수(또는 중합도)는 상기 식 (2), (3)을 만족하는 임의의 수를 취할 수 있는 것이다.Examples of the polymer-modified organosilicon compound containing a fluoropolyether group represented by the above formula (1) include those represented by the following formulas. The repeating number (or degree of polymerization) of each repeating unit constituting the fluorooxyalkyl group or the fluorooxyalkylene group in each of the formulas can take any number satisfying the above-mentioned formulas (2) and (3) .
(식 중, Z, g1, e는 상기와 동일하며, p1은 5~100의 정수, q1은 5~100의 정수이며, p1+q1은 10~105의 정수이다.)(Wherein Z, g1 and e are as defined above, p1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1 + q1 is an integer of 10 to 105.)
상기 식 (1)로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물의 조제 방법으로서는 예를 들면 하기와 같은 방법을 들 수 있다.Examples of the method for preparing the polymer-modified organosilicon compound containing a fluoropolyether group represented by the above formula (1) include the following methods.
우선, 분자쇄 말단에 산플루오라이드기, 산할라이드기, 산무수물기, 에스터기, 카복실산기, 아마이드기 등의 반응성기를 가지는 플루오로폴리에터기 함유 폴리머와, 구핵제와, 용제로서 예를 들면 1,3-비스(트라이플루오로메틸)벤젠, 테트라하이드로퓨란을 혼합하여, 0~80℃, 바람직하게는 50~70℃, 보다 바람직하게는 약 60℃에서, 1~6시간, 바람직하게는 3~5시간, 보다 바람직하게는 약 4시간 숙성한다.First, a fluoropolyether group-containing polymer having a reactive group such as an acid fluoride group, an acid halide group, an acid anhydride group, an ester group, a carboxylic acid group or an amide group at the molecular chain end, a nucleophilic agent, (Trifluoromethyl) benzene and tetrahydrofuran at a temperature of 0 to 80 ° C, preferably 50 to 70 ° C, more preferably about 60 ° C, for 1 to 6 hours, And aged for 3 to 5 hours, more preferably about 4 hours.
여기서 분자쇄 말단에 반응성기를 가지는 플루오로폴리에터기 함유 폴리머로서 구체적으로는 하기에 나타내는 것을 들 수 있다.Specific examples of the fluoropolyether group-containing polymer having a reactive group at the molecular chain terminal are shown below.
(식 중, Rf, α는 상기와 동일하다.)(Wherein Rf and? Are as defined above).
또 구핵제로서는 알릴마그네슘할라이드, 3-뷰테닐마그네슘할라이드, 4-펜테닐마그네슘할라이드, 5-헥세닐마그네슘할라이드 등을 사용할 수 있다. 또 대응하는 리튬 시약을 사용하는 것도 가능하다.As the nucleophilic agent, allylmagnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide and the like can be used. It is also possible to use a corresponding lithium reagent.
구핵제의 사용량은 상기 분자쇄 말단에 반응성기를 가지는 플루오로폴리에터기 함유 폴리머의 반응성기 1당량에 대하여 2~5당량, 보다 바람직하게는 2.5~3.5당량, 더욱 바람직하게는 약 3당량 사용할 수 있다.The amount of the nucleophilic agent to be used is 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and still more preferably about 3 equivalents, relative to 1 equivalent of the reactive group of the fluoropolyether group-containing polymer having a reactive group at the molecular chain end have.
계속해서 반응을 정지시키고, 분액 조작에 의해 수층과 불소 용제층을 분리한다. 얻어진 불소 용제층을 추가로 유기 용제로 세정하고, 용제를 증류제거함으로써, 하기 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머가 얻어진다.Subsequently, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by separating operation. The obtained fluorine solvent layer is further washed with an organic solvent and the solvent is distilled off to obtain a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the following formula (a).
(식 중, Rf, α는 상기와 동일하다. U는 2가의 탄화수소기이다.)(Wherein Rf and? Are as defined above, and U is a divalent hydrocarbon group).
상기 식 (a)에 있어서, U는 2가의 탄화수소기이며, 구체적으로는 메틸렌기, 에틸렌기, 프로필렌기(트라이메틸렌기, 메틸에틸렌기), 뷰틸렌기(테트라메틸렌기, 메틸프로필렌기), 헥사메틸렌기, 옥타메틸렌기 등의 탄소수 1~8의 알킬렌기, 페닐렌기 등의 탄소수 6~8의 아릴렌기를 포함하는 알킬렌기(예를 들면 탄소수 7~8의 알킬렌·아릴렌기 등) 등을 들 수 있다. U로서 바람직하게는 탄소수 1~4의 직쇄 알킬렌기이다.In the formula (a), U is a divalent hydrocarbon group and specifically includes a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group) An alkylene group having 7 to 8 carbon atoms such as an alkylene group having 1 to 8 carbon atoms such as a methylene group and an octamethylene group and an arylene group having an arylene group having a carbon number of 6 to 8 such as a phenylene group, . U is preferably a straight chain alkylene group having 1 to 4 carbon atoms.
이어서 필요에 따라 상기에서 얻어진 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머의 수산기의 수소 원자를 다른 기로 치환한다.Subsequently, if necessary, the hydrogen atom of the hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a) obtained above is substituted with another group.
수산기의 수소 원자를 -SiR3으로 표시되는 실릴기로 치환하는 방법으로서는 예를 들면 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머와 실릴화제를 아민류나 알칼리 금속계 염기 등의 염기의 존재하 필요에 따라 불소계 용제, 유기 용제 등의 용제를 사용하여 0~80℃, 바람직하게는 40~60℃, 보다 바람직하게는 약 50℃의 온도에서 1~24시간, 바람직하게는 2~10시간, 보다 바람직하게는 약 3시간 숙성한다.As a method for substituting the hydrogen atom of the hydroxyl group with the silyl group represented by -SiR 3 , for example, a method of reacting a silylation agent with a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal end represented by the formula (a) If necessary, in the presence of a base such as an alkali metal base at a temperature of 0 to 80 캜, preferably 40 to 60 캜, more preferably about 50 캜 for 1 to 24 hours , Preferably 2 to 10 hours, more preferably about 3 hours.
또 다른 방법으로서 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머와 하이드로실레인을 백금족 금속계 촉매나 붕소 촉매 등의 탈수소 촉매의 존재하 불소계 용제, 유기 용제 등의 용제를 사용하여 0~60℃, 바람직하게는 15~35℃, 보다 바람직하게는 약 25℃의 온도에서 10분~24시간, 바람직하게는 30분~2시간, 보다 바람직하게는 약 1시간 탈수소 반응을 행한다.As another method, a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a) is reacted with a fluorosolvent in the presence of a dehydrogenation catalyst such as a platinum group metal catalyst or a boron catalyst, Preferably 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably about 30 minutes to 2 hours, at a temperature of 0 to 60 ° C, preferably 15 to 35 ° C, more preferably about 25 ° C, Dehydrogenation reaction is carried out for 1 hour.
여기서 실릴화제로서는 예를 들면 실릴할라이드나 실릴트라이플레이트 등을 사용할 수 있고, 구체적으로는 트라이메틸실릴클로라이드, 트라이에틸실릴클로라이드, tert-뷰틸다이메틸클로라이드, 트라이아이소프로필실릴클로라이드, 트라이페닐실릴클로라이드, 트라이메틸실릴브로마이드, 트라이메틸실릴트라이플레이트, 트라이에틸실릴트라이플레이트, tert-뷰틸다이메틸트라이플레이트, 트라이아이소프로필실릴트라이플레이트 등을 들 수 있고, 또 염기를 사용하지 않는 경우, 헥사메틸다이실라잔, 트라이메틸실릴다이메틸아민, 트라이메틸실릴다이에틸아민, 트라이메틸실릴이미다졸을 사용해도 되고, 이 사용량은 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머의 수산기 1당량에 대하여 1~10당량, 보다 바람직하게는 1~4당량, 더욱 바람직하게는 약 2당량 사용할 수 있다.Examples of the silylating agent include silyl halide and silyl triflate. Specific examples thereof include trimethylsilyl chloride, triethylsilyl chloride, tert-butyldimethyl chloride, triisopropylsilyl chloride, triphenylsilyl chloride, Trimethylsilyl triflate, triethylsilyl triflate, tert-butyldimethyl triflate, triisopropylsilyl triflate and the like, and when no base is used, hexamethyldisilazane , Trimethylsilyldiethylamine, trimethylsilyldiethylamine, and trimethylsilylimidazole may be used, and the amount of the fluoropolyether having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a) Based on 1 equivalent of the hydroxyl group of the polymer containing 10 to 10 More preferably 1 to 4 equivalents, and still more preferably about 2 equivalents.
또 하이드로실레인으로서는 트라이메틸실레인, 트라이에틸실레인, tert-뷰틸다이메틸실레인, 트라이아이소프로필실레인, 트라이페닐실레인 등을 들 수 있고, 이 사용량은 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머의 수산기 1당량에 대하여 1~5당량, 보다 바람직하게는 1.5~3당량, 더욱 바람직하게는 약 2당량 사용할 수 있다.Examples of the hydrosilane include trimethylsilane, triethylsilane, tert-butyldimethylsilane, triisopropylsilane, and triphenylsilane. The amount of the hydrosilane to be used is such that the amount of the molecule represented by the formula (a) Preferably 1 to 5 equivalents, more preferably 1.5 to 3 equivalents, and still more preferably about 2 equivalents based on 1 equivalent of the hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the chain ends.
계속해서 반응을 정지시키고, 분액 조작에 의해 수층과 불소 용제층을 분리한다. 얻어진 불소 용제층을 추가로 유기 용제로 세정하고, 용제를 증류제거함으로써, 하기 식 (b)로 표시되는 분자쇄 말단에 실릴기 및 올레핀 부위를 가지는 플루오로옥시알킬기 함유 폴리머가 얻어진다.Subsequently, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by separating operation. The obtained fluorine solvent layer is further washed with an organic solvent and the solvent is distilled off to obtain a fluorooxyalkyl group-containing polymer having a silyl group and an olefin moiety at the molecular chain end represented by the following formula (b).
(식 중, Rf, R, U, α는 상기와 동일하다.)(Wherein Rf, R, U, and? Are as defined above).
또 수산기의 수소 원자를 -W-Q'-X로 표시되는 기로 치환하는 방법으로서는 예를 들면 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머와 SiH 기를 가지는 유기 규소 화합물을 붕소 촉매 등의 탈수소 촉매의 존재하 불소계 용제, 유기 용제 등의 용제를 사용하여 0~60℃, 바람직하게는 15~35℃, 보다 바람직하게는 약 25℃의 온도에서 10분~24시간, 바람직하게는 30분~2시간, 보다 바람직하게는 약 1시간 탈수소 반응을 행한다.As a method for replacing the hydrogen atom of the hydroxyl group with a group represented by -W-Q'-X, for example, a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a) Group in the presence of a dehydrogenation catalyst such as a boron catalyst at a temperature of 0 to 60 캜, preferably 15 to 35 캜, more preferably about 25 캜, using a solvent such as a fluorine-based solvent or an organic solvent. Deg.] To 24 hours, preferably 30 minutes to 2 hours, more preferably about 1 hour.
여기서 SiH 기를 가지는 유기 규소 화합물로서는 예를 들면 하기에 나타내는 것을 예시할 수 있다.Examples of the organosilicon compound having a SiH group include the following.
(식 중, g, e는 상기와 동일하며, c는 1~4의 정수이다.)(Wherein g and e are as defined above, and c is an integer of 1 to 4.)
이 사용량은 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머의 수산기 1당량에 대하여 1~10당량, 보다 바람직하게는 1.2~5당량 사용할 수 있다.This amount may be used in an amount of 1 to 10 equivalents, more preferably 1.2 to 5 equivalents based on 1 equivalent of the hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain end represented by the formula (a).
계속해서 반응을 정지시키고, 분액 조작에 의해 수층과 불소 용제층을 분리한다. 얻어진 불소 용제층을 추가로 유기 용제로 세정하고, 용제를 증류제거함으로써, 하기 식 (c)로 표시되는 분자쇄 말단에 올레핀 부위를 가지고, 수산기의 부분이 유기 규소 화합물기로 치환된 플루오로옥시알킬기 함유 폴리머가 얻어진다.Subsequently, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by separating operation. The resulting fluorine solvent layer is further washed with an organic solvent and the solvent is distilled off to obtain a fluorooxyalkyl group having an olefin moiety at the molecular chain terminal end represented by the following formula (c) and having a hydroxyl group moiety substituted with an organic silicon compound group Containing polymer is obtained.
(식 중, Rf, Q', X, U, α는 상기와 동일하며, W'는 단결합이다.)(Wherein Rf, Q ', X, U, and a are as defined above, and W' is a single bond.)
또한 수산기의 수소 원자를 -W-Q'-X로 표시되는 기로 치환하는 방법의 다른 방법으로서 우선 수산기의 수소 원자를 말단 불포화기로 치환하고, 그 후 이 말단불포화기(올레핀 부위)를 다른 올레핀 부위와 함께 SiH 기를 가지는 유기 규소 화합물과 반응시키는 방법을 들 수 있다.Further, as another method of replacing the hydrogen atom of the hydroxyl group with a group represented by -W-Q'-X, first, the hydrogen atom of the hydroxyl group is substituted with the terminal unsaturated group and then the terminal unsaturated group (olefin portion) With an organosilicon compound having a SiH group.
수산기의 수소 원자를 말단 불포화기로 치환하는 방법으로서는 예를 들면 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머와 올레핀 도입제를 아민류나 알칼리 금속계 염기 등의 염기의 존재하 필요에 따라 테트라뷰틸암모늄할라이드, 알칼리 금속계 할라이드 등의 반응성을 향상시키는 첨가제나, 불소계 용제, 유기 용제 등의 용제를 사용하여 0~90℃, 바람직하게는 60~80℃, 보다 바람직하게는 약 70℃의 온도에서 1~25시간, 바람직하게는 3~10시간, 보다 바람직하게는 약 6시간 숙성한다.Examples of the method for replacing the hydrogen atom of the hydroxyl group with the terminal unsaturated group include a method in which a fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety at the molecular chain terminal end represented by the formula (a) and an olefin- Preferably from 60 to 80 占 폚, more preferably from 60 to 80 占 폚, in the presence of a base such as tetrabutylammonium halide or an alkali metal halide in the presence of an additive for improving reactivity or a solvent such as a fluorine- Deg.] C, preferably about 70 [deg.] C for 1 to 25 hours, preferably 3 to 10 hours, more preferably about 6 hours.
여기서 올레핀 도입제로서는 예를 들면 알릴할라이드 등을 사용할 수 있고, 구체적으로는 알릴클로라이드, 알릴브로마이드, 알릴아이오다이드, 4-클로로-1-뷰텐, 4-브로모-1-뷰텐, 4-아이오도-1-뷰텐, 5-클로로-1-펜텐, 5-브로모-1-펜텐, 5-아이오도-1-펜텐 등을 들 수 있고, 이 사용량은 식 (a)로 표시되는 분자쇄 말단에 수산기 및 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머의 수산기 1당량에 대하여 1~10당량, 보다 바람직하게는 2.5~6당량, 더욱 바람직하게는 약 5당량 사용할 수 있다.As the olefin-introducing agent, for example, allyl halide and the like can be used. Specific examples thereof include allyl chloride, allyl bromide, allyl iodide, 4-chloro-1-butene, 4- 1-butene, 5-chloro-1-pentene, 5-bromo-1-pentene and 5-iodo-1-pentene. Preferably 1 to 10 equivalents, more preferably 2.5 to 6 equivalents, and still more preferably about 5 equivalents based on 1 equivalent of the hydroxyl group of the fluoropolyether group-containing polymer having a hydroxyl group and an olefin moiety.
계속해서 반응을 정지시키고, 분액 조작에 의해 수층과 불소 용제층을 분리한다. 얻어진 불소 용제층을 추가로 유기 용제로 세정하고, 용제를 증류제거함으로써, 하기 식 (d)로 표시되는 분자쇄 말단에 올레핀 부위를 가지는 플루오로옥시알킬기 함유 폴리머가 얻어진다.Subsequently, the reaction is stopped, and the aqueous layer and the fluorine solvent layer are separated by separating operation. The obtained fluorine solvent layer is further washed with an organic solvent and the solvent is distilled off to obtain a fluorooxyalkyl group-containing polymer having an olefin moiety at the molecular chain end represented by the following formula (d).
(식 중, Rf, U, α는 상기와 동일하다. V는 단결합 또는 2가의 탄화수소기이다.)(Wherein Rf, U and? Are as defined above, and V is a single bond or a divalent hydrocarbon group.)
상기 식 (d)에 있어서, V는 단결합 또는 2가의 탄화수소기이며, 2가의 탄화수소기로서 구체적으로는 메틸렌기, 에틸렌기, 프로필렌기(트라이메틸렌기, 메틸에틸렌기), 뷰틸렌기(테트라메틸렌기, 메틸프로필렌기), 헥사메틸렌기, 옥타메틸렌기 등의 탄소수 1~8의 알킬렌기, 페닐렌기 등의 탄소수 6~8의 아릴렌기를 포함하는 알킬렌기(예를 들면 탄소수 7~8의 알킬렌·아릴렌기 등) 등을 들 수 있다. V로서 바람직하게는 메틸렌기이다.In formula (d), V is a monovalent or divalent hydrocarbon group, and specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group An alkylene group having 7 to 8 carbon atoms such as an alkylene group having 7 to 8 carbon atoms such as an alkylene group having 1 to 8 carbon atoms such as a methylene group, Arylene group, etc.), and the like. V is preferably a methylene group.
이어서 상기에서 얻어진 식 (a)~(d)로 표시되는 분자쇄 말단에 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머의 어느 하나와, 분자 중에 SiH 기를 가지는 유기 규소 화합물을 하이드로실릴화 반응 촉매, 예를 들면 염화백금산/바이닐실록세인 착체의 톨루엔 용액 존재하 40~120℃, 바람직하게는 60~100℃, 보다 바람직하게는 약 80℃의 온도에서 1~72시간, 바람직하게는 20~36시간, 보다 바람직하게는 약 24시간 숙성시킨다.Subsequently, any one of the fluoropolyether group-containing polymers having the olefin sites at the molecular chain terminals represented by the above-mentioned formulas (a) to (d) and the organosilicon compound having SiH groups in the molecule are reacted with a hydrosilylation reaction catalyst, For example, in the presence of a toluene solution of a chloroplatinic acid / vinylsiloxane complex at a temperature of 40 to 120 ° C, preferably 60 to 100 ° C, more preferably about 80 ° C, for 1 to 72 hours, preferably 20 to 36 hours , More preferably about 24 hours.
여기서 분자 중에 SiH 기를 가지는 유기 규소 화합물로서는 하기 식으로 표시되는 화합물이 바람직하다.As the organic silicon compound having a SiH group in the molecule, a compound represented by the following formula is preferable.
(식 중, R1, R2, X, g, j는 상기와 동일하며, i는 1~6, 바람직하게는 1~4의 정수이며, i+j는 3~10, 바람직하게는 3~5의 정수이다.)(Wherein, R 1, R 2, X, g, j is the same as above, i is 1 to 6, preferably an integer of 1 - 4, i + j is from 3 to 10, preferably 3 to It is an integer of 5.
이와 같은 분자 중에 SiH 기를 가지는 유기 규소 화합물로서는 예를 들면 하기에 나타내는 것 등을 들 수 있다.Examples of such an organosilicon compound having SiH groups in the molecule include those shown below.
(식 중, g, g1, e는 상기와 동일하다.)(Wherein g, g1 and e are as defined above.)
분자 중에 SiH 기를 가지는 유기 규소 화합물의 사용량은 상기 식 (a)~(d)로 표시되는 분자쇄 말단에 올레핀 부위를 가지는 플루오로폴리에터기 함유 폴리머의 말단 불포화기 1당량에 대하여 5~20당량, 보다 바람직하게는 7.5~12.5당량, 더욱 바람직하게는 약 10당량 사용할 수 있다.The amount of the organosilicon compound having SiH groups in the molecule is preferably 5 to 20 equivalents based on 1 equivalent of the terminal unsaturated group of the fluoropolyether group-containing polymer having an olefin moiety at the molecular chain terminal end represented by the above formulas (a) to (d) , More preferably 7.5 to 12.5 equivalents, and still more preferably about 10 equivalents.
그 후, 용제 및 미반응물을 감압 증류제거함으로써, 상기 식 (1)로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 얻을 수 있다. 또한 상기 서술한 반응은 단독으로 행하는 것도 가능하고, 연속적으로 행하는 것도 가능하다.Thereafter, the solvent and the unreacted materials are distilled off under reduced pressure to obtain the polymer-modified organosilicon compound containing a fluoropolyether group represented by the formula (1). The above-described reaction can be carried out alone or continuously.
본 발명의 표면 처리제는 상기 식 (1)로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 함유한다.The surface treatment agent of the present invention contains the polymer-modified organosilicon compound containing a fluoropolyether group represented by the above formula (1).
본 발명의 표면 처리제에는 추가로 하기 일반식 (4)In the surface treatment agent of the present invention,
(식 중, A는 불소 원자 또는 말단이 -CF3기인 1가의 불소 함유기이며, Rf'는 2가의 플루오로옥시알킬렌기 함유 폴리머 잔기이다.)(Wherein A is a fluorine atom or a monovalent fluorine-containing group whose terminal is a -CF 3 group, and Rf 'is a divalent fluorooxyalkylene group-containing polymer residue).
로 표시되는 플루오로폴리에터기 함유 폴리머(이하, 무관능성 폴리머라고 칭한다)를 함유해도 된다.(Hereinafter, referred to as a non-functional polymer) represented by the following formula (1).
상기 식 (4)에 있어서, A는 불소 원자 또는 말단이 -CF3기인 1가의 불소 함유기이며, 바람직하게는 불소 원자, 탄소수 1~6의 직쇄상 퍼플루오로알킬기이며, 그 중에서도 -F기, -CF3기, -CF2CF3기, -CF2CF2CF3기가 바람직하다.In the above formula (4), A represents a fluorine atom or a monovalent fluorine-containing group having a -CF 3 group at the end, preferably a fluorine atom or a straight-chain perfluoroalkyl group having 1 to 6 carbon atoms, , -CF 3 group, -CF 2 CF 3 group and -CF 2 CF 2 CF 3 group are preferable.
또 Rf'는 2가의 플루오로옥시알킬렌기 함유 폴리머 잔기이며, Rf'로서는 하기에 나타내는 것이 바람직하다.Rf 'is a divalent fluorooxyalkylene group-containing polymer residue, and Rf' is preferably as shown below.
(식 중, p2는 5~200, 바람직하게는 10~100의 정수, q2는 5~200, 바람직하게는 10~100의 정수, r1은 10~200, 바람직하게는 20~100의 정수, t1은 5~200, 바람직하게는 10~100의 정수, t2는 10~200, 바람직하게는 20~100의 정수이며, t1+p2는 10~205, 바람직하게는 20~110의 정수, q2+p2는 10~205, 바람직하게는 20~110의 정수이다.)(Wherein p2 is an integer of 5 to 200, preferably 10 to 100, q2 is an integer of 5 to 200, preferably 10 to 100, r1 is an integer of 10 to 200, preferably 20 to 100, t1 Is an integer of 5 to 200, preferably 10 to 100, t2 is an integer of 10 to 200, preferably 20 to 100, t1 + p2 is an integer of 10 to 205, preferably 20 to 110, q2 + p2 Is an integer of 10 to 205, preferably 20 to 110.)
식 (4)로 표시되는 무관능성 폴리머로서는 하기의 것을 들 수 있다.Examples of the non-functional polymer represented by the formula (4) include the following.
(식 중, p2, q2, r1, t1, t2는 상기와 동일하다.)(Wherein p2, q2, r1, t1 and t2 are as defined above.)
식 (4)로 표시되는 무관능성 폴리머를 배합하는 경우의 사용량은 특별히 한정되지 않지만, 식 (1)로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물의 질량에 대하여 0.1~60질량%, 특히 10~40질량%의 범위가 바람직하고, 지나치게 많으면 밀착성의 문제가 생기는 경우가 있다.The amount of the non-functional polymer represented by the formula (4) to be used is not particularly limited, but is preferably 0.1 to 60% by mass, more preferably 0.1 to 60% by mass with respect to the mass of the fluoropolyether group-containing polymer-modified organosilicon compound represented by the formula (1) Particularly preferably from 10 to 40% by mass, and if it is excessively large, a problem of adhesion may occur.
이 표면 처리제는 적당한 용제를 포함해도 된다. 이와 같은 용제로서는 불소 변성 지방족 탄화수소계 용제(퍼플루오로헵테인, 퍼플루오로옥테인 등), 불소 변성 방향족 탄화수소계 용제(m-자일렌헥사플루오라이드(1,3-비스(트라이플루오로메틸)벤젠), 벤조트라이플루오라이드 등), 불소 변성 에터계 용제(메틸퍼플루오로뷰틸에터, 에틸퍼플루오로뷰틸에터, 퍼플루오로(2-뷰틸테트라하이드로퓨란) 등), 불소 변성 알킬아민계 용제(퍼플루오로트라이뷰틸아민, 퍼플루오로트라이펜틸아민 등), 탄화수소계 용제(석유 벤진, 미네랄 스피릿, 톨루엔, 자일렌 등), 케톤계 용제(아세톤, 메틸에틸케톤, 메틸아이소뷰틸케톤 등)를 예시할 수 있다. 이들 중에서는 용해성, 젖음성 등의 점에서 불소 변성된 용제가 바람직하고, 특히 m-자일렌헥사플루오라이드, 퍼플루오로(2-뷰틸테트라하이드로퓨란), 퍼플루오로트라이뷰틸아민, 에틸퍼플루오로뷰틸에터가 바람직하다.The surface treatment agent may contain a suitable solvent. Examples of the solvent include fluorine-modified aliphatic hydrocarbon solvents such as perfluoroheptane and perfluorooctane, fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride (1,3-bis (trifluoromethyl) ), Benzotriafluoride, etc.), fluorine-modified ether-based solvents (methyl perfluorobutylether, ethyl perfluorobutylether, perfluoro (2-butyltetrahydrofuran) (Such as benzene, mineral spirits, toluene, and xylene), ketone solvents (such as acetone, methyl ethyl ketone, methyl isobutyl Ketone, etc.) can be exemplified. Of these, fluorine-modified solvents are preferred from the viewpoints of solubility and wettability. Particularly preferred are m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine, Butyl ether is preferred.
상기 용제는 그 2종 이상을 혼합해도 되는데, 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 균일하게 용해시키는 것이 바람직하다. 또한 용제에 용해시키는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물의 최적 농도는 처리 방법에 따라 상이한데, 표면 처리제 중 0.01~40질량%, 특히 0.05~25질량%인 것이 바람직하다.The solvent may be a mixture of two or more kinds thereof, and it is preferable to uniformly dissolve the fluoropolyether group-containing polymer-modified organosilicon compound. The optimum concentration of the fluoropolyether group-containing polymer-modified organosilicon compound dissolved in the solvent differs depending on the treatment method, and it is preferably 0.01 to 40% by mass, particularly 0.05 to 25% by mass, in the surface treatment agent.
본 발명의 표면 처리제는 수지 필름이나 안경 렌즈와 같은 수지 제품에 표면 처리한다. 여기서 수지 제품으로서는 열가소성 수지로 이루어지는 것이 바람직하고, 구체적으로는 하드 코트 처리된 열가소성 수지 필름(하드 코트 필름), 연필경도 4H 이상이며 하드 코트가 시행되어 있지 않은 열가소성 수지 필름(고경도 수지 필름) 또는 반사 방지층을 구비한 열가소성 수지 필름(반사 방지 필름) 등이 바람직하게 사용된다.The surface treatment agent of the present invention is surface-treated with a resin product such as a resin film or a spectacle lens. Specifically, the resin product is preferably a thermoplastic resin film (hard coat film) having hard coat treatment, a thermoplastic resin film (hard resin film) having pencil hardness of 4H or more and not having hard coat, or the thermoplastic resin film And a thermoplastic resin film (antireflection film) having an antireflection layer are preferably used.
또 본 발명에 있어서는 상기 수지 제품을 미리 SiO2 처리한 것을 사용하는 것이 바람직하다. 여기서 SiO2 처리는 스퍼터법에 의해 SiO2 처리된 것이 상기 수지 제품과 처리제와의 밀착성을 향상시킨다는 점에서 바람직하다.In the present invention, it is preferable to use the resin product obtained by treating with SiO 2 in advance. Wherein SiO 2 treatment is that the SiO 2 by sputtering process preferred in view of improving the adhesiveness between the resin and of the treatment agent.
본 발명의 표면 처리제는 솔칠, 디핑, 스프레이, 증착 처리 등 공지의 방법으로 기재 상에 시여할 수 있다. 증착 처리시의 가열 방법은 저항 가열 방식, 전자 빔 가열 방식의 어느 쪽이어도 되고, 특별히 한정되는 것은 아니다. 또 후처리 조건은 후처리 방법에 따라 상이한데, 예를 들면 증착 처리나 스프레이 도공으로 시여한 경우는, 기재로서 SiO2 처리된 수지 필름을 사용한 경우, 실온(25℃)으로부터 200℃의 범위에서 5분~24시간, 특히 10분~12시간으로 할 수 있고, 가습하에서 후처리해도 된다. 특히 본 발명에 있어서는 실온이라도 10분~24시간, 특히 30분~12시간이면 충분하다. 또 피막의 막두께는 기재의 종류에 따라 적당히 선정되는데, 통상 0.1~100nm, 특히 1~25nm이다.The surface treatment agent of the present invention can be applied on a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method for the deposition treatment may be either of the resistance heating method and the electron beam heating method, and is not particularly limited. The post-treatment conditions differ depending on the post-treatment method. For example, in the case of deposition treatment or spray coating, when a SiO 2 -substantially treated resin film is used as the substrate, 5 minutes to 24 hours, particularly 10 minutes to 12 hours, and may be post-treated under humidification. Particularly, in the present invention, even at room temperature, 10 minutes to 24 hours, particularly 30 minutes to 12 hours, is sufficient. The film thickness of the coating film is suitably selected according to the kind of the substrate, and is usually 0.1 to 100 nm, particularly 1 to 25 nm.
본 발명의 상기 표면 처리제로 처리되는 수지 제품으로서는 카 내비게이션, 휴대전화, 디지털 카메라, 디지털 비디오 카메라, PDA, 포터블 오디오 플레이어, 카 오디오, 게임 기기, 안경 렌즈, 카메라 렌즈, 렌즈 필터, 선글래스, 위카메라 등의 의료용 기기, 복사기, PC, 액정 디스플레이, 유기 EL 디스플레이, 플라즈마 디스플레이, 터치패널 디스플레이, 보호 필름, 하드 코트 필름, 고경도 수지, 반사 방지 필름, 웨어러블 단말 등의 제품의 부품이나 일부로서 사용되는 광학 물품, 터치패널, 반사 방지 필름, 석영 기판 등이 바람직하다.Examples of the resin product treated with the surface treatment agent of the present invention include a car navigation system, a cellular phone, a digital camera, a digital video camera, a PDA, a portable audio player, a car audio, a game device, a spectacle lens, Used as parts or parts of products such as medical equipment such as a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, a hard coat film, a high hardness resin, An optical article, a touch panel, an antireflection film, a quartz substrate and the like are preferable.
본 발명의 수지 제품에 표면 처리하는 표면 처리제는 상기 물품에 실온 등의 온화한 조건하 단시간으로도 피막을 형성할 수 있고, 이 피막은 우수한 발수발유성이나 내구성을 나타내기 때문에, 특히 안경 렌즈, 터치패널 디스플레이, 하드 코트 필름, 고경도 수지, 반사 방지 필름, 웨어러블 단말 등의 발수발유층으로서 유용하다. 여기서 고경도 수지는 예를 들면 유리 대체 필름으로서 PR되고 있는 신닛테츠카가쿠사제 상품명 실플러스나, 군제사제 상품명 HD 필름 등의 연필경도 4H 이상의 수지를 성형한 제품을 가리키고, 특히 이 수지를 성형한 수지 필름을 가리키는데, 특히 상기한 제품에 제한되는 것은 아니다.The surface treatment agent for surface-treating the resin product of the present invention can form a film on the article even under a mild condition such as room temperature in a short time. Since the film exhibits excellent water and oil repellency and durability, Panel display, a hard coat film, a high hardness resin, an antireflection film, a wearable terminal or the like. Here, the high hardness resin refers to a product obtained by molding a resin having a pencil hardness of 4H or more, such as a product name of Shinpurusa Co., Ltd., manufactured by Shinnitetsu Kagaku Co., Refers to a resin film, and is not particularly limited to the above-mentioned products.
(실시예)(Example)
이하, 합성예, 실시예 및 비교예를 나타내어, 본 발명을 보다 상세하게 설명하는데, 본 발명은 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the following Examples.
실시예 및 비교예는 하기 합성예에 의해 얻어지는 화합물을 사용했다.In Examples and Comparative Examples, the compounds obtained by the following Synthesis Examples were used.
[합성예 1] 화합물 1의 합성[Synthesis Example 1] Synthesis of Compound 1
반응 용기에 테트라하이드로퓨란 150g, 1,3-비스(트라이플루오로메틸)벤젠 300g을 혼합하고, 0.7M의 알릴마그네슘브로마이드 160ml을 적하했다. 계속해서 하기 식 (A)150 g of tetrahydrofuran and 300 g of 1,3-bis (trifluoromethyl) benzene were mixed in a reaction vessel, and 160 ml of 0.7 M allyl magnesium bromide was added dropwise. (A)
로 표시되는 화합물 300g(4.8×10-2mol)을 천천히 적하한 후, 60℃에서 4시간 가열했다. 가열 종료 후, 실온까지 냉각하고, 1.2M 염산 수용액 300g 중에 용액을 적하하고 반응을 정지시켰다. 분액 조작에 의해 하층인 불소 화합물층을 회수 후, 아세톤으로 세정했다. 세정 후의 하층인 불소 화합물층을 다시 회수하고, 감압하 잔존 용제를 증류제거함으로써, 하기 식 (B)로 표시되는 플루오로폴리에터기 함유 폴리머 292g을 얻었다.(4.8 x 10 -2 mol) was slowly added dropwise, and the mixture was heated at 60 ° C for 4 hours. After the completion of the heating, the reaction mixture was cooled to room temperature, and the solution was dropped into 300 g of a 1.2 M aqueous hydrochloric acid solution to stop the reaction. The fluorine compound layer as a lower layer was recovered by separating operation, and then washed with acetone. The fluorine compound layer as the lower layer after the washing was again collected and the residual solvent was distilled off under reduced pressure to obtain 292 g of a fluoropolyether group-containing polymer represented by the following formula (B).
반응 용기에 하기 식 (B)The reaction vessel was charged with the following formula (B)
로 표시되는 화합물 80g(1.0×10-2mol)을 넣고, 1,3-비스(트라이플루오로메틸)벤젠 80g에 용해시키고, 염화백금산/바이닐실록세인 착체의 톨루엔 용액 8.0×10-2g(Pt 단체로서 2.1×10-6mol을 함유)과, 1,4-비스(다이메틸실릴)벤젠 37g(1.9×10-1mol)을 혼합하여, 80℃에서 7시간 숙성하고, 용제 및 미반응물을 감압 증류제거함으로써, 하기 식 (C)로 표시되는 플루오로폴리에터기 함유 폴리머(화합물 1) 70g을 얻었다.80 g (1.0 x 10 -2 mol) of a compound represented by the following formula (1) was dissolved in 80 g of 1,3-bis (trifluoromethyl) benzene and 8.0 x 10 -2 g of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (2.1 × 10 -6 mol as Pt group) and 37 g (1.9 × 10 -1 mol) of 1,4-bis (dimethylsilyl) benzene were mixed and aged at 80 ° C. for 7 hours, Was distilled off under reduced pressure to obtain 70 g of a fluoropolyether group-containing polymer (Compound 1) represented by the following formula (C).
[합성예 2] 화합물 2의 합성[Synthesis Example 2] Synthesis of Compound 2
반응 용기에 1,3-비스(트라이플루오로메틸)벤젠 100g, DBU(다이아자비사이클로운데센) 8.2g(5.4×10-2mol), 하기 식 (B)The reaction vessel was charged with 100 g of 1,3-bis (trifluoromethyl) benzene, 8.2 g (5.4 x 10 -2 mol) of DBU (diazabicycloundecene)
로 표시되는 화합물 100g(2.7×10-2mol)을 혼합한 후, 트라이메틸클로로실레인 5.8g(5.4×10-2mol)을 적하했다. 계속해서 50℃에서 3시간 가열했다. 가열 종료 후 실온까지 냉각하고, 염산 수용액을 적하했다. 분액 조작에 의해 하층인 불소 화합물층을 회수 후, 메탄올로 세정했다. 세정 후의 하층인 불소 화합물층을 다시 회수하고, 감압하 잔존 용제를 증류제거함으로써, 하기 식 (D)로 표시되는 플루오로폴리에터기 함유 폴리머 90g을 얻었다.(2.7 × 10 -2 mol) were mixed, and then 5.8 g (5.4 × 10 -2 mol) of trimethylchlorosilane was added dropwise. Subsequently, the mixture was heated at 50 DEG C for 3 hours. After the completion of heating, the reaction mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. The fluorine compound layer as the lower layer was recovered by separating operation and then washed with methanol. The fluorine compound layer as a lower layer after washing was again collected and the remaining solvent was distilled off under reduced pressure to obtain 90 g of a fluoropolyether group-containing polymer represented by the following formula (D).
반응 용기에 하기 식 (D)(D) represented by the following formula
로 표시되는 화합물 50g(1.4×10-2mol)을 넣고, 1,3-비스(트라이플루오로메틸)벤젠 50g에 용해시키고, 염화백금산/바이닐실록세인 착체의 톨루엔 용액 1.5×10-1g(Pt 단체로서 4.0×10-6mol을 함유)과, 1,3,5,7-테트라메틸사이클로테트라실록세인 33g(1.3×10-1mol)을 혼합하여, 80℃에서 19시간 숙성하고, 용제 및 미반응물을 감압 증류제거함으로써, 하기 식 (E)로 표시되는 플루오로폴리에터기 함유 폴리머(화합물 2) 56g을 얻었다.(1.4 x 10 -2 mol) of the compound represented by the formula (1) was dissolved in 50 g of 1,3-bis (trifluoromethyl) benzene and 1.5 x 10 -1 g of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (Containing 4.0 × 10 -6 mol as a Pt group) and 33 g (1.3 × 10 -1 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and aged at 80 ° C. for 19 hours, And the unreacted materials were distilled off under reduced pressure to obtain 56 g of a fluoropolyether group-containing polymer (Compound 2) represented by the following formula (E).
[합성예 3] 화합물 3의 합성[Synthesis Example 3] Synthesis of Compound 3
반응 용기에 하기 식 (B)The reaction vessel was charged with the following formula (B)
로 표시되는 화합물 150g(4.0×10-2mol)을 넣고, 1,3-비스(트라이플루오로메틸)벤젠 150g에 용해시키고, 염화백금산/바이닐실록세인 착체의 톨루엔 용액 8.0×10-2g(Pt 단체로서 4.0×10-6mol을 함유)과, 1,1,3,3,5,5-헥사메틸트라이실록세인 83g(4.0×10-1mol)을 혼합하여, 80℃에서 24시간 숙성하고, 용제 및 미반응물을 감압 증류제거함으로써, 하기 식 (F)로 표시되는 플루오로폴리에터기 함유 폴리머(화합물 3) 150g을 얻었다.Represented by Formula 150g (4.0 × 10 -2 mol) were dissolved, 1,3-bis (trifluoromethyl) benzene was dissolved in 150g, a toluene solution of a chloroplatinic acid / vinyl siloxane complex, 8.0 × 10 -2 g ( (4.0 x 10 < -6 > mol as a Pt group) and 83 g (4.0 x 10 -1 mol) of 1,1,3,3,5,5-hexamethyltrisiloxane were mixed and aged at 80 ° C for 24 hours , And the solvent and unreacted materials were distilled off under reduced pressure to obtain 150 g of a fluoropolyether group-containing polymer (Compound 3) represented by the following formula (F).
[합성예 4] 화합물 4의 합성[Synthesis Example 4] Synthesis of Compound 4
반응 용기에 하기 식 (B)The reaction vessel was charged with the following formula (B)
로 표시되는 화합물 50g(1.4×10-2mol)을 넣고, 1,3-비스(트라이플루오로메틸)벤젠 50g에 용해시키고, 염화백금산/바이닐실록세인 착체의 톨루엔 용액 8.0×10-2g(Pt 단체로서 1.3×10-6mol을 함유)과, 1,1,3,3,5,5,7,7-옥타메틸테트라실록세인 40g(1.4×10-1mol)을 혼합하여, 80℃에서 4시간 숙성하고, 용제 및 미반응물을 감압 증류제거함으로써, 하기 식 (G)로 표시되는 플루오로폴리에터기 함유 폴리머(화합물 4) 41g을 얻었다.Was dissolved in 50 g of 1,3-bis (trifluoromethyl) benzene, and a toluene solution of chloroplatinic acid / vinylsiloxane complex in an amount of 8.0 × 10 -2 g (1.4 × 10 -2 mol) (1.3 x 10 < -6 > mol as Pt group) and 40 g (1.4 x 10 -1 mol) of 1,1,3,3,5,5,7,7-octamethyltetrasiloxane were mixed, , And the solvent and unreacted materials were distilled off under reduced pressure to obtain 41 g of a fluoropolyether group-containing polymer (Compound 4) represented by the following formula (G).
[합성예 5] 화합물 5의 합성[Synthesis Example 5] Synthesis of Compound 5
반응 용기에 하기 식 (B)The reaction vessel was charged with the following formula (B)
로 표시되는 화합물 20g(0.5×10-2mol)을 넣고, 1,3-비스(트라이플루오로메틸)벤젠 20g에 용해시키고, 염화백금산/바이닐실록세인 착체의 톨루엔 용액 2.0×10-2g(Pt 단체로서 0.5×10-6mol을 함유)과, 하기 식 (H)(0.5 x 10 -2 mol) of the compound represented by the formula (1) was dissolved in 20 g of 1,3-bis (trifluoromethyl) benzene, and a toluene solution of chloroplatinic acid / vinylsiloxane complex of 2.0 × 10 -2 g (0.5 x 10 < -6 > mol as Pt group) and the following formula (H)
로 표시되는 데카실록세인 40g(0.5×10-1mol)을 혼합하여, 80℃에서 7시간 숙성하고, 용제 및 미반응물을 감압 증류제거함으로써, 하기 식 (I)로 표시되는 플루오로폴리에터기 함유 폴리머(화합물 5) 10g을 얻었다.(0.5x10 < -1 > mol) represented by the following formula (I), and aged at 80 DEG C for 7 hours. The solvent and the unreacted material were distilled off under reduced pressure to obtain a fluoropolyether Containing compound (Compound 5).
[합성예 6] 화합물 6의 합성[Synthesis Example 6] Synthesis of Compound 6
반응 용기에 하기 식 (B)The reaction vessel was charged with the following formula (B)
로 표시되는 화합물 50g(1.3×10-2mol)을 넣고, 1,3-비스(트라이플루오로메틸)벤젠 50g에 용해시키고, 염화백금산/바이닐실록세인 착체의 톨루엔 용액 5.0×10-2g(Pt 단체로서 1.4×10-6mol을 함유)과, 펜타메틸다이실록세인 20g(1.4×10-1mol)을 혼합하여, 80℃에서 8시간 숙성하고, 용제 및 미반응물을 감압 증류제거함으로써, 하기 식 (J)로 표시되는 플루오로폴리에터기 함유 폴리머(화합물 6) 54g을 얻었다.Represented by compound 50g (1.3 × 10 -2 mol) were dissolved, 1,3-bis (trifluoromethyl) was dissolved in 50g of benzene, toluene solution of chloroplatinic acid / vinyl siloxane complex, 5.0 × 10 -2 g ( (1.4 x 10 < -6 > mol as a Pt group) and 20 g (1.4 x 10 -1 mol) of pentamethyldisiloxane were mixed and aged at 80 DEG C for 8 hours. The solvent and unreacted materials were distilled off under reduced pressure, 54 g of a fluoropolyether group-containing polymer (Compound 6) represented by the following formula (J) was obtained.
[합성예 7] 화합물 7의 합성[Synthesis Example 7] Synthesis of Compound 7
반응 용기에 하기 식 (B)The reaction vessel was charged with the following formula (B)
로 표시되는 화합물 50g(1.3×10-2mol)을 넣고, 1,3-비스(트라이플루오로메틸)벤젠 50g에 용해시키고, 염화백금산/바이닐실록세인 착체의 톨루엔 용액 1.0×10-1g(Pt 단체로서 2.8×10-6mol을 함유)과, 1-뷰테인-데카메틸펜타실록세인 13g(3.2×10-2mol)을 혼합하여, 80℃에서 20시간 숙성하고, 용제 및 미반응물을 감압 증류제거함으로써, 하기 식 (K)로 표시되는 플루오로폴리에터기 함유 폴리머(화합물 7) 54g을 얻었다.(1.3 x 10 -2 mol) of the compound represented by the formula (1) was dissolved in 50 g of 1,3-bis (trifluoromethyl) benzene and 1.0 10 -1 g of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (2.8 × 10 -6 mol as Pt group) and 13 g (3.2 × 10 -2 mol) of 1-butene-decamethylpentasiloxane were mixed and aged at 80 ° C. for 20 hours, And then vacuum distilled off to obtain 54 g of a fluoropolyether group-containing polymer (Compound 7) represented by the following formula (K).
[합성예 8] 화합물 8의 합성[Synthesis Example 8] Synthesis of Compound 8
반응 용기에 하기 식 (B)The reaction vessel was charged with the following formula (B)
로 표시되는 화합물 25g(0.7×10-2mol)을 넣고, 1,3-비스(트라이플루오로메틸)벤젠 25g에 용해시키고, 염화백금산/바이닐실록세인 착체의 톨루엔 용액 2.5×10-2g(Pt 단체로서 0.7×10-6mol을 함유)과, 비스(다이메틸실릴)메테인 8.9g(0.7×10-1mol)을 혼합하여, 80℃에서 24시간 숙성하고, 용제 및 미반응물을 감압 증류제거함으로써, 하기 식 (L)로 표시되는 플루오로폴리에터기 함유 폴리머(화합물 8) 10g을 얻었다.Represented by compound 25g (0.7 × 10 -2 mol) were dissolved, 1,3-bis (trifluoromethyl) benzene was dissolved in 25g, chloroplatinic acid / vinyl siloxane in toluene solution, 2.5 × 10 -2 g of the complex ( (0.7 x 10 < -6 > mol as a Pt group) and 8.9 g (0.7 x 10 -1 mol) bis (dimethylsilyl) methane were mixed and aged at 80 ° C for 24 hours. Followed by distillation to obtain 10 g of a fluoropolyether group-containing polymer (Compound 8) represented by the following formula (L).
[합성예 9] 화합물 9의 합성[Synthesis Example 9] Synthesis of Compound 9
반응 용기에 하기 식 (M)(M) represented by the following formula
으로 표시되는 화합물 200g(2.6×10-2mol), 1,3-비스(트라이플루오로메틸)벤젠 200g, 1,1,3,3,5,5-헥사메틸트라이실록세인 108g(5.2×10-3mol), 및 염화백금산/바이닐실록세인 착체의 톨루엔 용액 6.0×10-1g(Pt 단체로서 1.6×10-5mol을 함유)을 혼합하여, 80℃에서 40시간 숙성시켰다. 그 후, 용제 및 미반응물을 감압 증류제거했다. 계속해서 분자 증류 장치에 의해 잔존하는 저비점 성분, 고비점 성분을 제거하여, 액상의 생성물(화합물 9) 200g을 얻었다.(2.6 x 10 -2 mol), 200 g of 1,3-bis (trifluoromethyl) benzene, 108 g of 1,1,3,3,5,5-hexamethyltrisiloxane (5.2 x 10 < -3 mol), and a toluene solution of chloroplatinic acid / vinylsiloxane complex (6.0 × 10 -1 g) (containing 1.6 × 10 -5 mol as a unit of Pt) were mixed and aged at 80 ° C. for 40 hours. Thereafter, the solvent and the unreacted material were distilled off under reduced pressure. Subsequently, the remaining low boiling point component and high boiling point component were removed by a molecular distillation apparatus to obtain 200 g of a liquid product (Compound 9).
얻어진 화합물 9는 1H-NMR에 의해 하기 식 (N)으로 표시되는 구조인 것이 확인되었다.The resulting Compound 9 was confirmed to have the structure represented by the following formula (N) by 1 H-NMR.
[합성예 10] 화합물 10(비교품)의 합성[Synthesis Example 10] Synthesis of Compound 10 (comparative product)
반응 용기에 하기 식 (B)The reaction vessel was charged with the following formula (B)
로 표시되는 화합물 200g(2.6×10-2mol), 1,3-비스(트라이플루오로메틸)벤젠 200g, 트라이메톡시실레인 12.7g(1.1×10-1mol), 및 염화백금산/바이닐실록세인 착체의 톨루엔 용액 6.0×10-1g(Pt 단체로서 1.6×10-5mol을 함유)을 혼합하여, 80℃에서 40시간 숙성시켰다. 그 후, 용제 및 미반응물을 감압 증류제거했다. 계속해서 분자 증류 장치에 의해 잔존하는 저비점 성분, 고비점 성분을 제거하여, 액상의 생성물(화합물10) 201g을 얻었다.(2.6 x 10 < -2 > mol), 1,3-bis (trifluoromethyl) benzene 200 g, trimethoxysilane 12.7 g (1.1 x 10 -1 mol), and chloroplatinic acid / a mixture of toluene solution of 6.0 × 10 -1 g of hexanes complex (as Pt Groups containing 1.6 × 10 -5 mol), was aged at 80 ℃ 40 hours. Thereafter, the solvent and the unreacted material were distilled off under reduced pressure. Subsequently, the remaining low boiling point component and high boiling point component were removed by a molecular distillation apparatus to obtain 201 g of a liquid product (Compound 10).
얻어진 화합물 10은 1H-NMR에 의해 하기 식 (O)로 표시되는 구조인 것이 확인되었다.It was confirmed by the 1 H-NMR that the obtained compound 10 had a structure represented by the following formula (O).
또한 비교예에는 이하의 화합물을 사용했다.The following compounds were used in Comparative Examples.
[화합물 11][Compound 11]
[화합물 12][Compound 12]
[실시예 1~9, 비교예 1~3][Examples 1 to 9 and Comparative Examples 1 to 3]
표면 처리제의 조제 및 피막의 형성Preparation of surface treatment agent and formation of coating film
상기 화합물 1~12를 농도 20질량%가 되도록 Novec 7200(3M사제, 에틸퍼플루오로뷰틸에터)에 용해시켜 표면 처리제를 조제했다. 표면 처리제 조제 후, 수지 필름(타이골드사제)을 플라즈마 처리(Ar: 10cc, O2: 80cc, 출력: 250W, 시간: 30초)로 세정하고, 그 위에 상기 표면 처리제 10mg을 진공 증착하여(처리 조건은 압력: 2.0×10-2Pa, 가열 온도: 700℃), 25℃, 습도 50% RH의 분위기하에서 24시간 후에 막두께 15nm의 피막을 형성했다. 또한 수지 필름은 폴리에틸렌테레프탈레이트제이며, 필름 표면에 아크릴 하드 코트 처리를 시행한 후, 최표면에 SiO2를 100nm의 두께로 스퍼터 처리한 것을 사용했다.The above compounds 1 to 12 were dissolved in Novec 7200 (ethyl perfluorobutylether manufactured by 3M) to a concentration of 20% by mass to prepare a surface treating agent. After preparing the surface treatment agent, 10 mg of the surface treatment agent was vacuum-deposited on the surface of the resin film (manufactured by Taito Gold Co., Ltd.) by plasma treatment (Ar: 10 cc, O 2 : 80 cc, power: 250 W, Under the conditions of a pressure of 2.0 x 10 < -2 > Pa and a heating temperature of 700 DEG C), and a film having a film thickness of 15 nm was formed after 24 hours in an atmosphere of 25 DEG C and a humidity of 50% RH. The resin film is a polyethylene terephthalate first, and then underwent an acrylic hard coat treatment on the film surface, it was used a sputtering process the SiO 2 in 100nm thickness of the outermost surface.
화합물 1~9를 사용하여 형성된 피막을 실시예 1~9, 화합물 10~12를 사용하여 형성된 피막을 비교예 1~3으로 했다.The coatings formed using the compounds 1 to 9 were used as Comparative Examples 1 to 3, and the coatings formed using the compounds 1 to 9 and 10 to 12 were used.
실시예 1~9 및 비교예 1~3의 피막을 하기의 방법에 의해 평가했다. 어느 시험도 25℃, 습도 50% RH에서 실시했다.The coatings of Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated by the following methods. All tests were conducted at 25 캜 and 50% RH.
[내마모성의 평가][Evaluation of abrasion resistance]
얻어진 피막에 있어서, 천(벰코트)에 대한 내마모성을 트라이보기어 TYPE: 30S(신토카가쿠사제)를 사용하여 측정했다.The abrasion resistance of the resultant coating film was measured with a Trife type TYPE 30S (manufactured by Shintokagaku Co., Ltd.).
하기의 조건에 의해, 수 접촉각이 100° 미만이 된 시점에서 시험 종료로 했다. 수 접촉각 100° 이상을 유지하는 마모 횟수에 의해 내마모성의 평가로 했다.The test was terminated when the water contact angle became less than 100 degrees under the following conditions. The abrasion resistance was evaluated by the number of times of abrasion that maintained the water contact angle of 100 DEG or more.
접촉 면적: 10mm×30mmContact area: 10mm × 30mm
하중: 1.5kgLoad: 1.5kg
내 천 마모성My cloth abrasion
천: BEMCOT M-3II(아사히카세이사제)Cloth: BEMCOT M-3II (made by Asahi Chemical Industry Co., Ltd.)
이동 거리(편도) 20mmTravel distance (one way) 20mm
이동 속도 1,800mm/분Movement speed 1,800mm / min
하중: 0.5kg/cm2 Load: 0.5 kg / cm 2
또 수 접촉각은 접촉각계 DropMaster(교와카이멘카가쿠사제)를 사용하여, 피막의 물(액적: 2μl)에 대한 접촉각을 측정했다. 또한 수 접촉각은 2μl의 액적을 샘플 표면에 착적(着滴)시킨 후, 1초 후에 측정했다.In addition, the contact angle with water (droplet: 2 mu l) of the coating film was measured by using a contact angle meter DropMaster (manufactured by Kyowa Kaimenkagaku Co., Ltd.). The water contact angle was measured after 1 second after 2 占 퐇 of droplets were deposited on the sample surface.
상기 표 1에 의하면, 비교예 1, 2 및 3에서는 표면 처리제를 기재 표면에 증착 도공하고, 후처리 후에 내마모 시험을 행하면, 내마모 횟수는 0회이며, 마모 내구성은 나타나지 않았다. 이에 대해, 실시예 1~9에서는 표면 처리제를 기재 표면에 증착 도공하고, 후처리 후에 내마모 시험을 행하면, 우수한 내마모성을 발현했다. 실시예 1~9는 실록세인 결합, 실페닐렌 구조, 또는 실알킬렌 구조를 분자쇄 말단(분자의 연결기 부분)에 가지기 때문에, 특히 이들 연결기 부분의 SiCH3 부분이 기재 표면의 SiO2 층의 SiO2 유래의 OH 기 부분과 분자간력에 의해 상호작용하여, 표면 처리제 중의 폴리머가 배향하기 쉬워지는 점에서, 말단기에 가수분해성기를 가지지 않아도, 비교예의 표면 처리제에 비해 기재로의 밀착성이 향상되어 있는 것이라고 생각된다.According to Table 1, in Comparative Examples 1, 2 and 3, when the surface treatment agent was coated on the surface of the substrate and subjected to the abrasion resistance test after the post-treatment, the number of times of abrasion wear was 0, and the abrasion durability was not exhibited. On the other hand, in Examples 1 to 9, excellent abrasion resistance was exhibited when the surface treatment agent was coated on the surface of the base material and subjected to the abrasion resistance test after the post-treatment. Example 1-9 is a siloxane bond, room-phenylene structure, or room alkylene structure the molecular chain terminals because it has the (linking group of the molecule), in particular a SiO 2 layer of the SiCH 3 parts The base surfaces of these linking parts The OH group portion originating from SiO 2 interacts with each other due to the intermolecular force, and the polymer in the surface treatment agent is easily oriented, so that the adhesion to the substrate is improved compared with the surface treatment agent of the comparative example It is thought that there is.
본 발명의 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 포함하는 표면 처리제에 의해 방오성의 표면층을 형성한 수지는 우수한 마모 내구성을 나타낼 수 있다. 본 발명의 표면 처리제에 의해 방오성의 표면층을 형성한 수지는 특히 안경 렌즈, 선글래스, 터치패널 디스플레이, 반사 방지 필름 등의 표면의 방오 처리가 필요한 용도에 적합에 사용할 수 있다.The resin obtained by forming the surface layer of the antifouling effect by the surface treatment agent containing the fluoropolyether group-containing polymer-modified organosilicon compound of the present invention can exhibit excellent wear durability. The resin having the antifouling surface layer formed by the surface treatment agent of the present invention can be suitably used particularly in applications requiring an antifouling treatment on the surfaces of spectacle lenses, sunglasses, touch panel displays, antireflection films and the like.
(산업상 이용가능성)(Industrial applicability)
본 발명의 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물을 함유하는 표면 처리제에 의해 표면 처리된 물품은 우수한 마모 내구성을 나타낸다. 본 발명의 표면 처리제에 의해 표면 처리된 수지 제품은 특히 터치패널 디스플레이, 반사 방지 필름, 안경 렌즈 등 유지의 부착이 상정되는 수지 제품으로서 유효하다.An article surface-treated with a surface treatment agent containing a polymer-modified organosilicon compound containing a fluoropolyether group of the present invention shows excellent wear durability. The resin product surface-treated with the surface treatment agent of the present invention is particularly effective as a resin product to which adhesion of the oil, such as a touch panel display, an anti-reflection film, and a spectacle lens, is assumed.
Claims (10)
[식 중, Rf는 1가의 플루오로옥시알킬기 또는 2가의 플루오로옥시알킬렌기 함유 폴리머 잔기이며, Y는 독립적으로 2가의 탄화수소기이며, Q는 독립적으로 2가의 직쇄상 혹은 환상 오가노실록세인 잔기, 실알킬렌기 또는 실아릴렌기이며, X는 독립적으로 수소 원자, 탄소수 1~4의 알킬기 또는 페닐기이며, Z는 독립적으로 수소 원자, 하기 식
(식 중, R은 독립적으로 탄소수 1~4의 알킬기 또는 페닐기이다.)
으로 표시되는 기, 또는 하기 식
(식 중, X는 상기와 동일하며, W는 단결합 또는 2가의 탄화수소기이며, Q'는 실록세인 결합, 실알킬렌 구조 및 실아릴렌 구조로부터 선택되는 구조를 가지는 2가의 기이다.)
으로 표시되는 기이며, α는 1 또는 2이다.]
로 표시되는 플루오로폴리에터기 함유 폴리머 변성 유기 규소 화합물.(1)
Wherein Rf is a monovalent fluorooxyalkyl group or a divalent fluorooxyalkylene group-containing polymer residue, Y is independently a divalent hydrocarbon group, Q is independently a divalent linear or cyclic organosiloxane residue , X is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, Z is independently a hydrogen atom, a group represented by the following formula
(Wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group)
Or a group represented by the following formula
(Wherein X is as defined above, W is a single bond or a divalent hydrocarbon group, and Q 'is a divalent group having a structure selected from siloxane bonds, alkylalkylene structures and silarylene structures.)
And? Is 1 or 2.]
And the fluoro polyether group-containing polymer modified organosilicon compound represented by the formula
(식 중, p, q, r, s는 각각 0~200의 정수이며, p+q+r+s=3~200이며, 각 반복 단위는 직쇄상이어도 되고 분기상이어도 되며, 각 반복 단위끼리는 랜덤으로 결합되어 있어도 되고, d는 1~3의 정수이며, 이 단위는 직쇄상이어도 되고 분기상이어도 된다.)The fluoro polyether group-containing polymer-modified organosilicon compound according to claim 1, wherein in the formula (1),? Is 1 and the Rf group is a group represented by the following formula (2).
(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, D may be an integer of 1 to 3, and the unit may be linear or branched.
(식 중, p, q, r, s는 각각 0~200의 정수이며, p+q+r+s=3~200이며, 각 반복 단위는 직쇄상이어도 되고 분기상이어도 되며, 각 반복 단위끼리는 랜덤으로 결합되어 있어도 되고, d는 1~3의 정수이며, 이 단위는 직쇄상이어도 되고 분기상이어도 된다.)The polymer-modified organosilicon compound containing fluoropolyether group according to claim 1, wherein in the formula (1),? Is 2 and the Rf group is a group represented by the following formula (3).
(Wherein p, q, r and s are each an integer of 0 to 200, and p + q + r + s = 3 to 200. Each repeating unit may be linear or branched, D may be an integer of 1 to 3, and the unit may be linear or branched.
(식 중, X는 상기와 동일하며, R1은 독립적으로 탄소수 1~4의 알킬기 또는 페닐기이며, R2는 탄소수 1~4의 알킬렌기 또는 탄소수 6~12의 아릴렌기이다. g는 1~20의 정수이며, j는 1~8의 정수이다.)The fluoro polyether group-containing polymer-modified organosilicon compound according to any one of claims 1 to 4, wherein Q in the formula (1) is a group selected from groups represented by the following formulas.
(In the formula, X is the same as above, R 1 is independently an alkyl group or a phenyl group having from 1 to 4 carbon atoms, R 2 is an aryl group having from 1 to 4 carbon atoms, an alkylene group or carbon number of 6-12 in. G is 1 to 20, and j is an integer of 1 to 8.)
(식 중, g1은 2~20의 정수이며, e는 0~3의 정수이다.)6. The fluorine-containing polymer according to any one of claims 1 to 5, wherein in the formula (1), Z is a hydrogen atom and a group selected from the following groups: compound.
(Wherein g1 is an integer of 2 to 20, and e is an integer of 0 to 3.)
(식 중, Z는 상기와 동일하며, p1은 5~100의 정수, q1은 5~100의 정수이며, p1+q1은 10~105의 정수이다. g1은 2~20의 정수이며, e는 0~3의 정수이다.)The fluoropolyether-modified organosilicon compound according to any one of claims 1 to 6, wherein the fluoropolyether group-containing polymer-modified organosilicon compound represented by the formula (1) is represented by any one of the following formulas: Containing polymer modified organosilicon compound.
P1 is an integer of 5 to 100, q1 is an integer of 5 to 100, and p1 + q1 is an integer of 10 to 105. g1 is an integer of 2 to 20, and e is It is an integer from 0 to 3.)
(식 중, A는 말단이 -CF3기인 1가의 불소 함유기이며, Rf'는 2가의 플루오로옥시알킬렌기 함유 폴리머 잔기이다.)
로 표시되는 플루오로폴리에터기 함유 폴리머를 함유하는 것을 특징으로 하는 표면 처리제.The surface treatment agent according to claim 8,
(Wherein A is a monovalent fluorine-containing group whose terminal is a -CF 3 group and Rf 'is a divalent fluorooxyalkylene group-containing polymer residue).
And a fluoropolyether group-containing polymer represented by the following general formula (1).
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