KR101539262B1 - Polymer composition using diol including fluorine and surface-treated article using the same - Google Patents
Polymer composition using diol including fluorine and surface-treated article using the same Download PDFInfo
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- KR101539262B1 KR101539262B1 KR1020140132597A KR20140132597A KR101539262B1 KR 101539262 B1 KR101539262 B1 KR 101539262B1 KR 1020140132597 A KR1020140132597 A KR 1020140132597A KR 20140132597 A KR20140132597 A KR 20140132597A KR 101539262 B1 KR101539262 B1 KR 101539262B1
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- silane compound
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- 150000002009 diols Chemical class 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 title claims description 17
- 229910052731 fluorine Inorganic materials 0.000 title description 7
- 239000011737 fluorine Substances 0.000 title description 7
- 229920000642 polymer Polymers 0.000 title description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title 1
- -1 modified silane compound Chemical class 0.000 claims abstract description 61
- 239000000126 substance Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims description 46
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 27
- 239000012948 isocyanate Substances 0.000 claims description 22
- 150000002513 isocyanates Chemical class 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000005799 fluoromethylation reaction Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000001351 alkyl iodides Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000010408 film Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 230000003373 anti-fouling effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- IOPSRMSWKGMMAB-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene trifluoromethylbenzene Chemical compound FC(C1=CC(=CC=C1)C(F)(F)F)(F)F.FC(F)(F)C1=CC=CC=C1 IOPSRMSWKGMMAB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282575 Gorilla Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- JLHADLTXDDGZFX-UHFFFAOYSA-L [[acetyloxy(dibutyl)stannyl]oxy-dibutylstannyl] acetate Chemical compound CCCC[Sn](CCCC)(OC(C)=O)O[Sn](CCCC)(CCCC)OC(C)=O JLHADLTXDDGZFX-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000003426 chemical strengthening reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
Abstract
본원발명은 하기 화학식 1의 구조를 가지는 불소화 변성 실란 화합물 및 이를 이용한 표면처리물에 관한 것이다.
[화학식 1]
(상기 화학식 1에서 A는 
[Chemical Formula 1]
(Wherein A in the above formula
Description
본 발명은 불소함유 Diol을 이용한 폴리머 조성물 및 이를 이용한 표면처리물에 관한 것으로, 상세하게는 피착체와의 밀착성 및 내스크래치성이 우수하여 외관관리성이 우수하고, 발수성, 발유성이 발현되어 지문 및 먼지 부착을 방지할 수 있는 불소함유 Diol을 이용한 폴리머 조성물 및 이를 이용한 표면처리물에 관한 것이다.The present invention relates to a polymer composition using a fluorine-containing diol and a surface treated product using the fluorine-containing diol. More particularly, the present invention relates to a polymer composition using a fluorine-containing diol, which is excellent in adhesion and scratch resistance to an adherend, And a fluorine-containing diol capable of preventing dust adhesion, and a surface treated product using the polymer composition.
오늘날 모든 전자제품들은 아날로그 방식에서 디지털 방식으로 전환되고 있고, 사용자들의 편의성을 고려하여 디스플레이 장치를 장착시키고 있다. 이러한 디스플레이 장치는 단순히 제품의 용도 및 작동과정에 의한 정보를 사용자에게 제공해 주는 표시장치로서의 기능뿐만 아니라, 좀 더 적극적으로 사용자들이 필요한 정보를 입력할 수 있도록 하는 입력장치로서의 기능을 수행할 수 있도록 진화되고 있다. 이러한 디스플레이 장치로서 대표적인 것이 터치스크린을 포함한 액정표시장치이다. Today, all electronic products are being converted from analog to digital, and display devices are being installed for users' convenience. Such a display device has not only a function as a display device for providing information to a user through the use of the product and an operation process but also a function as an input device for enabling users to input necessary information more positively . A representative example of such a display device is a liquid crystal display device including a touch screen.
이러한 추세를 감안하여, 휴대폰, 컴퓨터, PDA, TV 등은 물론이고, 전통적으로 디스플레이가 없었던 냉장고, 일반전화기 등의 제품에도 새롭게 디스플레이 장치 및 터치스크린이 채용되고 있다. 이러한 현상은 비단 전자제품뿐만 아니라, 산업용품 및 건축물에 사용되는 디스플레이에 있어서도 마찬가지이다. In view of this tendency, display devices and touch screens have been newly adopted in products such as a mobile phone, a computer, a PDA, a TV, and a refrigerator and a general telephone which have not traditionally displayed. This phenomenon is the same not only for electronic products but also for displays used in industrial products and buildings.
터치스크린은, 종래의 물리적인 키보드와 같은 입력수단 대신에, 디스플레이 화면에 나타난 문자 또는 기호 신호에 따라 사용자가 펜 또는 손가락 끝을 이용하여 일정한 정도 이상의 압력을 가할 경우, 그 가압된 위치를 파악하여 내부에 저장된 소프트웨어에 의해 필요한 정보를 입력시키도록 된 화면을 말한다. 전자제품에 터치스크린을 설치할 경우, 키보드 또는 키패드와 같은 물리적인 입력수단을 별도로 형성할 필요가 없으므로, 전자제품을 소형화시킬 수 있고, 간단하고 제조할 수 있는 장점이 있다. 또한, 수요자의 입장에서도 경박단소형 제품이 휴대하기 용이하고 사용하기 편리한 측면이 있으므로, 전자제품에 대한 터치스크린의 탑재는 보편화되어가는 경향이다In place of input means such as a conventional physical keyboard, when a user applies a pressure of a certain level or more using a pen or a finger tip according to a character or a symbol signal displayed on a display screen, the touch screen grasps the pressed position It is a screen to input necessary information by software stored in the inside. When a touch screen is mounted on an electronic product, there is no need to separately form a physical input means such as a keyboard or a keypad, thereby making it possible to miniaturize the electronic product and to manufacture the touch screen. Also, from the viewpoint of the consumer, since the light and compact small-sized product is easy to carry and easy to use, mounting of the touch screen to the electronic product tends to become common
한편 이러한 터치스크린의 사용이 일반화되면서 외부로부터의 충격이나 오염으로부터 보호하기 위한 소재의 개발이 급속히 진행되고 있다. 예를 들어 필름 표면에 먼지 또는 기타 오염물질이 묻어 잔류하는 것을 방지하기 위해 대전방지 필름의 형태를 적용하거나 지문이 남는 것을 방지하기 위해 지문방지 필름을 도입하기도 한다.Meanwhile, as the use of such a touch screen is becoming common, development of a material for protecting it from external impact or contamination is proceeding rapidly. For example, in order to prevent dust or other contaminants from adhering to the surface of the film, an antistatic film may be applied or an anti-fingerprint film may be introduced to prevent fingerprints from remaining.
이러한 단점을 해결하는 방법 중 하나로 필름을 구성하는 조성물에 표면자유에너지가 아주 낮은 불소화합물을 도입할 수 있다. 불소화합물은 표면자유에너지가 10 dyne/㎝ 정도로 발수성, 발유성, 이형성, 방오성, 윤활성, 내화학성 등의 기능이 동시에 구현될 수 있어 오염으로부터 터치스크린을 보호할 수 있는 장점이 있다. 그러나 외부로부터의 충격이나 스크래치 등에 취약하여 장시간 사용하기 어렵다는 단점이 있다.As a method for solving such a disadvantage, a fluorine compound having a very low surface free energy can be introduced into a composition constituting the film. The fluorine compound has a surface free energy of about 10 dyne / cm and has the advantage of protecting the touch screen from contamination because the functions such as water repellency, oil repellency, releasing property, antifouling property, lubricity and chemical resistance can be realized at the same time. However, this method is disadvantageous in that it is vulnerable to external shocks and scratches, and thus is difficult to use for a long time.
또한 내스크래치성을 확보하기 위해 실리콘류를 포함하여 필름을 조성할 수 있으나, 유성물질인 지문 등이 필름에 잔존하기 쉬워 방오성을 확보하기 곤란하다는 단점이 있다.In order to ensure scratch resistance, it is possible to form a film containing a silicone fluid, but it is difficult to secure antifouling properties since fingerprints, which are oily substances, are likely to remain on the film.
상기와 같이 피착체와의 밀착성, 방오성 및 내구성을 모두 가질 수 있는 디스플레이 보호용 조성물의 개발이 절실히 요구되고 있다.There is a desperate need to develop a display protective composition having both adherence to an adherend, antifouling property and durability as described above.
본 발명은 상기와 같은 문제점을 해결하기 위해 도출된 것으로, 불소화 디올과 이소시아네이트 관능성 실란을 1차로 반응시키고, 2차로 실란 화합물을 플루오로메틸화(fluoromethylation)하여 우수한 내오염성 및 내스크래치성을 가지는 불소화 변성 실란 화합물의 제공을 목적으로 한다.SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a method for producing a fluorinated polyisocyanate, which comprises reacting a fluorinated diol with an isocyanate functional silane in a primary reaction and fluoromethylating a silane compound in a second order, To provide a modified silane compound.
본 발명의 다른 목적은 상기 불소화 변성 실란 화합물을 포함하는 코팅막의 제공을 목적으로 한다.Another object of the present invention is to provide a coating film containing the fluorinated modified silane compound.
본 발명은 불소함유 Diol을 이용한 폴리머 조성물 및 이를 이용한 표면처리물에 관한 것이다.The present invention relates to a polymer composition using a fluorine-containing diol and a surface treatment product using the polymer composition.
본 발명의 일 양태는 하기 화학식 1의 구조를 가지는 불소화 변성 실란 화합물에 관한 것이다.One aspect of the present invention relates to a fluorinated modified silane compound having a structure represented by the following formula (1).
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서 A는 
D는 수소, -CF3, 
a는 1 내지 11이고;a is 1 to 11;
m은 1 내지 40, n은 1 내지 40, 20 ≤ m+n ≤ 80이며;m is 1 to 40, n is 1 to 40, and 20? m + n? 80;
a, m 및 n은 모두 정수이다.)a, m, and n are all integers.)
본 발명에서 상기 불소화 변성 실란 화합물은 중량평균분자량이 1,850 내지 5,000일 수 있다.In the present invention, the fluorinated modified silane compound may have a weight average molecular weight of 1,850 to 5,000.
본 발명의 다른 양태는 Another aspect of the present invention is
a) 불소화 디올, 이소시아네이트 관능성 실란 및 촉매를 포함하는 조성물을 반응시켜 실란 화합물을 제조하는 단계;a) reacting a composition comprising a fluorinated diol, an isocyanate functional silane and a catalyst to produce a silane compound;
b) 상기 실란 화합물을 플루오로메틸화하여 불소화 변성 실란 화합물을 제조하는 단계; 및 b) subjecting the silane compound to fluoromethylation to produce a fluorinated modified silane compound; And
c) 상기 불소화 변성 실란 화합물을 세척하는 단계;c) washing the fluorinated modified silane compound;
를 포함하는 불소화 변성 실란 화합물 제조방법에 관한 것이다.To a fluorinated modified silane compound.
본 발명에서 상기 불소화 디올은 하기 화학식 2의 구조를 가질 수 있으며, 상기 이소시아네이트 관능성 실란은 하기 화학식 3 또는 4의 구조를 가질 수 있다.In the present invention, the fluorinated diol may have a structure of the following formula (2), and the isocyanate functional silane may have a structure of the following formula (3) or (4).
[화학식 2](2)
(상기 화학식 2에서 m은 1 내지 40, n은 1 내지 40, 20 ≤ m+n ≤ 80이다.)(In the formula (2), m is 1 to 40, n is 1 to 40, and 20? M + n? 80.)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
본 발명에서 상기 촉매는 1,4-디아자비시클로옥탄, 테트라메틸부탄디아민, 주석 옥토에이트, 디부틸틴디라우레이트, 1,3-디아세톡시테트라부틸디스탄노옥산, 디부틸틴디트리메틸실록산, 디부틸틴디트리에톡시실록사이드 및 디부틸틴디트리메톡시실록산에서 선택되는 어느 하나 또는 둘 이상일 수 있다.In the present invention, the catalyst is preferably selected from the group consisting of 1,4-diazabicyclooctane, tetramethylbutane diamine, tin octoate, dibutyl tin dilaurate, 1,3-diacetoxytetrabutyldistannooxane, Dibutyl tin dimethoxy siloxane, dibutyl tin dimethoxy siloxane, dibutyl tin dimethoxy siloxane and dibutyl tin dimethoxy siloxane.
또한 상기 플루오로메틸화는 실란 화합물에 하기 화학식 5의 알킬아이오드 2 내지 3 ㎖/min의 공급속도로 20 내지 40 분간 공급하여 진행할 수 있다.The fluoromethylation may be carried out by supplying the silane compound at a feed rate of alkyl iodide of the following formula (5): 2 to 3 ml / min for 20 to 40 minutes.
[화학식 5][Chemical Formula 5]
CF3(CF2)oICF 3 (CF 2 ) o I
(상기 화학식 5에서 o는 0 내지 11의 정수이다.)(Wherein o is an integer of 0 to 11).
또한 실란 화합물은 불소화 디올 100 중량부에 대하여, 이소시아네이트 관능성 실란 3 내지 30 중량부 및 촉매 0.1 내지 2 중량부를 포함하여 이루어질 수 있다.Also, the silane compound may comprise 3 to 30 parts by weight of an isocyanate functional silane and 0.1 to 2 parts by weight of a catalyst, based on 100 parts by weight of the fluorinated diol.
본 발명의 또 다른 양태는 상기 불소화 변성 실란 화합물을 포함하는 코팅막에 관한 것으로 상기 코팅막은 피착체가 세라믹 또는 금속일 수 있다.Another aspect of the present invention relates to a coating film comprising the fluorinated modified silane compound, wherein the coating film may be ceramic or metal.
본 발명에 따른 불소화 변성 실란 화합물은 불소화 디올과 이소시아네이트 관능성 실란을 1차로 반응시키고, 2차로 실란 화합물을 플루오로메틸화(fluoromethylation)하여 탁월한 내오염성 및 내스크래치성을 가진다. 또한 발수, 발유 및 오염제거능을 가지며, 낮은 동마찰계수 등이 발현되며, 졸-겔 반응(sol-gel reaction)의 중간원료로도 적용이 가능하다. 이를 바탕으로 자동차용, 주거용 또는 디스플레이용 세라믹 피착체 및 금속 피착체의 표면 보호막, 방오막 등의 다양한 분야에 적용할 수 있다.The fluorinated modified silane compound according to the present invention has excellent stain resistance and scratch resistance by firstly reacting a fluorinated diol with an isocyanate functional silane and fluoromethylating the silane compound in a second order. It also has water repellent, oil and decontamination ability, exhibits low kinetic friction coefficient, and is applicable as an intermediate raw material for sol-gel reaction. Based on this, it can be applied to various fields such as a surface protective film of a ceramic adherend for a car, a residence or a display, a metal adherend, and an antifouling film.
이하 구체예 또는 실시예를 통해 본 발명에 따른 불소화 변성 실란 화합물 및 이의 제조방법을 더욱 상세히 설명한다. 다만 하기 구체예 또는 실시예는 본 발명을 상세히 설명하기 위한 하나의 참조일 뿐 본 발명이 이에 한정되는 것은 아니며, 여러 형태로 구현될 수 있다. Hereinafter, the fluorinated modified silane compound according to the present invention and a method for producing the same will be described in more detail with reference to specific examples or examples. It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.
또한 달리 정의되지 않은 한, 모든 기술적 용어 및 과학적 용어는 본 발명이 속하는 당업자 중 하나에 의해 일반적으로 이해되는 의미와 동일한 의미를 갖는다. 본원에서 설명에 사용되는 용어는 단지 특정 구체예를 효과적으로 기술하기 위함이고 본 발명을 제한하는 것으로 의도되지 않는다.Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
또한 명세서 및 첨부된 특허청구범위에서 사용되는 단수 형태는 문맥에서 특별한 지시가 없는 한 복수 형태도 포함하는 것으로 의도할 수 있다.Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.
본 발명자는 기존의 표면 보호막에 요구되는 방오성, 발수성 및 내스크래치성을 모두 확보하는 막을 제조하기 위해 예의 연구를 거듭하던 중, 불소화 디올과 이소시아네이트 관능성 실란을 1차로 반응시켜 실란 화합물을 제조하고, 2차로 주쇄에 존재하며 내마찰성 및 발수성, 발유성에 악영향을 끼치는 수소기를 트리플루오르메틸기(trifluoromethyl)로 치환할 경우, 탁월한 내오염성 및 내스크래치성을 발현하는 것을 발견하여 본 발명을 완성하게 되었다.DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to produce films having both antifouling properties, water repellency and scratch resistance, which are required for existing surface protective films, while reacting fluorinated diols and isocyanate functional silanes in a primary reaction to prepare silane compounds, The present inventors have found that when a hydrogen group existing in the main chain and having adverse effects on resistance to abrasion, water repellency and oil repellency is replaced with trifluoromethyl, excellent stain resistance and scratch resistance are exhibited.
본 발명에 따른 불소화 변성 실란 화합물은 하기 화학식 1의 구조를 가질 수 있다.The fluorinated modified silane compound according to the present invention may have a structure represented by the following formula (1).
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서 A는 
D는 수소, -CF3, 
a는 1 내지 11이고;a is 1 to 11;
m은 1 내지 40, n은 1 내지 40, 20 ≤ m+n ≤ 80이며;m is 1 to 40, n is 1 to 40, and 20? m + n? 80;
a, m 및 n은 모두 정수이다.)a, m, and n are all integers.)
본 발명에 따른 화학식 1의 불소화 변성 실란 화합물은 The fluorinated modified silane compound of the formula (1)
a) 불소화 디올, 이소시아네이트 관능성 실란 및 촉매를 포함하는 조성물을 반응시켜 실란 화합물을 제조하는 단계;a) reacting a composition comprising a fluorinated diol, an isocyanate functional silane and a catalyst to produce a silane compound;
b) 상기 실란 화합물을 플루오로메틸화하여 불소화 변성 실란 화합물을 제조하는 단계; 및 b) subjecting the silane compound to fluoromethylation to produce a fluorinated modified silane compound; And
c) 상기 불소화 변성 실란 화합물을 세척하는 단계;c) washing the fluorinated modified silane compound;
를 포함하여 진행할 수 있다. 이를 상세히 설명하면, 먼저 불소화 디올, 이소시아네이트 관능성 실란 및 촉매를 포함하는 조성물을 반응시켜 실란 화합물을 제조할 수 있다.. ≪ / RTI > In detail, a silane compound can be prepared by reacting a composition containing a fluorinated diol, an isocyanate functional silane, and a catalyst.
본 발명에서 상기 불소화 디올은 하기 화학식 2의 구조를 가질 수 있다.In the present invention, the fluorinated diol may have a structure represented by the following formula (2).
[화학식 2](2)
(상기 화학식 2에서 m은 1 내지 40, n은 1 내지 40, 20 ≤ m+n ≤ 80이다.)(In the formula (2), m is 1 to 40, n is 1 to 40, and 20? M + n? 80.)
상기 화학식 2에서 반복되는 단위(m, n)는 블록공중합체 형태를 이룰 수도 있으나, 랜덤하게 결합될 수도 있다. 또한 20 ≤ m+n ≤ 80일 수 있으며, 더욱 바람직하게는 20 ≤ m+n ≤ 60이 좋다. m+n이 20 미만인 경우 이소시아네이트 관능성 실란과의 반응은 용이하게 진행될 수 있으나 내오염성을 기대하기 어려우며, m+n이 80 초과인 경우 이소시아네이트 관능성 실란과의 반응이 제대로 진행되지 않아 경화성이 떨어질 수 있으며, 결과적으로 내마모성이 하락할 수 있다.The repeating unit (m, n) in the above formula (2) may be a block copolymer or may be randomly bonded. 20? M + n? 80, more preferably 20? M + n? 60. When m + n is less than 20, the reaction with the isocyanate functional silane can proceed easily, but it is difficult to expect the stain resistance. When m + n exceeds 80, the reaction with the isocyanate functional silane does not progress properly and the curability is poor And as a result, wear resistance may deteriorate.
본 발명에서 상기 이소시아네이트 관능성 실란은 피착체 표면에 하이드록시기(-OH)와 반응하며, 말단의 실란에 의해 습기 경화형 가교 메커니즘에 의해 피착물에 반응 접착될 수 있도록 한다. 이를 상세히 설명하면, 제조된 불소화 변성 실란 화합물은 주쇄의 말단에 메톡시기(-OCH3)를 가지며, 화합물을 피착체에 얇은 박막형태로 코팅되면, 피착체 표면에 하이드록시와 쉽게 반응한다. 이때 탈알콜 및 탈에테르 반응이 함께 일어나게 되며, 메탄올이 생성되지만 휘발성이 높기 때문에 쉽게 방출된다. 그리고 동시에 피착체와 화합물의 하이드록시기 간에 탈수축합반응이 일어나 경화될 수 있다. 이를 반응식으로 나타내면 하기 반응식 1과 같다.In the present invention, the isocyanate functional silane reacts with the hydroxyl group (-OH) on the surface of the adherend, and is allowed to react and adhere to the adherend by the moisture-setting crosslinking mechanism by the terminal silane. In detail, the produced fluorinated modified silane compound has a methoxy group (-OCH 3 ) at the end of the main chain. When the compound is coated on the adherend in the form of a thin film, it readily reacts with hydroxy on the adherend surface. At this time, dehalogenation and deether reaction occur together, and methanol is produced but easily released because of high volatility. And at the same time, a dehydration condensation reaction between the adduct and the hydroxyl group of the compound occurs and can be cured. The reaction scheme is shown in the following reaction scheme 1.
[반응식 1][Reaction Scheme 1]
상기 이소시아네이트 관능성 실란은 하기 화학식 3 또는 4의 구조를 가질 수 있다.The isocyanate functional silane may have the structure of the following formula (3) or (4).
[화학식 3](3)
[화학식 4][Chemical Formula 4]
본 발명에서 상기 이소시아네이트 관능성 실란으로 더욱 바람직하게는 상기 화학식 3의 실란을 사용하는 것이 좋다. 규소에 치환된 알킬기의 탄소수가 많아질수록 피착체와의 가수분해 반응 속도가 느려지게 되며, 제조되는 실란 화합물의 경화속도에 영향을 줄 수 있으므로, 메톡시실란을 사용하는 것이 좋다.In the present invention, it is more preferable to use the silane of the above formula (3) as the isocyanate functional silane. The higher the carbon number of the alkyl group substituted with silicon is, the slower the hydrolysis reaction rate with the adherend becomes, and it may be preferable to use methoxysilane since it affects the curing rate of the produced silane compound.
본 발명에서 상기 a) 단계는 기체유입구가 구비된 반응용기에 불소화 디올 및 이소시아네이트 관능성 실란을 투입하여 진행할 수 있다. 이때 반응용기 내부는 진공 또는 감압상태를 유지하는 것이 좋으며, 균일한 혼합을 위해 50 내지 100℃로 가열하면서 교반하는 것이 좋다. 또한 불소화 디올을 먼저 투입한 후 이소시아네이트 관능성 실란을 투입하고 교반하는 것이 좋은데, 이때 실란이 디올에 점진적으로 혼합되도록 교반속도를 최소화하여 진행하는 것이 좋다. 또한 교반시간은 조성물의 양에 따라 자유롭게 조절할 수 있으며, 본 발명이 이에 한정되는 것은 아니다. 또한 본 발명에서 상기 이소시아네이트 관능성 실란은 불소화 디올 100 중량부에 대하여 3 내지 30 중량부 포함하는 것이 좋다.In the present invention, the step a) may be carried out by introducing a fluorinated diol and an isocyanate functional silane into a reaction vessel equipped with a gas inlet. At this time, it is preferable to maintain the inside of the reaction vessel under a vacuum or a reduced pressure, and it is preferable to stir while heating to 50 to 100 캜 for uniform mixing. It is also preferable that the fluorinated diol is added first and then the isocyanate functional silane is added and stirred. It is preferable that the stirring speed is minimized so that the silane is gradually mixed with the diol. Further, the agitation time can be freely adjusted according to the amount of the composition, and the present invention is not limited thereto. In the present invention, it is preferable that the isocyanate functional silane is contained in an amount of 3 to 30 parts by weight based on 100 parts by weight of the fluorinated diol.
다음으로 촉매를 투입하여 반응을 더욱 진행시킨다. 본 발명에서 상기 촉매는 우레탄 중합반응을 촉진할 수 있는 물질이라면 종류에 한정하지 않으며, 최소의 첨가량으로 투입하기 위해 용매에 희석시켜 사용하는 것이 바람직하다. The catalyst is then added to further advance the reaction. In the present invention, the catalyst is not limited to any kind as far as it can promote the urethane polymerization reaction, and it is preferable to use the catalyst in a diluted solvent for the addition in the minimum amount.
본 발명에서 사용 가능한 촉매로 예를 들면, 1,4-디아자비시클로옥탄(1,4-Diazabicyclooctane, DABCO), 테트라메틸부탄디아민(Tetramethyl butanediamine, TMBDA), 주석 옥토에이트(Tin octoate, SnOct), 디부틸틴디라우레이트(Dibutyltindilaurate, DBTDL), 1,3-디아세톡시테트라부틸디스탄노옥산(1,3-Diacetoxy tetrabutyl distannoxane), 디부틸틴디트리메틸실록산(Dibutyltin di(trimethylsiloxide)), 디부틸틴디트리에톡시실록사이드(Dibutyltin di(triethoxysiloxide)) 및 디부틸틴디트리메톡시실록산(Dibutyltin di(trimethoxhy siloxide))에서 선택되는 어느 하나 또는 둘 이상을 사용할 수 있으며, 바람직하게는 DBTDL를 사용하는 것이 좋다.Examples of the catalyst that can be used in the present invention include 1,4-diazabicyclooctane (DABCO), tetramethyl butanediamine (TMBDA), tin octoate (SnOct) Dibutyltindilaurate (DBTDL), 1,3-diacetoxy tetrabutyl distannoxane, dibutyltin di (trimethylsiloxide), dibutyl tin dilaurate (Dibutyltin di (triethoxysiloxide)) and dibutyltin di (trimethoxysiloxane) can be used, and it is preferable to use DBTDL .
본 발명에서 촉매를 용해시키기 위한 용매는 불소화 디올과 이소시아네이트 관능성 실란 모두에 친화성이 있는 물질이라면 종류에 한정하지 않으며, 바람직하게는 1,3-비스트리플루오르메틸벤젠(1,3-bis(trifluoromethyl)benzene), 에틸노나플루오로부틸에테르(ethylnonafluorobutylether), 퍼플루오르카본류(perfluorocarbon)류, 하이드로플루오르에테르(hydrofluoroether)류를 사용하는 것이 좋다.In the present invention, the solvent for dissolving the catalyst is not limited to any kind as long as it is compatible with both the fluorinated diol and the isocyanate functional silane, and preferably 1,3-bis (trifluoromethyl) benzene trifluoromethyl benzene, ethylnonafluorobutylether, perfluorocarbon, hydrofluoroether, etc., are preferably used.
본 발명에서 상기 촉매는 불소화 디올 100 중량부에 대하여 0.1 내지 2 중량부 포함하는 것이 좋으며, 촉매에 희석 시 0.1 내지 1 %의 희석율(rate of dilution)을 유지하는 것이 좋다. 또한 촉매를 투입한 후 가열 및 교반하여 반응을 완성할 수 있다. 이때 가열 온도 및 교반 속도는 촉매 투입 전 가열 온도 및 교반 속도와 동일 또는 상이할 수 있다.In the present invention, the catalyst is preferably contained in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the fluorinated diol, and it is preferable to maintain a rate of dilution of 0.1 to 1% when diluted with the catalyst. The reaction may be completed by adding a catalyst and heating and stirring. In this case, the heating temperature and stirring speed may be the same as or different from the heating temperature and stirring speed before the catalyst is introduced.
반응이 종료되어 실란 화합물이 생성되면 b) 단계와 같이 상기 실란 화합물을 플루오로메틸화하여 불소화 변성 실란 화합물을 제조할 수 있다.When the reaction is completed to produce a silane compound, the fluorinated silane compound may be prepared by fluoromethylating the silane compound as in step b).
상기 플루오로메틸화(fluoromethylation)는 상기 실란 화합물의 주쇄를 구성하는 우레탄기(-CONH-)의 수소를 플루오로알킬로 치환하기 위한 것으로, 실란 화?물에 하기 화학식 5의 알킬아이오드 기체를 공급하여 진행할 수 있다.The fluoromethylation is for replacing the hydrogen of the urethane group (-CONH-) constituting the main chain of the silane compound with the fluoroalkyl, and the alkyl iodide gas of the following general formula .
[화학식 5][Chemical Formula 5]
CF3(CF2)oICF 3 (CF 2 ) o I
(상기 화학식 5에서 o는 0 내지 11의 정수이다.)(Wherein o is an integer of 0 to 11).
상기 알킬아이오드는 상기 실란 화합물의 플루오로메틸화를 더욱 용이하게 진행하기 위해 기체 상태로 공급할 수 있으며, 이때 2 내지 3 ㎖/min의 공급속도로 20 내지 40분간 공급하여 진행하는 것이 바람직하다. The alkyl iodide may be supplied in a gaseous state in order to facilitate the fluoromethylation of the silane compound. In this case, the alkyl iodide is preferably supplied for 20 to 40 minutes at a feed rate of 2 to 3 ml / min.
알킬아이오드를 공급하여 플루오로메틸화를 충분히 진행한 후, 감압을 해제하고 온도를 낮춘 상태에서 교반시킨다. 이때 교반 온도는 40 내지 60℃, 교반속도는 100 내지 250rpm으로 진행할 수 있다. 그리고 c) 단계와 같이 실란 화합물을 세척하여 미 반응물, 잔존 촉매 등의 불순물을 제거할 수 있다. The alkyl iodide is fed to proceed sufficiently in the fluoromethylation, and then the decompression is released and the temperature is lowered. At this time, the stirring temperature may be 40 to 60 ° C, and the stirring speed may be 100 to 250 rpm. The silane compound may be washed as in step c) to remove impurities such as unreacted materials and residual catalyst.
상기 c) 단계는 두 가지 이상의 용매를 혼합하여 세척용액으로 할 수 있다. 이는 상기 불소화 변성 실란 화합물을 녹일 수 있는 제 1용매와, 미 반응물, 잔존 촉매 등의 불순물만을 용해하는 제 2용매로 나눌 수 있다. In the step c), a washing solution may be prepared by mixing two or more solvents. This can be divided into a first solvent capable of dissolving the fluorinated modified silane compound and a second solvent dissolving only impurities such as unreacted materials and residual catalyst.
상기 제 1 용매는 상기 촉매 용해 시 사용한 불소계 용매를 사용하는 것이 좋으며, 바람직하게는 1,3-비스트리플루오르메틸벤젠을 사용하는 것이 좋다. 또한 제 2 용매는 알콜류 또는 아세테이트류, 바람직하게는 메탄올, 에탄올, 이소프로필알콜, 노말프로필알콜, 이소부탄올, 노말부탄올, 아밀알코올, 펜타놀 및 헥산올, 에틸 아세테이트 등을 사용하는 것이 좋다.The first solvent is preferably a fluorine-based solvent used for dissolving the catalyst, and 1,3-bistrifluoromethylbenzene is preferably used. The second solvent is preferably an alcohol or an acetate, preferably methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutanol, n-butanol, amyl alcohol, pentanol and hexanol, ethyl acetate and the like.
상기 세척용액을 반응기에 투입하면, 무게가 가벼운 제 2용매는 상층부에 존재하며, 제 1 용매는 반응용기의 하층부에 존재하여 상분리가 일어나게 된다. 상분리 후에 제 2용매를 제거함으로써 제 2용매에 용해된 불순물을 효과적으로 제거할 수 있다. 그리고 메탄올을 제거한 용액을 다시 감압하여 최종 수득물인 불소화 변성 실란 화합물을 얻을 수 있다.When the cleaning solution is introduced into the reactor, the lightweight second solvent is present in the upper layer, and the first solvent is present in the lower layer of the reaction vessel, resulting in phase separation. The impurities dissolved in the second solvent can be effectively removed by removing the second solvent after the phase separation. The methanol-removed solution is further reduced in pressure to obtain a fluorinated modified silane compound as a final product.
본 발명에 따른 불소화 변성 실란 화합물은 중량평균분자량이 1,850 내지 5,000일 수 있다. 또한 관능성 실란을 1차로 반응시키고, 2차로 실란 화합물을 플루오로메틸화(fluoromethylation)하여 탁월한 내오염성 및 내스크래치성을 가진다. 또한 발수, 발유 및 오염제거능을 가지며, 낮은 동마찰계수 등이 발현되며, 졸-겔 반응(sol-gel reaction)의 중간원료로도 적용할 수 있는 장점이 있다.The fluorinated modified silane compound according to the present invention may have a weight average molecular weight of 1,850 to 5,000. Also, the functional silane is firstly reacted and the silane compound is subjected to fluoromethylation in the second stage, thereby having excellent stain resistance and scratch resistance. In addition, it has water repellent, oil and decontamination ability, low kinetic friction coefficient and the like, and is also applicable as an intermediate material of a sol-gel reaction.
본 발명은 또한 상기 불소화 변성 실란 화합물을 포함하는 코팅막을 제공할 수 있다. 이때 코팅막의 제조방법은 본 발명에서 한정하지 않으며, 예를 들어 롤코팅, 스크린프린팅, 닥터블레이드, 스핀코팅, 딥코팅, 스프레이코팅, 옵셋프린팅, 감압 여과식 및 노멀캐스팅 등의 방법으로 진행할 수 있다.The present invention can also provide a coating film containing the fluorinated modified silane compound. At this time, the method for producing the coating film is not limited to the present invention, and can be carried out by, for example, roll coating, screen printing, doctor blade, spin coating, dip coating, spray coating, offset printing, vacuum filtration and normal casting .
상기 코팅막은 피착체의 표면을 오염 및 스크래치 등으로부터 보호하기 위한 것으로, 상기 피착체는 전자제품의 디스플레이, 자동차 창문, 건축용 창문 등의 세라믹 또는 금속일 수 있다.
The coating film is for protecting the surface of an adherend from contamination and scratches, and the adherend may be a ceramic or metal such as a display for an electronic product, an automobile window, a window for a building, or the like.
이하 실시예 및 비교예를 들어 본 발명에 따른 불소화 변성 실란 화합물 및 이의 제조방법을 더욱 상세히 설명한다. 다만 하기 실시예 및 비교예는 본 발명을 더욱 상세히 설명하기 위한 하나의 예시일 뿐, 본 발명이 하기 실시예 및 비교예에 의해 제한되는 것은 아니다.Hereinafter, the fluorinated modified silane compound according to the present invention and a method for producing the same will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.
하기 실시예 및 비교예를 통해 제조된 시편의 물성을 다음과 같이 측정하였다.The physical properties of the specimens prepared through the following examples and comparative examples were measured as follows.
(시편 제작 방법)(Method of specimen production)
① 피착체 : Corning 사의 gorilla 2319 0.55㎜(크기 60× 140㎜, 화학강화깊이 40㎛)를 사용하였다. 피착체의 전광선투과율은 91.2%, 굴절율은 1.51이다.1) Adherend: gorilla 2319 0.55 mm (size 60 × 140 mm, chemical strengthening depth 40 μm) of Corning was used. The total light transmittance of the adherend is 91.2% and the refractive index is 1.51.
② 시편 : 각 실시예 및 비교예를 통해 제조된 불소화 변성 실란 화합물을 ethylnonafluorobutylether(HFE7200, Novec)에 0.1% 고형분 함량이 되도록 용해하여 시편용액을 제조하였다. 그리고 시편용액 500g을 스프레이 코터에 투입하고 피착체에 분무하여 건조 후 두께가 20㎚이 되도록 코팅하였다. 코팅이 끝난 피착체는 170℃ 오븐에서 10분간 경화하여 시편을 완성하였다.(2) Specimen: A fluorine-modified silane compound prepared through each of Examples and Comparative Examples was dissolved in ethylnonafluorobutylether (HFE 7200, Novec) to have a solids content of 0.1% to prepare a test solution. Then, 500 g of the sample solution was put into a spray coater, sprayed on the adherend, dried and coated to a thickness of 20 nm. The coated adherend was cured in a 170 ° C oven for 10 minutes to complete the specimen.
(접촉각)(Contact angle)
코팅된 피착체 표면에 접촉각 측정기(Kruss사)로 초순수를 3㎕ 접적하고 1초 후의 접촉각을 측정하였다.The surface of the coated adherend was contacted with 3 초 of ultrapure water by a contact angle meter (Kruss Co.), and the contact angle after 1 second was measured.
(내오염성)(Stain resistance)
코팅된 피착체 표면에 유성 네임펜 블랙(모나미)을 사용하여 타원형 철망구조(ℓℓℓ, 최장지름길이 10㎜) 3개를 표시하고, 10분간 방치하였다. 그리고 와이퍼 중형(유한킴벌리)을 이용하여 1㎏ 하중으로 닦아내고 다음의 기준에 따라 육안 관측하였다.Three elliptical wire netting structures (ℓℓℓ, 10 mm of the longest shortest path) were marked on the surface of the coated adherend using an oil-based nampen black (Monami), and left for 10 minutes. The wipers were wiped with a weight of 1 kg using a wiper middle type (Yuhan-Kimberly) and observed with the naked eye according to the following criteria.
A : 1회 왕복으로 완전히 지워짐.A: It is completely erased by one round trip.
B : 1회 왕복으로 타원형 흔적이 희미하게 남음.B: One round trip oval traces remain faint.
C : 1회 왕복으로 타원형 흔적이 선명함.C: Oval traces are clear with one round trip.
D : 1회 왕복으로 타원형 흔적이 전혀 안지워짐.D: Oval traces are not cleared at one round trip.
(내마모성)(Abrasion resistance)
러빙 Tester CT-RB5(5축, 코아테크사)을 사용하여 지우개에 500g 하중을 인가하고 코팅면에 올려 1회 왕복거리 40㎜, 분당 40회 왕복 속도로 1,500회 왕복한 후의 접촉각을 측정하였다.A 500 g load was applied to the eraser using a rubbing tester CT-RB5 (5-axis, manufactured by Core Tech Co., Ltd.), and the contact angle was measured after the reciprocating distance of 40 mm and the reciprocating speed of 40 times per minute.
(내찰상성)(Scratch resistance)
CT-RB1(1축, 코아테크사)을 사용하여 지우개 대신 steel wool #0000을 고정하고 500g 하중을 인가하여 분당 100㎝ 속도로 500회 왕복한 후 접촉각을 측정하였다.
Instead of an eraser, steel wool # 0000 was fixed using a CT-RB1 (1-axis, manufactured by Core Tech Co., Ltd.), and 500 g load was applied.
(실시예 1)(Example 1)
마크네틱바 및 가스주입구가 부착된 유리반응용기에 불소화 디올(Fomblin D2, Solvay사, total equivalent weight 1734) 617g과 이소시아네이트 관능성 실란(Silquest A-link35, Momentive사, purity 96.4%) 151.6g을 넣고 진공감압 0.8bar를 유지하면서 평균온도 85℃로 가열 교반하였다. 이때 상층부의 이소시아네이트 관능성 실란이 하부 불소화 디올액에 점진적으로 스며들도록 교반 속도를 최소화하여 2시간 유지하였다.617 g of fluorinated diol (Fomblin D2, Solvay, total equivalent weight 1734) and 151.6 g of isocyanate-functional silane (Silquest A-link 35, Momentive Inc., purity 96.4%) were placed in a glass reaction vessel equipped with a Markette bar and a gas inlet The mixture was heated and stirred at an average temperature of 85 DEG C while maintaining a vacuum pressure of 0.8 bar. At this time, the stirring speed was kept to a minimum so that the isocyanate functional silane in the upper layer gradually permeated into the lower fluorinated diol liquid, and maintained for 2 hours.
다음으로 0.5% 고형분 함량으로 1,3-비스(트리플루오르메틸)벤젠(Aldrich)에 희석된 DBTDL 5g을 투입한 후 같은 온도 및 교반속도로 2시간동안 교반하였다. 다음으로 가스주입구를 통해 메틸아이오드(CF3I, Aldrich)를 3 ㎖/min의 공급속도로 30분간 공급하여 플루오로메틸화하였다. 그리고 감압 해제 후 온도를 50℃로 낮추고 1시간 동안 교반시키고 1,3-비스트리플루오르메틸벤젠 500g 및 메탄올 250g을 동시 투입하고 교반하여 두 용매 간 상분리를 유도하였다. 그리고 상부에 잔존하는 메탄올을 제거한 후 다시 0.8 bar로 감압하여 하기 화학식 6의 불소화 변성 실란 화합물 750g을 수득하였다.Next, 5 g of DBTDL diluted in 1,3-bis (trifluoromethyl) benzene (Aldrich) was added thereto at a 0.5% solids content, and the mixture was stirred at the same temperature and stirring speed for 2 hours. Next, methyl iodide (CF 3 I, Aldrich) was fed through the gas inlet at a feed rate of 3 ml / min for 30 minutes to fluoromethylation. After the decompression was released, the temperature was lowered to 50 캜, stirred for 1 hour, 500 g of 1,3-bistrifluoromethylbenzene and 250 g of methanol were added simultaneously and stirred to induce phase separation between the two solvents. After removing methanol remaining on the upper portion, the pressure was reduced to 0.8 bar to obtain 750 g of a fluorinated modified silane compound represented by the following formula (6).
[화학식 6][Chemical Formula 6]
(상기 화학식 6에서 m + n = 25이고, m/n = 0.9이며, 중량평균분자량은 2400이었다.)(M + n = 25, m / n = 0.9, and weight average molecular weight of 2,400 in Formula 6).
(실시예 2)(Example 2)
마크네틱바 및 가스주입구가 부착된 유리반응용기에 불소화 디올(Fomblin D4000, Solvay사, total equivalent weight 3940) 394g과 이소시아네이트 관능성 실란(Silquest A-link35, Momentive사, purity 96.4%) 42.6g을 넣고 진공감압 0.8bar를 유지하면서 평균온도 85℃로 가열 교반하였다. 이때 상층부의 이소시아네이트 관능성 실란이 하부 불소화 디올액에 점진적으로 스며들도록 교반 속도를 최소화하여 2시간 유지하였다.394 g of fluorinated diol (Fomblin D4000, Solvay, total equivalent weight 3940) and 42.6 g of isocyanate-functional silane (Silquest A-link 35, Momentive, purity 96.4%) were placed in a glass reaction vessel equipped with a magnetic stir bar and gas inlet The mixture was heated and stirred at an average temperature of 85 DEG C while maintaining a vacuum pressure of 0.8 bar. At this time, the stirring speed was kept to a minimum so that the isocyanate functional silane in the upper layer gradually permeated into the lower fluorinated diol liquid, and maintained for 2 hours.
다음으로 0.5% 고형분 함량으로 1,3-비스(트리플루오르메틸)벤젠(Aldrich)에 희석된 DBTDL 5g을 투입한 후 같은 온도 및 교반속도로 2시간동안 교반하였다. 다음으로 가스주입구를 통해 메틸아이오드(CF3I, Aldrich)를 3 ㎖/min의 공급속도로 30분간 공급하여 플루오로메틸화하였다. 그리고 감압 해제 후 온도를 50℃로 낮추고 1시간 동안 교반시키고 퍼플루오로카본(PF 5058, 3M) 400g 및 에틸아세테이트 200g을 동시 투입하고 교반하여 두 용매 간 상분리를 유도하였다. 그리고 상부에 잔존하는 에틸아세테이트를 제거한 후 다시 0.8bar로 감압하여 하기 화학식 6의 불소화 변성 실란 화합물 430g을 수득하였다.Next, 5 g of DBTDL diluted in 1,3-bis (trifluoromethyl) benzene (Aldrich) was added thereto at a 0.5% solids content, and the mixture was stirred at the same temperature and stirring speed for 2 hours. Next, methyl iodide (CF 3 I, Aldrich) was fed through the gas inlet at a feed rate of 3 ml / min for 30 minutes to fluoromethylation. After the decompression was released, the temperature was lowered to 50 캜, stirred for 1 hour, 400 g of perfluorocarbon (PF 5058, 3M) and 200 g of ethyl acetate were simultaneously added and stirred to induce phase separation between the two solvents. Then, the remaining ethyl acetate was removed, and the pressure was further reduced to 0.8 bar to obtain 430 g of a fluorinated modified silane compound represented by the following formula (6).
[화학식 6][Chemical Formula 6]
(상기 화학식 6에서 m + n = 45, m/n = 0.9, 중량평균분자량 4500이었다.) (M + n = 45, m / n = 0.9, and weight average molecular weight of 4500 in Formula 6).
(비교예 1)(Comparative Example 1)
플루오르메틸화 및 불순물 세척을 거치지 않은 것을 제외하고 실시예 1과 동일한 방법으로 제조하여 불소화 변성 실란 화합물 750g을 수득하였다.750 g of a fluorinated modified silane compound was obtained in the same manner as in Example 1, except that fluoromethylation and impurity washing were not carried out.
(비교예 2)(Comparative Example 2)
불순물 세척을 거치지 않은 것을 제외하고 실시예 1과 동일한 방법으로 제조하여 불소화 변성 실란 화합물 750g을 수득하였다.750 g of a fluorinated modified silane compound was obtained in the same manner as in Example 1, except that the impurity was not washed.
(비교예 3)(Comparative Example 3)
플루오르메틸화 및 불순물 세척을 거치지 않은 것을 제외하고 실시예 2와 동일한 방법으로 제조하여 불소화 변성 실란 화합물 420g을 수득하였다.420 g of a fluorinated modified silane compound was obtained in the same manner as in Example 2 except that fluoromethylation and impurity washing were not carried out.
(비교예 4)(Comparative Example 4)
불순물 세척을 거치지 않은 것을 제외하고 실시예 2와 동일한 방법으로 제조하여 불소화 변성 실란 화합물 420g을 수득하였다.
420 g of a fluorinated modified silane compound was obtained in the same manner as in Example 2, except that the impurity was not washed.
[표 1][Table 1]
상기 표 1과 같이 실시예 1, 2는 마찰계수가 낮아 초기 접촉각이 110° 이상임을 확인할 수 있다. 또한 내오염성, 내마모성 및 내찰상성이 우수한 것을 확인할 수 있다. 다만 실시예 1과 2의 접촉각 차이는 실란 화합물의 분자량 차이에 기인하는 것으로 확인할 수 있으며, 좀 더 고분자량의 실시예 2가 실시예 1에 비해 초기 접촉각 및 기타 물성에서 우수한 것을 확인할 수 있다.As shown in Table 1, Examples 1 and 2 have a low coefficient of friction and can confirm that the initial contact angle is 110 ° or more. Also, it can be confirmed that it is excellent in stain resistance, abrasion resistance and scratch resistance. However, it can be confirmed that the difference in the contact angle between Examples 1 and 2 is due to the difference in molecular weight of the silane compound, and that the higher molecular weight of Example 2 is superior to that of Example 1 in terms of initial contact angle and other physical properties.
이에 반해 비교예 1 내지 4는 초기 접촉각이 상대적으로 낮으며, 특히 비교예 3, 4는 고분자량의 실란 화합물을 이용하였음에도 불구하고 내오염성, 내마모성, 내찰상성 등이 저분자량의 실란 화합물을 사용한 실시예 1에 미치지 못하는 것을 확인할 수 있다.On the other hand, Comparative Examples 1 to 4 had a relatively low initial contact angle. Particularly, Comparative Examples 3 and 4 used silane compounds having a low molecular weight such as stain resistance, abrasion resistance, scratch resistance and the like even though high molecular weight silane compounds were used. It can be confirmed that it does not reach to Example 1.
Claims (9)
[화학식 1]
(상기 화학식 1에서 A는
D는 수소, -CF3,
a는 1 내지 11이고;
m은 1 내지 40, n은 1 내지 40, 20 ≤ m+n ≤ 80이며;
a, m 및 n은 모두 정수이다.)
[화학식 2]
(상기 화학식 2에서 m은 1 내지 40, n은 1 내지 40, 20 ≤ m+n ≤ 80이다.)
[화학식 3]
[화학식 4]
[Chemical Formula 1]
(Wherein A in the above formula
D is hydrogen, -CF 3,
a is 1 to 11;
m is 1 to 40, n is 1 to 40, and 20? m + n? 80;
a, m, and n are all integers.)
(2)
(In the formula (2), m is 1 to 40, n is 1 to 40, and 20? M + n? 80.)
(3)
[Chemical Formula 4]
상기 불소화 변성 실란 화합물은 중량평균분자량이 1,850 내지 5,000인 불소화 변성 실란 화합물.The method according to claim 1,
The fluorinated modified silane compound has a weight average molecular weight of 1,850 to 5,000.
b) 상기 불소화 실란 화합물을 플루오로메틸화하여 하기 화학식 1의 불소화 변성 실란 화합물을 제조하는 단계; 및
c) 상기 불소화 변성 실란 화합물을 세척하는 단계;
를 포함하는 불소화 변성 실란 화합물 제조방법.
[화학식 1]
(상기 화학식 1에서 A는
D는 수소, -CF3,
a는 1 내지 11이고;
m은 1 내지 40, n은 1 내지 40, 20 ≤ m+n ≤ 80이며;
a, m 및 n은 모두 정수이다.)
[화학식 2]
(상기 화학식 2에서 m은 1 내지 40, n은 1 내지 40, 20 ≤ m+n ≤ 80이다.)
[화학식 3]
[화학식 4]
b) subjecting the fluorinated silane compound to fluoromethylation to produce a fluorinated modified silane compound of Formula 1; And
c) washing the fluorinated modified silane compound;
By weight based on the weight of the fluorinated modified silane compound.
[Chemical Formula 1]
(Wherein A in the above formula
D is hydrogen, -CF 3,
a is 1 to 11;
m is 1 to 40, n is 1 to 40, and 20? m + n? 80;
a, m, and n are all integers.)
(2)
(In the formula (2), m is 1 to 40, n is 1 to 40, and 20? M + n? 80.)
(3)
[Chemical Formula 4]
상기 촉매는 1,4-디아자비시클로옥탄, 테트라메틸부탄디아민, 주석 옥토에이트, 디부틸틴디라우레이트, 1,3-디아세톡시테트라부틸디스탄노옥산, 디부틸틴디트리메틸실록산, 디부틸틴디트리에톡시실록사이드 및 디부틸틴디트리메톡시실록산에서 선택되는 어느 하나 또는 둘 이상인 불소화 변성 실란 화합물 제조방법.5. The method of claim 4,
The catalyst may be selected from the group consisting of 1,4-diazabicyclooctane, tetramethylbutane diamine, tin octoate, dibutyl tin dilaurate, 1,3-diacetoxytetrabutyldistannooxane, dibutyl tinti trimethyl siloxane, dibutyl tin Wherein the fluorinated modified silane compound is at least one compound selected from the group consisting of diethoxy siloxane, ditriethoxy siloxane, and dibutyl tin di trimethoxy siloxane.
상기 플루오로메틸화는 실란 화합물에 하기 화학식 5의 알킬아이오드 2 내지 3㎖/min의 공급속도로 20 내지 40분간 공급하는 것인 불소화 변성 실란 화합물 제조방법.
[화학식 5]
CF3(CF2)oI
(상기 화학식 5에서 o는 0 내지 11의 정수이다.)5. The method of claim 4,
Wherein the fluoromethylation is carried out for 20 to 40 minutes at a feed rate of 2 to 3 ml / min of alkyl iodide of the following formula (5) to the silane compound.
[Chemical Formula 5]
CF 3 (CF 2 ) o I
(Wherein o is an integer of 0 to 11).
상기 실란 화합물은 불소화 디올 100 중량부에 대하여, 이소시아네이트 관능성 실란 3 내지 30 중량부 및 촉매 0.1 내지 2 중량부를 포함하는 불소화 변성 실란 화합물 제조방법.
5. The method of claim 4,
Wherein the silane compound comprises 3 to 30 parts by weight of an isocyanate functional silane and 0.1 to 2 parts by weight of a catalyst relative to 100 parts by weight of a fluorinated diol.
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