KR20190141443A - Polyurethane resin for rubber surface treating paint - Google Patents
Polyurethane resin for rubber surface treating paint Download PDFInfo
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- KR20190141443A KR20190141443A KR1020180068222A KR20180068222A KR20190141443A KR 20190141443 A KR20190141443 A KR 20190141443A KR 1020180068222 A KR1020180068222 A KR 1020180068222A KR 20180068222 A KR20180068222 A KR 20180068222A KR 20190141443 A KR20190141443 A KR 20190141443A
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
Description
본 발명은 자동차 웨더스트립(weatherstrip) 등의 고무 표면 처리 도료용 폴리우레탄 수지를 제조함에 있어, 종래에 동시 구현되지 못한 두 물성(내마모성과 슬립성 등)을 동시에 구현가능하도록 하는, 고무 표면 처리 도료용 폴리우레탄 수지에 관한 것이다.The present invention, in the production of polyurethane resin for rubber surface treatment paint, such as automotive weatherstrip, rubber surface treatment paint, which enables to simultaneously realize two properties (such as wear resistance and slip resistance) that have not been simultaneously implemented in the prior art It relates to a polyurethane resin for.
일반적으로 자동차 웨더스트립(weatherstrip)은 자동차의 고정된 창이나 도어(door) 등의 개폐 부위에 위치하여, 비, 바람, 먼지 등의 실내 유입을 방지하고, 외부로부터의 소음을 차단하며, 도어 개폐 시 자동차의 진동을 차단하는 역할을 수행한다.In general, the vehicle weatherstrip is located at the opening or closing part of a fixed window or door of the car, and prevents rain, wind, dust, etc. from entering the interior, blocks noise from the outside, and opens and closes the door. It serves to block the vibration of the city car.
이러한 자동차용 웨더스트립은 발포 처리된 EPDM(ethylene propylene diene monomer) 상부에 코팅층이 도포되며, 코팅층은 웨더스트립의 슬립성 및 내마모성 등의 성능을 결정하는 중요한 요소로 작용한다.The automotive weather strip is coated with a coating layer on the foamed EPDM (ethylene propylene diene monomer), the coating layer serves as an important factor in determining the performance of the weather strip slip resistance and wear resistance.
종래의 대부분의 자동차 웨더스트립용 코팅액은 PU(polyurethane) 수지를 이용하여 내마모성을 부여하고, 특허문헌 1 등에서와 같이 실리콘 오일(silicone oil) 등을 이용하여 슬립성을 구현하고자 하였으나, 두 성분 간에 불가항력적으로 발생하는 전기적 상호작용에 의해 상용성이 미흡하여 두 가지 물성을 동시에 만족시키기 어려운 문제점이 있다.Most of the conventional coating coating for automotive weather strip to give abrasion resistance by using a PU (polyurethane) resin, and as shown in
보다 구체적으로 종래 자동차 웨더스트립용 도료의 대부분은 폴리우레탄 수지와 실리콘 오일을 단순히 혼합함으로서 내마모성 및 슬립성을 발현시키고자 하고 있으나, 우레탄과 실리콘 소재는 이종의 분자 간에 발생하는 전기적 상호 작용에 의해 분자가 응집되거나 뭉치는 현상을 방지하기 어렵고 이에 따라 실리콘 수지의 슬립성 및 우레탄 수지의 내마모성이 동시에 상쇄되어 의도된 기능이 충분이 구현되지 못하며, 명도, 조도 등의 조절을 위하여 첨가되는 소광제 등으로 인해 장기 보관 시 도료의 저장안정성이 저하되는 문제점이 있다.More specifically, most of the conventional automotive weather strip paints are intended to express wear resistance and slip resistance by simply mixing a polyurethane resin and a silicone oil. However, urethane and silicone materials may be formed by an electrical interaction between heterogeneous molecules. Is difficult to prevent agglomeration or agglomeration, and thus, the slip resistance of the silicone resin and the abrasion resistance of the urethane resin are simultaneously canceled, so that the intended function is not sufficiently realized, and a matting agent is added to control brightness and roughness. Due to the long-term storage there is a problem that the storage stability of the paint is lowered.
따라서, 자동차 웨더스트립용 코팅소재의 내구성 확보를 통한 고객 신뢰도 증가 및 자동차에 대한 정숙성 요구를 만족시키기 위하여 내마모성 및 슬립성을 동시에 발현하는 자동차 웨더스트립용 코팅액의 개발이 요구되고 있으며, 또한 부품소재 산업의 꾸준한 성장과 표면처리 분야의 수요 확대, 기술발전에 따른 내수 활성화, 정보통신기기산업 발전에 따른 기능성 씰링(sealing) 요구 및 수요 증대 등의 요소를 만족시키기 위하여 새로운 코팅소재의 개발이 시급한 실정이다.Accordingly, in order to increase customer reliability and to satisfy the demand for quietness of automobiles by securing durability of coating material for automotive weather strip, it is required to develop coating solution for automotive weather strip that simultaneously expresses abrasion resistance and slip resistance. Development of new coating materials is urgently needed to satisfy the factors such as the steady growth of the market, the expansion of demand in the surface treatment field, domestic demand for technology development, and the increasing demand for functional sealing due to the development of the information and communication equipment industry. .
본 발명은 상술한 문제점을 해결하기 위한 것으로, 고무 표면 처리 도료용 폴리우레탄 수지를 제조함에 있어, 실리콘 변성 폴리올(silicone modified polyol) 또는 불소 변성 폴리올(fluorine modified polyol)을 이용하여 폴리우레탄을 합성함으로써, 높은 마찰계수를 가져 내마모성이 우수한 폴리우레탄 수지와, 표면장력 조절을 통한 슬립성 부여가 가능한 관능기를 가진 실리콘 또는 불소를 화학적으로 결합할 수 있도록 하며, 이로 인해 종래에 동시 구현되지 못한 두 물성(내마모성과 슬립성 등)을 동시에 구현가능할 뿐만 아니라 저장안정성 등을 향상시킬 수 있도록 함을 과제로 한다.The present invention is to solve the above problems, in preparing a polyurethane resin for rubber surface treatment paint, by synthesizing a polyurethane using a silicone modified polyol (silicone modified polyol) or fluorine modified polyol (fluorine modified polyol) It is possible to chemically combine a polyurethane resin with high abrasion resistance with a high friction coefficient and a silicone or fluorine having a functional group capable of providing slip property through surface tension control, and thus two physical properties ( The problem is that not only the wear resistance and the slip resistance, etc. can be realized at the same time, but also the storage stability can be improved.
본 발명은 고무 표면 처리 도료용 폴리우레탄 수지에 있어서, 폴리올, 실리콘 변성 폴리올 또는 불소 변성 폴리올 및 이소시아네이트를 교반 및 반응시켜 이루어지는 것을 특징으로 하는, 고무 표면 처리 도료용 폴리우레탄 수지를 과제의 해결 수단으로 한다.The present invention is a polyurethane resin for rubber surface treatment paint, wherein the polyurethane resin for rubber surface treatment paint is formed by stirring and reacting a polyol, a silicone-modified polyol or a fluorine-modified polyol, and an isocyanate. do.
보다 구체적으로 본 발명은 폴리올 100 중량부에 대하여, 실리콘 변성 폴리올 또는 불소 변성 폴리올 0.1 ~ 10 중량부 및 이소시아네이트 1 ~ 20 중량부를 교반 및 반응시키되, 상기 이소시아네이트는 첨가량의 90 ~ 95 중량%를 먼저 교반 및 1차 반응시킨 후, 나머지 5 ~ 10 중량%는 2 ~ 6회 분할하여 순차적으로 혼합 및 교반하여, 폴리올과 이소시아네이트의 NCO/OH 비가 0.9 ~ 1.1이 되도록 반응시켜 제조하는 것이 바람직하다.More specifically, the present invention stirs and reacts 0.1 to 10 parts by weight of silicone-modified polyol or fluorine-modified polyol and 1 to 20 parts by weight of isocyanate with respect to 100 parts by weight of polyol, wherein the isocyanate is first stirred at 90 to 95% by weight of the added amount. And after the first reaction, the remaining 5 to 10% by weight is divided into 2 to 6 times by mixing and stirring sequentially, it is preferable to prepare by reacting so that the NCO / OH ratio of the polyol and isocyanate is 0.9 to 1.1.
본 발명은 고무 표면 처리 도료용 폴리우레탄 수지를 제조함에 있어, 실리콘 변성 폴리올 또는 불소 변성 폴리올을 이용하여 폴리우레탄을 합성함으로써, 높은 마찰계수를 가져 내마모성이 우수한 폴리우레탄 수지와, 표면장력 조절을 통한 슬립성 부여가 가능한 관능기를 가진 실리콘 또는 불소를 화학적으로 결합할 수 있도록 하며, 이로 인해 종래에 동시 구현되지 못한 두 물성(내마모성과 슬립성 등)을 동시에 구현가능할 뿐만 아니라 저장안정성 등을 향상시킬 수 있는 효과가 있다.In the present invention, in preparing a polyurethane resin for rubber surface treatment paint, by using a silicone modified polyol or a fluorine-modified polyol to synthesize a polyurethane, has a high friction coefficient and excellent wear resistance, and through the surface tension control It is possible to chemically bond silicon or fluorine having a functional group capable of providing slip property, and thus, it is possible not only to simultaneously implement two properties (abrasion resistance and slip property, etc.) that have not been simultaneously realized, but also to improve storage stability. It has an effect.
도 1은 본 발명에 따른 실리콘 변성 폴리올을 적용한 폴리우레탄의 합성 메커니즘을 나타낸 도면
도 2는 본 발명에 따른 불소 변성 폴리올을 적용한 폴리우레탄의 합성 메커니즘을 나타낸 도면1 is a view showing the synthesis mechanism of the polyurethane to which the silicone-modified polyol according to the present invention is applied
2 is a view showing the synthesis mechanism of the polyurethane to which the fluorine-modified polyol according to the present invention is applied
상기의 효과를 달성하기 위한 본 발명은 고무 표면 처리 도료용 폴리우레탄 수지에 관한 것으로, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.The present invention for achieving the above effect relates to a polyurethane resin for rubber surface treatment paint, and only the parts necessary for understanding the technical configuration of the present invention will be described, the description of other parts will not disturb the gist of the present invention. Note that it will be omitted.
이하, 본 발명에 따른 고무 표면 처리 도료용 폴리우레탄 수지를 상세히 설명하면 다음과 같다.Hereinafter, the polyurethane resin for rubber surface treatment paint according to the present invention will be described in detail.
본 발명은 고무 표면 처리 도료용 폴리우레탄 수지에 있어서, 폴리올, 실리콘 변성 폴리올 또는 불소 변성 폴리올 및 이소시아네이트를 교반 및 반응시켜 이루어지는 것을 특징으로 한다.The present invention is characterized in that the polyurethane resin for rubber surface treatment paint is obtained by stirring and reacting a polyol, a silicone-modified polyol or a fluorine-modified polyol and an isocyanate.
보다 구체적으로 본 발명은 폴리올 100 중량부에 대하여, 실리콘 변성 폴리올 또는 불소 변성 폴리올 0.1 ~ 10 중량부 및 이소시아네이트 1 ~ 20 중량부를 교반 및 반응시키되, 상기 이소시아네이트는 첨가량의 90 ~ 95 중량%를 먼저 교반 및 1차 반응시킨 후, 나머지 5 ~ 10 중량%는 2 ~ 6회 분할하여 순차적으로 혼합 및 교반하여, 폴리올과 이소시아네이트의 NCO/OH 비가 0.9 ~ 1.1이 되도록 반응시켜 제조한다.More specifically, the present invention stirs and reacts 0.1 to 10 parts by weight of silicone-modified polyol or fluorine-modified polyol and 1 to 20 parts by weight of isocyanate with respect to 100 parts by weight of polyol, wherein the isocyanate is first stirred at 90 to 95% by weight of the added amount. And after the first reaction, the remaining 5 to 10% by weight is divided into two to six times, mixed and stirred sequentially, the reaction is prepared by reacting the NCO / OH ratio of the polyol and isocyanate is 0.9 to 1.1.
예를 들면, 이소시아네이트를 첨가량의 90 중량%를 먼저 교반하여 폴리올과 이소시아네이트의 NCO/OH 비가 0.9가 되도록 1차 반응시킨 후, 이후 첨가량의 5 중량%(NCO/OH 비 0.95), 첨가량의 1 중량%(NCO/OH 비 0.96), 첨가량의 1 중량%(NCO/OH 비 0.97), 첨가량의 1 중량%(NCO/OH 비 0.98), 첨가량의 1 중량%(NCO/OH 비 0.99), 첨가량의 1 중량%(NCO/OH 비 1.0)씩 순차적으로 6회 분할하여 교반 및 반응시켜 제조한다.For example, 90% by weight of the isocyanate is first stirred to first react the polyol and the isocyanate so that the NCO / OH ratio is 0.9, and then 5% by weight (NCO / OH ratio 0.95) and 1% of the amount % (NCO / OH ratio 0.96), 1% by weight (NCO / OH ratio 0.97), 1% by weight (NCO / OH ratio 0.98), 1% by weight (NCO / OH ratio 0.99), Prepared by stirring and reacting by dividing six times in sequence by 1% by weight (NCO / OH ratio 1.0).
한편, 상기 각 물질의 함량 및 NCO/OH비 등은 내마모성과 슬립성 및 저장안정성 등의 향상효율을 고려하여 상기 범위가 바람직하지만 반드시 상기 범위에 한정되는 것은 아니고 본 발명에 따른 수지의 사용환경, 적용 고무의 종류 등에 따라 가변적일 수 있다.On the other hand, the content of each material and the NCO / OH ratio is preferably in the above range in consideration of the improvement efficiency, such as wear resistance and slip resistance and storage stability, but is not necessarily limited to the above range, the use environment of the resin according to the present invention, It may vary depending on the type of rubber applied.
아울러, 여기에 폴리우레탄 합성 분야에서 이미 널리 공지된 촉매(DBTDL(dibutyltin dilaurate) 등), 용매(MEK(methylethylketone) 등), 쇄연장제(EG(ethyleneglycol) 등) 등을 필요에 따라 공지된 범위내에서 적용이 가능하다.In addition, a well-known catalyst (DBTDL (dibutyltin dilaurate), etc.), a solvent (MEK (methylethylketone, etc.), a chain extender (EG (ethyleneglycol, etc.), etc.) already well known in the field of polyurethane synthesis, etc. It can be applied within.
한편, 상기 폴리올은 폴리에스테르 폴리올(polyester polyol), 폴리프로필렌 글리콜(polypropylene glycol), 폴리에틸렌 글리콜(polyethylene glycol)등 이미 공지된 다양한 폴리올의 적용이 가능하다.On the other hand, the polyol can be applied to a variety of known polyols, such as polyester polyol (polyester polyol), polypropylene glycol (polypropylene glycol), polyethylene glycol (polyethylene glycol).
그리고, 상기 실리콘 변성 폴리올은 아래 [화학식 1]과 같은 구조를 가지는 것으로, 이의 적용 시 도 1에 도시된 바와 같은 반응 메카니즘에 의해 종래에 동시 구현되지 못한 두 물성(내마모성과 슬립성 등)을 동시에 구현가능하게 된다.In addition, the silicone-modified polyol has a structure as shown in [Formula 1] below, at the same time the two physical properties (wear resistance and slip properties, etc.) that are not simultaneously implemented by the reaction mechanism as shown in Figure 1 when applied thereto It becomes possible to implement it.
[화학식 1][Formula 1]
여기서, R은 C1 ~ C12의 알킬기이고, n은 1이상의 정수이다. Wherein, R is an alkyl group of C 1 ~ C 12, n is an integer of 1 or more.
보다 구체적으로 도 1을 참조하여 설명하면, 폴리유기실록산은 주사슬이 유·무기화합물로 된 R2-Si-O 결합으로 이루어져 있어 그 특성이 유연하고 내수성 및 열안정성 및 산화안정성이 매우 우수한 것으로 알려져 있다. 즉, 실리콘 고분자의 주사슬은 Si-O로 이루어진 실록산 구조로 구성되어 있으며, 다른 탄화수소 고분자와 달리 강한 결합 에너지를 가져, 결합각이 크고 길기 때문에 유연성이 매우 높다. 또한 여러 종류의 유기 관능기를 치환하는 것이 용이하기 때문에 치환된 유기 관능기에 따라 다양한 특성을 부여할 수 있다. 따라서 양말단에 하이드록실 그룹(hydroxyl group)을 갖는 폴리유기실록산(polyorganosiloxane)을 폴리올과 함께 소프트 세그먼트로 도입해 줌으로써 폴리유기실록산 폴리우레탄(polyorganosiloxane polyurethane) 수지를 제조하고 이를 코팅제로 활용할 수 있으며, 이를 통해 우레탄의 구조적 강인성에서 기인한 내마모성의 발현 및 실리콘 원소를 통해 슬립성, 수분에 대한 저항성의 증가, 열적 특성을 개선할 수 있다.More specifically, with reference to FIG. 1, polyorganosiloxane is composed of R2-Si-O bonds in which the main chain is an organic / inorganic compound is known to be flexible, excellent in water resistance, thermal stability, and oxidation stability. have. That is, the main chain of the silicon polymer is composed of a siloxane structure composed of Si-O, and unlike other hydrocarbon polymers, has a strong binding energy, and the bonding angle is large and long, so the flexibility is very high. In addition, since it is easy to substitute several kinds of organic functional groups, various characteristics can be provided according to the substituted organic functional group. Therefore, by introducing a polyorganosiloxane having a hydroxyl group in the sock end together with a polyol as a soft segment, a polyorganosiloxane polyurethane resin can be prepared and used as a coating agent. Through the expression of abrasion resistance due to the structural toughness of the urethane and the silicon element, it is possible to improve the slip property, resistance to moisture and thermal properties.
아울러, 불소 변성 폴리올을 적용한 경우에도 상술한 실리콘 변성 폴리올을 적용한 폴리우레탄 수지와 동일한 효과를 구현할 수 있다. 보다 구체적으로 아래 [화학식 2]와 같은 불소 변성 폴리올을 적용할 경우 도 2에 도시된 바와 같은 반응 메카니즘에 의해 종래에 동시 구현되지 못한 두 물성(내마모성과 슬립성 등)을 동시에 구현가능하게 된다. In addition, even when the fluorine-modified polyol is applied, the same effects as the polyurethane resin to which the silicone-modified polyol is applied may be realized. More specifically, when the fluorine-modified polyol as shown in [Formula 2] is applied, two physical properties (abrasion resistance and slippage, etc.) not simultaneously realized by the reaction mechanism as shown in FIG. 2 can be simultaneously implemented.
[화학식 2][Formula 2]
여기서, F는 불소기이다.Here, F is a fluorine group.
보다 구체적으로 불소원자는 강한 전기음성도를 갖고 있고, 견고한 C-F 결합을 형성함으로써, 이를 함유한 퍼플러 알킬 그룹(perfluoro alkyl group)은 분자간 응집력이 매우 커서 C-C 결합을 갖는 화합물 보다 분자수준의 팩킹(packing)이 용이하며, 폴리우레탄 탄성체에 이런 불소기를 도입하면, 표면 에너지의 감소를 가져와, 표면특성이 크게 변하게 된다. 즉 고분자의 주사슬이나 곁사슬에 불소를 도입하게 되면 종래에 동시 구현되지 못한 두 물성(내마모성과 슬립성 등)을 동시에 구현가능하게 된다.More specifically, the fluorine atom has a strong electronegativity and forms a strong CF bond, so that the perfluoro alkyl group containing it has a very high intermolecular cohesion and packs at a molecular level than a compound having a CC bond. ), The introduction of such a fluorine group into the polyurethane elastomer, the surface energy is reduced, the surface properties are greatly changed. In other words, when fluorine is introduced into the main chain or the side chain of the polymer, two physical properties (abrasion resistance and slip resistance, etc.) that have not been simultaneously implemented at the same time can be simultaneously implemented.
상기 이소시아네이트는, TDI(Toluene Diisocyanate), HDI(Hexamethylene diisocyanate), MDI(Methylene Diphenyl Diisocyanate), IPDI(Isophorone Diisocyanate), H12MDI(dicyclohexylmethane diisocyanate), TMXDI(Tetramethylxylene Diisocyanate), NDI(naphthalene-1,5-diisocyanate), XDI(m-xylene diisocyanate), CHDI(1,4-cyclohexyl diisocyanate) 또는 DDI(Diphenylmethane diisocyanate)의 둘 이상의 이성질체, 다이머, 트라이머, 및 혼합물 또는 조합물를 적용할 수 있으나, 여기에 한정되는 것은 아니고 이미 공지된 다양한 종류의 이소시아네이트의 적용이 가능하다.The isocyanate is toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), methylene diphenyl diisocyanate (MDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), tetramethylxylene Diisocyanate (NDI), NDI-di-diane, NDI ), Two or more isomers, dimers, trimers, and mixtures or combinations of m-xylene diisocyanate (XDI), 1,4-cyclohexyl diisocyanate (CHDI) or diphenylmethane diisocyanate (DDI) may be applied, but are not limited thereto. And various known isocyanates are possible.
이하, 본 발명의 실시 예를 들면서 상세히 설명하는 바 본 발명이 다음의 실시예에 의해서만 반드시 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not necessarily limited to the following Examples.
1. 고무 표면 처리 도료용 폴리우레탄 수지의 제조1. Preparation of polyurethane resin for rubber surface treatment paint
(실시예 1)(Example 1)
폴리에스테르 폴리올 100 중량부에 대하여, 실리콘 변성 폴리올 0.1 중량부 및 이소시아네이트(TDI) 1 중량부를 교반 및 반응시키되, 이소시아네이트의 경우 첨가량의 90 중량%를 85℃에서 150 rpm으로 2시간 교반 및 1차 반응시킨 후, 나머지 10 중량%를 6회 분할하여 순차적으로 혼합 및 교반하여, 폴리올과 이소시아네이트의 NCO/OH 비가 1.0이 되도록 반응시켜 제조하였다.With respect to 100 parts by weight of polyester polyol, 0.1 parts by weight of silicone-modified polyol and 1 part by weight of isocyanate (TDI) are stirred and reacted, in the case of isocyanates, 90% by weight of the addition amount is stirred for 2 hours at 85 rpm and 150 rpm for 2 hours. After the preparation, the remaining 10% by weight was divided six times, mixed and stirred sequentially, and prepared by reacting the polyol and the isocyanate so that the NCO / OH ratio was 1.0.
(실시예 2)(Example 2)
폴리에스테르 폴리올 100 중량부에 대하여, 불소 변성 폴리올 10 중량부 및 이소시아네이트(TDI) 20 중량부를 교반 및 반응시키되, 이소시아네이트의 경우 첨가량의 95 중량%를 85℃에서 150 rpm으로 2시간 교반 및 1차 반응시킨 후, 나머지 5 중량%를 2회 분할하여 순차적으로 혼합 및 교반하여, 폴리올과 이소시아네이트의 NCO/OH 비가 1.0이 되도록 반응시켜 제조하였다.10 parts by weight of fluorine-modified polyol and 20 parts by weight of isocyanate (TDI) are stirred and reacted with respect to 100 parts by weight of polyester polyol, in the case of isocyanates, 95% by weight of the addition amount is stirred for 2 hours at 85 rpm and 150 rpm for 2 hours. After the mixing, the remaining 5% by weight was divided twice, mixed and stirred sequentially, and prepared by reacting the polyol and the isocyanate so that the NCO / OH ratio was 1.0.
(비교예 1)(Comparative Example 1)
실시예 1과 동일하게 제조하되, 실리콘 변성 폴리올을 사용하지 않았다. 그리고 이소시아네이트를 한번에 전량 첨가하였다.Prepared in the same manner as in Example 1, but did not use a silicone-modified polyol. And all the isocyanate was added at once.
(비교예 2)(Comparative Example 2)
실시예 2와 동일하게 제조하되, 불소 변성 폴리올을 사용하지 않았다. 그리고 이소시아네이트를 한번에 전량 첨가하였다.Prepared in the same manner as in Example 2, but did not use a fluorine-modified polyol. And all the isocyanate was added at once.
2. 고무 표면 처리 도료용 폴리우레탄 수지의 평가2. Evaluation of Polyurethane Resin for Rubber Surface Treatment Paint
실시예 1, 2 및 비교예 1, 2에 따라 제조된 우레탄 수지의 내마모성과 슬립성(접촉각)를 평가하였으며, 그 시험규격 및 결과를 아래 [표 1]에 나타내었다.The wear resistance and slip resistance (contact angle) of the urethane resins prepared according to Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated, and the test specifications and the results are shown in [Table 1] below.
(회/1.1kg)Wear resistance
(Sashimi /1.1kg)
상기 [표 1]에서와 같이 본 발명에 따른 실시예 1, 2의 경우 실리콘 변성 폴리올 또는 불소 변성 폴리올을 이용하고, 또한 소시아네이트를 순차적으로 첨가하여 폴리우레탄을 합성함으로써, 종래에 동시 구현되지 못한 두 물성(내마모성과 슬립성 등)을 동시에 구현가능함을 알 수 있다.In Examples 1 and 2 according to the present invention as shown in Table 1, by using a silicone-modified polyol or a fluorine-modified polyol, and also by adding a socyanate sequentially to synthesize a polyurethane, it was not conventionally implemented simultaneously It can be seen that both physical properties (such as wear resistance and slip resistance) can be simultaneously implemented.
상술한 바와 같은, 본 발명의 바람직한 실시예에 따른 고무 표면 처리 도료용 폴리우레탄 수지를 상기한 설명 및 도면에 따라 설명하였지만 이는 예를 들어 설명한 것에 불과하며 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 변화 및 변경이 가능하다는 것을 이 분야의 통상적인 기술자들은 잘 이해할 수 있을 것이다.As described above, the polyurethane resin for rubber surface treatment paint according to the preferred embodiment of the present invention has been described according to the above description and the drawings, but this is only an example and within the scope not departing from the technical spirit of the present invention. It will be appreciated by those skilled in the art that various changes and modifications are possible.
Claims (4)
폴리올, 실리콘 변성 폴리올 또는 불소 변성 폴리올 및 이소시아네이트를 교반 및 반응시켜 이루어지는 것을 특징으로 하는, 고무 표면 처리 도료용 폴리우레탄 수지.
In the polyurethane resin for rubber surface treatment paint,
Polyurethane, silicone-modified polyol or fluorine-modified polyol and isocyanate are made by stirring and reacting, The polyurethane resin for rubber surface treatment coatings characterized by the above-mentioned.
상기 고무 표면 처리 도료용 폴리우레탄 수지는,
폴리올 100 중량부에 대하여, 실리콘 변성 폴리올 또는 불소 변성 폴리올 0.1 ~ 10 중량부 및 이소시아네이트 1 ~ 20 중량부를 교반 및 반응시키되,
상기 이소시아네이트는 첨가량의 90 ~ 95 중량%를 먼저 교반 및 1차 반응시킨 후,
나머지 5 ~ 10 중량%는 2 ~ 6회 분할하여 순차적으로 혼합 및 교반하여, 폴리올과 이소시아네이트의 NCO/OH 비가 0.9 ~ 1.1이 되도록 반응시켜 제조하는 것을 특징으로 하는, 고무 표면 처리 도료용 폴리우레탄 수지.
The method of claim 1,
The polyurethane resin for rubber surface treatment paints,
To 100 parts by weight of polyol, 0.1 to 10 parts by weight of silicone-modified polyol or fluorine-modified polyol and 1 to 20 parts by weight of isocyanate are stirred and reacted,
The isocyanate is first stirred and first reacted with 90 to 95% by weight of the added amount,
The remaining 5 to 10% by weight is divided into two to six times, mixed and stirred sequentially, and produced by reacting the polyol and isocyanate so that the NCO / OH ratio is 0.9 to 1.1. .
상기 실리콘 변성 폴리올은 아래 [화학식 1]과 같은 구조를 가지는 것을 특징으로 하는, 고무 표면 처리 도료용 폴리우레탄 수지.
[화학식 1]
여기서, R은 C1 ~ C12의 알킬기이고, n은 1이상의 정수이다.
The method of claim 1,
The silicone-modified polyol has a structure as shown in the following [Formula 1], a polyurethane resin for rubber surface treatment paint.
[Formula 1]
Wherein, R is an alkyl group of C 1 ~ C 12, n is an integer of 1 or more.
상기 불소 변성 폴리올은 아래 [화학식 2]와 같은 구조를 가지는 것을 특징으로 하는, 고무 표면 처리 도료용 폴리우레탄 수지.
[화학식 2]
여기서, F는 불소기이다.The method of claim 1,
The fluorine-modified polyol has a structure as shown in the following [Formula 2], polyurethane resin for rubber surface treatment paint.
[Formula 2]
Here, F is a fluorine group.
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| KR100731879B1 (en) | 2004-07-01 | 2007-06-25 | 주식회사 화승티엔씨 | A composition of paints surface treatment for rubber |
| KR100915321B1 (en) * | 2007-08-03 | 2009-09-03 | 진도화성주식회사 | silicone modified polyurethane waterproofing paint and manufacturing method thereof |
| CN102492111A (en) * | 2011-12-01 | 2012-06-13 | 合肥工业大学 | Method for preparing high-protective polyurethane paint used on silicon rubber surface |
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| KR102112312B1 (en) | 2020-06-04 |
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