KR20010044682A - Coating agent for textile - Google Patents

Coating agent for textile Download PDF

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Publication number
KR20010044682A
KR20010044682A KR1020010013498A KR20010013498A KR20010044682A KR 20010044682 A KR20010044682 A KR 20010044682A KR 1020010013498 A KR1020010013498 A KR 1020010013498A KR 20010013498 A KR20010013498 A KR 20010013498A KR 20010044682 A KR20010044682 A KR 20010044682A
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South Korea
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weight
coating composition
fiber
fiber coating
water
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KR1020010013498A
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Korean (ko)
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박청기
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박청기
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Priority to KR1020010013498A priority Critical patent/KR20010044682A/en
Publication of KR20010044682A publication Critical patent/KR20010044682A/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial

Abstract

PURPOSE: A fiber coating agent having water proofing, water repellent, oil repellent and soil repellent function is provided, which is easy for use without need of expensive equipments and special technique and has a far infrared radiation radioactive, ultraviolet light-shielding and aromatic function. CONSTITUTION: The coating composition comprises 20 to 55% by weight of polytetrafluoroethylene, 5 to 15% by weight of paraffin, 8 to 20% by weight of pyroligenous acid, 3 to 10% by weight of deacetylated chitosan, 12 to 25% by weight of hydrogen, 5 to 10% by weight of melamine resin and 2 to 10% by weight of silicon resin, wherein water is used in an amount of 30 to 100 times that of the fiber coating composition.

Description

섬유 코팅제{Coating agent for textile}Textile coating agent {Coating agent for textile}

본 발명은 섬유 코팅용 조성물에 관한 것으로 더욱 상세하게는, 불소수지계열의 화합물과 기타 물질을 일정비율로 혼합하여 제조한 발수, 발유 및 방오기능을 가진 다기능성 섬유 코팅용 조성물에 관한 것이다.The present invention relates to a fiber coating composition, and more particularly, to a multi-functional fiber coating composition having a water-repellent, oil-repellent and antifouling function prepared by mixing a compound of the fluorine resin series and other materials in a certain ratio.

종래는 상기와 같은 목적을 달성하기 위해서는 고가의 설비를 갖춘 염색소나 가공소에서 각기 다른 성질을 가진 별도의 물질들을 작업자가 정밀한 계량없이 경험에 의해서 원단염색시 또는 가공시에 물과 함께 투입하거나 대충의 량을 물에 넣어 사용하였다.Conventionally, in order to achieve the above object, separate materials having different properties in dyeing facilities or processing facilities with expensive facilities are added or roughly mixed with water during fabric dyeing or processing by the user's experience without precise weighing. Was used in water.

그러나 이러한 방법으로는 각 물질 사이에 성질 차이로 인해 융합이나 결합이 제대로 되지 않아 상기 각 기능을 동시에 얻기가 매우 어렵거나 얻었다 하더라도 그 기능이 미약하거나 지속성이 현저히 떨어졌다.However, in this method, even if it is very difficult to obtain each function at the same time due to the difference in properties between each material is not properly fused or combined, the function is weak or the durability is significantly reduced.

그리고 이렇게 해서 만든 섬유코팅용 조성물은 그 처리방법 또한 160∼220℃의 고온의 원단가공기에서 1∼4분 정도의 열처리를 하여야 그 기능을 얻을 수 있었다. 더구나 이러한 처리방법으로는 의류 등 섬유완제품에는 그 처리가 불가능하였고 완제품에 처리할 수 있는 방법이 현재까지는 없다.And the composition for the fiber coating thus made must be heat treated for about 1 to 4 minutes in a high-temperature fabric processing machine of 160-220 ° C. to obtain its function. Moreover, such treatment was not possible for finished textile products such as clothing, and there is no method for treating finished products.

따라서 수차례 세탁후에는 그 기능이 약해지거나 소멸되며 이렇게 되어도 일반인들은 기능을 되살릴 수 있는 방법이 전혀 없었다.Therefore, after washing several times, its function is weakened or extinguished, and there is no way for the general public to restore the function.

본 발명의 목적은 일반인이 고가의 설비나 전문기술이 없이도 용이하게 코팅처리할 수 있는, 섬유제품에 방수, 발수, 발유 및 방오기능을 가진 섬유코팅용 조성물을 제공하는 것이다.An object of the present invention is to provide a fiber coating composition having a waterproof, water-repellent, oil-repellent and antifouling function in the textile product, which can be easily coated by the public without expensive equipment or expertise.

본 발명의 또 다른 목적은 상기 기능외에 원적외선을 방사하는 기능, 자외선을 차단하는 기능, 향기를 발산하는 방향기능 등 다양한 보조기능을 가진 섬유코팅용 조성물을 제공하는 것이다.Still another object of the present invention is to provide a composition for coating a fiber having various auxiliary functions such as a function of emitting far infrared rays, a function of blocking ultraviolet rays, and an aromatic function of emitting fragrance in addition to the above functions.

본 발명은 폴리테트라플루오로에틸렌 20∼55 중량%, 파라핀 5∼15 중량%, 목초액 8∼20 중량%, 80∼99% 탈아세틸화된 키토산 3∼10 중량%, 수소 13∼25 중량%, 멜라민수지 5∼10 중량%, 및 실리콘수지 2∼10 중량%가 혼합되어 이루어지는 섬유코팅용 조성물을 제공한다. 목초액은 참나무나 소나무의 것을 사용하며, 시판되고 있는 것을 사용할 수 있고, 제조는 참나무나 소나무 숯제조시 나오는 연기를 냉각하여 얻는다. 연기는 처음에 나오는 것은 유해성분이 많이 들어 있으므로 중간에 나오는 온도가 80∼150℃인 황백연기를 사용하는 것이 바람직하고, 냉각하여 얻은 액체는 6개월에서 1년가량 정치하여 상하층은 버리고 중간층의 엷은 노란색을 띠는 투명한 부분을 사용한다.The present invention is 20 to 55% by weight of polytetrafluoroethylene, 5 to 15% by weight of paraffin, 8 to 20% by weight of wood vinegar, 3 to 10% by weight of deacetylated chitosan, 13 to 25% by weight of hydrogen, Provided is a fiber coating composition comprising 5 to 10% by weight of melamine resin and 2 to 10% by weight of silicone resin. Wood grass liquor is made of oak or pine, and commercially available ones can be used. The preparation is obtained by cooling the smoke from the manufacture of oak or pine charcoal. Since smoke comes out first, it contains a lot of harmful components, so it is preferable to use sulfur white smoke with the temperature in the middle of 80 ~ 150 ℃, and the liquid obtained by cooling is left for 6 months to 1 year. Use the yellow transparent part.

상기 조성물은 물로 희석하여 사용하는데, 희석은 물과 상기 섬유코팅용 조성물을 혼합하기 위한 혼합통내에서 행해진다. 혼합통은 유리섬유 또는 석면재질의 격막으로 분리되어 격막의 일측에는 구리봉으로 된 양극이 설치되고, 격막의 타측에는 탄소봉으로 된 음극이 설치되어 있다. 희석은 혼합통에 전류를 통과시키면서 혼합하여 행한다. 양극사이에 걸어주는 전압은 희석하고자 하는 조성물의 양에 따라 달라지며 3∼15 V가 적당하다. 이와같이 하면 조성물의 각 성분사이의 결합이 원활해지며 제품의 사용시 저온(40℃정도)에서도 조성물의 각 성분이 반응하여 기능을 발휘함으로써 사용하기가 편해진다. 이 때 물은 상기 섬유코팅용 조성물에 중량비로 30∼100배의 양으로 사용한다. 또 혼합통내의 원료 투입구와 배출구에는 필요에 따라 활성탄을 두어 상기 조성물의 불순물과 특유의 냄새를 제거한다.The composition is used after dilution with water, and dilution is performed in a mixing vessel for mixing water and the fiber coating composition. The mixing cylinder is separated into a glass fiber or asbestos diaphragm, and one side of the diaphragm is provided with a copper rod anode, and the other side of the diaphragm is provided with a carbon rod anode. Dilution is carried out by mixing while passing a current through the mixing vessel. The voltage applied between the anodes depends on the amount of the composition to be diluted, with 3-15 V being suitable. In this way, the bonding between the components of the composition is facilitated, and the use of the product is facilitated by the reaction of each component of the composition even at low temperatures (about 40 ° C.). At this time, water is used in an amount of 30 to 100 times by weight in the composition for the fiber coating. The raw material inlet and outlet in the mixing vessel are provided with activated carbon as necessary to remove impurities and peculiar smell of the composition.

한편 본 발명의 섬유코팅용 조성물에는 원적외선 방사제, 자외선차단제, 방향제, 정전기 방지제, 항균제, 살균제, 방취제 및 탈취제 등의 보조제를 하나 또는 그 이상 추가로 첨가하여 사용할 수 있다. 보조제는 공지의 것을 사용할 수 있으며, 이에 대한 특별한 제한은 없다.Meanwhile, the composition for textile coating of the present invention may be used by adding one or more auxiliary agents such as far-infrared radiant, sunscreen, fragrance, antistatic agent, antibacterial agent, bactericide, deodorant and deodorant. Adjuvants can use a well-known thing, There is no restriction | limiting in particular.

본 발명 조성물의 주요한 용도는 섬유제품인데, 본 발명 조성물의 사용방법은 의류제품을 예로 들어 설명하면 다음과 같다. 세탁기 사용시 헹굼때 적당량 첨가후 건조할 수도 있고, 손세탁시 헹굼완료후 본 제품이 적당량 첨가된 물에 담근 후 그대로 건조할 수도 있고, 다림질시 본 제품이 적당량 첨가된 물을, 다림질하는 옷 전체가 촉촉히 젖도록 분무하거나 할 수 있는데, 본 발명의 섬유코팅용 조성물의 기능은 열에 의해서만 발휘되므로, 건조후 반드시 다림질하거나 헤어 드라이어 또는 열풍기 등으로 처리해 주어야 한다.The main use of the composition of the present invention is a textile product, the method of using the composition of the present invention is described as an example of a garment product. When using a washing machine, you can dry it after adding the proper amount when rinsing, or after the rinse is completed by hand washing, the product can be soaked in the appropriate amount of water and dried as it is. It can be sprayed to get wet, the function of the fiber coating composition of the present invention is only exerted by heat, it must be ironed after drying or treated with a hair dryer or a hot air blower.

본 발명의 섬유코팅용 조성물은 합성섬유, 면제품, 실크, 모피, 우의, 넥타이, 스포츠웨어, 작업복, 교복, 바바리코트, 군복 등 의류; 소파류, 커텐, 카페트, 침구류, 벽지, 의자 등 실내가구 및 홈인테리어 용품; 구두, 핸드백, 천연가죽제 및 인조가죽제 부츠, 장갑, 가방, 자켓 등 가죽제품; 기타 우산, 천막, 등산복, 골프용품 등에 사용할 수 있다.The composition for the fiber coating of the present invention is synthetic fibers, cotton products, silk, fur, raincoats, ties, sportswear, work clothes, school uniforms, barbary coats, military clothing, etc .; Indoor furniture and home interior goods such as sofas, curtains, carpets, bedding, wallpaper, and chairs; Leather products such as shoes, handbags, natural leather and artificial leather boots, gloves, bags and jackets; It can be used for other umbrellas, tents, hiking suits and golf equipment.

이하, 본 발명의 구체적인 방법을 실시예를 들어 상세히 설명하지만, 본 발명의 권리범위는 이들 실시예에만 한정되는 것은 아니다.Hereinafter, the specific method of the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited only to these Examples.

실시예 1: 본 발명의 섬유코팅용 조성물의 제조Example 1 Preparation of the Composition for Textile Coatings of the Present Invention

폴리테트라플루오로에틸렌 3 g, 파라핀 1 g, 목초액 1.5 g, 80∼99% 탈아세틸화된 키토산 0.5 g, 수소 2 g, 멜라민수지 0.5 g, 및 실리콘수지 0.5 g과 물 91 mL를, 석면재질의 격막으로 분리되어 격막의 일측에는 구리봉으로 된 양극이 설치되고, 격막의 타측에는 탄소봉으로 된 음극이 설치된 혼합통에 넣고 3 V의 전압을 걸어 전기분해를 하면서 상기 성분들을 혼합하여 섬유코팅용 조성물을 제조하였다.3 g polytetrafluoroethylene, 1 g paraffin, 1.5 g wood vinegar, 0.5 g 80-99% deacetylated chitosan, 2 g hydrogen, 0.5 g melamine resin, 0.5 g silicone resin and 91 mL water Separating into the diaphragm of the membrane, one side of the diaphragm is a copper rod anode is installed, the other side of the diaphragm is placed in a mixing vessel equipped with a carbon rod negative electrode and subjected to electrolysis by applying a voltage of 3 V to the fiber coating composition Was prepared.

실시예 2: 본 발명의 섬유 코팅용 조성물의 성능시험Example 2: Performance Test of the Composition for Textile Coatings of the Present Invention

(1)항균성시험(1) Antibacterial test

상기 실시예 1에서 제조한 본 발명의 섬유 코팅용 조성물의 항균성을 한국원사직물시험연구원에 의뢰하여 상기 연구원의 항균성시험법 (KS K 0693)에 따라 시험하였다. 섬유시료로는 면직물을 사용하였다. 사용공시균주는 스타필로코쿠스 아우레우스 ATCC 6538(Staphylococcus aureus ATCC 6538)과 클렙스질라 뉴모니애 (Klebsiella pneumoniae ATCC 4352) 이었다.The antimicrobial properties of the fiber coating composition of the present invention prepared in Example 1 were commissioned by the Korea Textile Testing Institute, and tested according to the antimicrobial test method (KS K 0693). Cotton fabric was used as the fiber sample. The strains used were Staphylococcus aureus ATCC 6538 and Klebsiella pneumoniae ATCC 4352.

본 발명의 섬유코팅조성물을 처리하기 전과 후를 비교해보니 양 균주 모두에 대해 균감소율이 99.9%이었다.Comparing the before and after treatment of the fiber coating composition of the present invention, the reduction rate was 99.9% for both strains.

(2)발수도시험(2) Water repellency test

상기 실시예 1에서 제조한 본 발명의 섬유 코팅용 조성물의 발수도를 한국원사직물시험연구원에 의뢰하여 상기 연구원의 발수도시험방법 (KS K 0590, 스프레이법)에 따라 시험하였다. 섬유시료로는 폴리에스테르/스판, 면직물 나염지와 면직물을 사용하였다. 발수도 시험은 각 섬유시료에 대해 3회 실시하였다.The water repellency of the fiber coating composition of the present invention prepared in Example 1 was commissioned by the Korea Textile Testing Institute, and tested according to the water repellency test method (KS K 0590, spray method). As the fiber samples, polyester / span, cotton printed paper and cotton were used. The water repellency test was conducted three times for each fiber sample.

시험 결과, 발수도는 사용한 섬유시료 모두에 대해 80으로 나타났다.The test showed that the water repellency was 80 for all of the fiber samples used.

이상, 상기 실시예를 통하여 설명한 바와 같이 본 발명의 섬유 코팅용 조성물은 섬유에 흡수되어 섬유주변에 분자보호막을 형성함으로써 외부의 충격이나 자극으로부터 섬유를 보호해주고 수성 또는 유성 오염물질로부터 섬유를 보호하는 효과가 있으며 기타 흙, 먼지 등이 직물에 스며들지 않고 쉽게 제거되도록 한다. 물 등을 비롯한 이러한 오염물질은 직물에 스며들지 않고 표면에서 구슬처럼 뭉쳐 굴러 떨어지므로 자국이 남지 않고 쉽게 제거된다. 또 이러한 기능은 여러번 세탁후에도 효과가 지속된다.As described above, the fiber coating composition of the present invention is absorbed by the fiber to form a molecular protective film around the fiber to protect the fiber from external impact or irritation and to protect the fiber from aqueous or oily contaminants It works and allows other dirt and dust to be easily removed without getting into the fabric. These contaminants, including water, do not penetrate the fabric and are rolled up like beads from the surface and are easily removed without leaving traces. This feature also persists after multiple washes.

또한 본 발명의 조성물은 세균 및 냄새를 근원적으로 막아준다. 모든 섬유류는 일정 수분을 함유하고 있으며, 또한 끊임없이 주변의 수분과 공기중의 냄새를 흡수하려는 섬유 본래의 성질이 있다. 이러한 섬유의 성질이 미생물 및 각종 세균류가 활동하고 번식할 수 있는 좋은 환경과 자양분을 제공해주어 일반적인 세균방지제로는 좋은 효과를 얻을 수 없다. 본 발명의 조성물은 이러한 섬유의 수분, 냄새 및 공기 흡습기능 자체를 차단하여 미생물이나 세균류가 일체 잔류하지 못하도록 해주고 냄새를 방지해주고 탈취해 준다.In addition, the composition of the present invention prevents bacteria and odors. All fibers contain a certain amount of moisture and also have the inherent nature of the fiber, which constantly tries to absorb the surrounding moisture and odors in the air. The properties of these fibers provide a good environment and nourishment for microorganisms and various bacteria to act and propagate. The composition of the present invention blocks the moisture, odor and air-absorbing function of the fibers themselves to prevent microorganisms or bacteria from remaining at all, to prevent odor and to deodorize.

또한 본 발명의 조성물은 얇은 실크나 두꺼운 울에 이르기까지 어떤 직물에 처리하더라도 색상, 촉감 등 섬유 본래의 성질 및 외관을 그대로 유지시켜 준다.In addition, the composition of the present invention maintains the original properties and appearance of the fiber, such as color, touch, even if treated to any fabric, even thin silk or thick wool.

또한 본 발명의 조성물은 섬유에 코팅처리시 공기순환을 방해하는 고무코팅이나 라미네이트 층을 형성하지 않아 직물 본래의 숨쉬는 기능을 그대로 유지시켜 준다. 더욱이 세탁후 섬유사이의 오염물질이 깨끗이 제거되므로 직물의 올 사이로 통과하는 공기의 양이 많아져 통기성이 향상되고 인체의 땀 등 각종 수분을 흡수하여 증발시키는 수분 증발력도 향상된다.In addition, the composition of the present invention does not form a rubber coating or a laminate layer that interferes with the air circulation during the coating treatment to maintain the original fabric breathing function. Furthermore, since the contaminants between the fibers are removed after washing, the amount of air passing through all the fabrics is increased to improve breathability, and the moisture evaporation power to absorb and evaporate various moisture such as human sweat is also improved.

또한 본 발명의 섬유조성물은 자연을 보호하는 환경친화적 제품이다. 본 제품은 오염이나 때를 막아주는 기능이 강하여 세탁을 자주 할 필요가 없으며 세탁시에도 경미한 오염은 세제를 사용하지 않아도 오염 및 때가 제거된다. 세제사용시에도 극히 소량만 사용하여도 충분한 효과가 있다. 또한 헹굼기능만으로도 높은 세탁효과를 발휘하여 보통의 오염물질, 때 등은 제거되므로 물의 사용량을 대폭 줄일 수 있다.In addition, the fiber composition of the present invention is an environmentally friendly product that protects nature. This product does not need to be frequently washed because it has a strong function to prevent contamination or stains. Even the slightest stains during washing can be removed without using detergent. Even when using detergents, only a small amount is sufficient for the effect. In addition, since only the rinsing function shows a high washing effect, ordinary contaminants, stains, etc. are removed, thereby significantly reducing the amount of water used.

또한 본 발명의 섬유조성물은 무색, 무해하고 항균제나 항취제를 첨가할 경우 세균 및 곰팡이균으로부터 보호해줄 뿐만아니라 냄새도 막아주며 스며들지 못하게 해준다.In addition, the fiber composition of the present invention is colorless, harmless, and when added to the antibacterial or antibacterial agent not only protects from bacteria and fungi, but also prevents odor and prevents penetration.

Claims (4)

폴리테트라플루오로에틸렌 20∼55 중량%, 파라핀 5∼15 중량%, 목초액 8∼20 중량%, 80∼99% 탈아세틸화된 키토산 3∼10 중량%, 수소 13∼25 중량%, 멜라민수지 5∼10 중량%, 및 실리콘수지 2∼10 중량%가 혼합되어 이루어지는 섬유코팅용 조성물.20 to 55 wt% polytetrafluoroethylene, 5 to 15 wt% paraffin, 8 to 20 wt% wood vinegar, 80 to 99% 3 to 10 wt% deacetylated chitosan, 13 to 25 wt% hydrogen, melamine resin 5 Fiber coating composition comprising-10% by weight, and 2 to 10% by weight of silicone resin. 제 1항 기재의 섬유코팅용 조성물과 물을, 유리섬유 또는 석면재질의 격막으로 분리되어 격막의 일측에는 구리봉으로 된 양극이 설치되고, 격막의 타측에는 탄소봉으로 된 음극이 설치된 혼합통내에 넣고, 전류를 통과시키면서 혼합하는 것으로 이루어지는 섬유코팅용 조성물의 희석방법.The fiber coating composition of claim 1 and water are separated into a glass fiber or asbestos-like diaphragm, and one side of the diaphragm is placed in a mixing vessel provided with a copper rod anode, and the other side of the diaphragm is provided with a carbon rod negative electrode. Dilution method of the composition for fiber coating consisting of mixing while passing a current. 제 2항에 있어서, 물은 제 1항 기재의 섬유코팅용 조성물에 중량비로 30∼100배의 양으로 사용하는 것을 특징으로 하는 섬유코팅용 조성물의 희석방법.The method for diluting a fiber coating composition according to claim 2, wherein water is used in an amount of 30 to 100 times by weight ratio to the fiber coating composition according to claim 1. 제 1항에 있어서, 상기 섬유코팅용 조성물이 원적외선 방사제, 자외선차단제, 방향제, 항균제, 살균제, 방취제 및 탈취제, 정전기 방지제로 이루어지는 군으로부터 선택된 하나 또는 그 이상의 보조제를 추가 함유하는 것을 특징으로 하는 섬유코팅용 조성물.The fiber according to claim 1, wherein the fiber coating composition further contains one or more auxiliaries selected from the group consisting of far-infrared radiators, sunscreens, fragrances, antibacterial agents, fungicides, deodorants and deodorants, and antistatic agents. Coating composition.
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KR101223330B1 (en) * 2012-06-21 2013-01-16 주식회사 혜성지테크 Paint composition comprising a natural vegetable resin component and manufacturing method thereof
WO2017192109A1 (en) * 2016-05-03 2017-11-09 Bioarge Bitiksel Kozmetik Arastirma Gelistirme Muhendislik Ltd. Sti. Natural soap composition and manufacturing process
KR102621692B1 (en) * 2023-06-09 2024-01-05 주식회사 엠에스알 Manufacturing method of leather fabric recycling natural leather wastes

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JPH04120148A (en) * 1990-09-12 1992-04-21 Mitsui Toatsu Chem Inc Resin composition and use thereof
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* Cited by examiner, † Cited by third party
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KR101223330B1 (en) * 2012-06-21 2013-01-16 주식회사 혜성지테크 Paint composition comprising a natural vegetable resin component and manufacturing method thereof
WO2017192109A1 (en) * 2016-05-03 2017-11-09 Bioarge Bitiksel Kozmetik Arastirma Gelistirme Muhendislik Ltd. Sti. Natural soap composition and manufacturing process
KR102621692B1 (en) * 2023-06-09 2024-01-05 주식회사 엠에스알 Manufacturing method of leather fabric recycling natural leather wastes

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