KR910009948B1 - The method of preparation of coated fabric having superior antibiosis,deodorizing property and hygroscopicity - Google Patents
The method of preparation of coated fabric having superior antibiosis,deodorizing property and hygroscopicity Download PDFInfo
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- KR910009948B1 KR910009948B1 KR1019890016545A KR890016545A KR910009948B1 KR 910009948 B1 KR910009948 B1 KR 910009948B1 KR 1019890016545 A KR1019890016545 A KR 1019890016545A KR 890016545 A KR890016545 A KR 890016545A KR 910009948 B1 KR910009948 B1 KR 910009948B1
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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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
- D06M11/42—Oxides or hydroxides of copper, silver or gold
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/015—Biocides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
Abstract
Description
본 발명은 우리의 일상생활과 밀접한 관계가 있는 의류에 항균성 제오라이트(Zeolite)를 부여하여 미생물의 번식으로 인한 섬유재료의 취화, 착생오염 및 악취를 방지할 뿐만 아니라, 흡습성능을 향상시켜 항상 쾌적한 느낌을 주는 코팅직물의 제조에 관한 것이다. 기존에 이용되고 있는 의류용 코팅직물은 직물상태에 폴리우레탄등의 합성중합체를 이용하여 미다공을 형성시킨 제품으로서 격렬한 운동등 땀을 많이 흘리는 경우, 투습·방수성에 한계가 있어 인체내에서 발산되는 땀이 의복내에 축척되어 인체에 불쾌감을 줄 뿐만 아니라 미생물의 번식에 좋은 조건을 제공하여 악취 및 기타 미생물에 의한 오염을 야기시키는 문제점이 있었다.The present invention imparts antimicrobial zeolites to clothing which is closely related to our daily lives, thereby preventing embrittlement, physiological contamination and odor of fiber materials due to the growth of microorganisms, as well as improving hygroscopic performance to always feel comfortable. Relates to the production of coated fabrics. The coating fabric for clothes used in the past is a product that forms micropores by using synthetic polymers such as polyurethane in the fabric state. The sweat accumulates in the garments, which not only causes discomfort to the human body, but also provides a good condition for the growth of microorganisms, causing contamination by odors and other microorganisms.
본 발명은 이러한 문제점을 해결하기 위해 향균성, 탈취성 및 흡습성이 우수한 제오라이트를 폴리우레탄 수지에 균일하게 분산시켜 섬유포지에 코팅함으로써 항균성, 탈취성 및 흡습성이 우수한 코팅직물을 얻는데 그 목적이 있다. 본 발명에 사용되는 포지로서는 폴리에스테르, 나이론, 폴리에스테르/면혼방, 나일론/면혼방 직물이 좋다.In order to solve this problem, an object of the present invention is to uniformly disperse zeolite with excellent antibacterial, deodorant and hygroscopic properties in a polyurethane resin and to coat the fiber cloth to obtain a coating fabric having excellent antimicrobial, deodorizing and hygroscopic properties. Forge used in the present invention is preferably polyester, nylon, polyester / cotton blend, nylon / cotton blend fabric.
본 발명에서는 화학섬유로 된 직물에 피막을 형성시키기 위한 코팅액으로 디메틸포름아마이드를 용제로 사용한 고형분 20±1%의 폴리우레탄 수지 100중량부(고형분 기준)에 대해 제오라이트의 한종류인 모더나이트(Mordenite)를 강산으로 비등(沸騰)처리하여 실리카/알루미나비(silica/alumina mole ratio)를 10 내지 33으로 저절한 후 은, 구리, 아연 등의 살균성 금속을 이온교환시켜 평균 입자크기를 0.5㎛ 내지 2.5㎛로 조절한 제오라이트를 5내지 50중량부(폴리우레탄 수지의 유효성분 기준), 유효성분 100%인 비이온 계면활성제를 5 내지 15중량부(폴리우레탄 수지의 유효성분 기준), 고형분 75%인 폴리이소시아네이트를 5 내지 25중량부(폴리우레탄 수지의 유효성분 기준)을 혼합하고 디메틸포름아마이드로 점도를 조절하여 사용한다. 코팅에 사용한 폴리우레탄 수지는 4, 4-디페닐메탄디이소시아네이트(4,4′-Diphenylmethane-diisocyanate)와 1, 4-부탄디올(1, 4-Butanediol)과 아디프산(Adipic acid)을 중합한 중합도 100 내지 200정도의 폴리올(Polyol)을 중합한 것으로 점도 20,000 내지 30,000cps(25℃)인 것을 사용하였다. 비이온 계면활성제로는 폴리프로필렌글리콜(Polypro-pylene glycol)과 폴리에틸렐글리콜(Polyethylene glycol)의 블록공중합체를 사용하였는데, 비이온 계면활성제는 폴리우레탄 중합체 용액을 응고욕에 침지시킬 때에 중합체 용액중의 디메틸 포름아마이드의 응고욕으로의 용출속도를 조절하여 미다공질 피막의 기공을 균일하고 미세하게 형성시키는 역할을 한다.In the present invention, mordenite, which is a kind of zeolite, based on 100 parts by weight (based on solids) of polyurethane resin having a solid content of 20 ± 1% using dimethylformamide as a coating liquid for forming a film on a fabric made of chemical fibers. Was boiled with strong acid to reduce the silica / alumina mole ratio to 10 to 33, and then ion-exchanged germicidal metals such as silver, copper, and zinc to obtain an average particle size of 0.5 μm to 2.5 μm. 5 to 50 parts by weight of zeolite adjusted to (based on the active ingredient of polyurethane resin), 5 to 15 parts by weight of nonionic surfactant 100% of the active ingredient (based on the active ingredient of polyurethane resin), poly 75% solids Isocyanate is used by mixing 5 to 25 parts by weight (based on the active ingredient of the polyurethane resin) and adjusting the viscosity with dimethylformamide. The polyurethane resin used for the coating was a polymerization of 4,4-diphenylmethane-diisocyanate, 1,4-butanediol, and adipic acid. A polyol having a degree of polymerization of 100 to 200 was polymerized, and a viscosity of 20,000 to 30,000 cps (25 ° C.) was used. As nonionic surfactants, block copolymers of polypro-pylene glycol and polyethylene glycol were used. The nonionic surfactant is a polymer solution when the polyurethane polymer solution is immersed in a coagulation bath. It controls the elution rate of dimethyl formamide in the coagulation bath to uniformly and finely form pores of the microporous coating.
(단, M:원자가 n의 금속, x+y:단위격자당 사면체의 수 z:물분자의 mole수)로 표시되는 제오라이트는 비표면적이 대단히 큰 다공성 물질로서 실리카-알루미나(silica-alumina)가 주성분 원소이고 TO4(T=Si, Al)사면체가 서로 산소원자를 공유하면서 3차원으로 구성되어 있는 결정체이다. 구조내에서 산소원자는 두 개의 사면체를 공유하기 때문에 격자는 음(-)의 전기를 띠게 되며 따라서 구조내 교환성능이 있는 양이온과 균형을 이루게 된다.However, zeolite represented by (M: metal of atomic n, x + y: number of tetrahedrons per unit lattice z: number of moles of water molecules) is a porous material having a very large specific surface area, and is composed of silica-alumina. It is a crystalline main component element and TO 4 (T = Si, Al) tetrahedron is composed of three dimensions while sharing oxygen atoms with each other. Because oxygen atoms share two tetrahedrons within the structure, the lattice is negatively charged, thus balancing the cations with exchange performance in the structure.
이러한 구조를 가진 제오라이트에 은, 구리, 아연등의 살균성 금속을 이온교환법으로 담지시키면 살균성 금속은 제오라이트내에 안정한 상태로 결합되어 균일하게 분포되기 때문에 세균류에 대하여 대단히 활성도가 높은 항균성 조성물이 된다.When a germicidal metal such as silver, copper, zinc, etc. is supported on the zeolite having such a structure by ion exchange method, the germicidal metal is bonded in a stable state in the zeolite and distributed uniformly, resulting in an extremely antimicrobial composition highly active against bacteria.
따라서 이러한 방법으로 조성된 항균성 조성물을 살균에 이용하는 경우, 살균성의 은, 구리, 아연등의 이온은 제오라이트 모체중에 활성점을 갖고, 접촉표면적이 커서 살균력이 증대되며 특히 살균성 금속이 안정한 상태로 제오라이트내에 결합되어 금속이온의 용출이 거의 무시되기 때문에 향균력의 지속성, 내수압, 내열성등이 대단히 우수하다.Therefore, when the antimicrobial composition prepared in this way is used for sterilization, the bactericidal silver, copper and zinc ions have an active point in the zeolite matrix, the contact surface area is large, and the bactericidal power is increased. Since the leaching of metal ions is almost ignored, the antimicrobial persistence, water pressure and heat resistance are excellent.
이온교환 능력측면에서도 제오라이트소재는 본 발명에 필요한 살균성 금속을 이온 교환시키기에 충분하다. 일반적으로 살균을 목적으로 Na명 제오라이트에 이온교환시 음이온은 0.01 내지 0.04중량%(무수기준), 구리이온은 0.03 내지 10중량%(무수기준), 아연이온은 0.04 내지 14중량%(무수기준)가 좋다고 알려져 있다.In terms of ion exchange capacity, the zeolite material is sufficient to ion exchange the bactericidal metal required for the present invention. In general, for the purpose of sterilization, the Na-name zeolite is ionized at 0.01 to 0.04 wt% (anhydrous basis), 0.03 to 10 wt% (anhydrous basis), and zinc ion is 0.04 to 14 wt% (anhydrous basis). Is known to be good.
본 발명에서는 합성 모더나이트를 강산으로 비등 처리하여 실리카/알루미나비(silica/alumina mole ratio)를 조절한 후 살균성 금속인 은, 구리, 아연등을 담지하여 평균입자크기를 0.5㎛ 내지 2.5㎛로 결정수 함유상태 또는 무수상태의 항균성 조성물을 조제하여 사용한다.In the present invention, the synthetic mordenite is boiled with a strong acid to adjust silica / alumina mole ratio, and then the average particle size is determined to be 0.5 μm to 2.5 μm by supporting silver, copper, zinc, etc., which are bactericidal metals. A water-containing or anhydrous antimicrobial composition is prepared and used.
이하 실시예에 의거 본 발명을 구체적으로 설명한다.The present invention will be described in detail with reference to the following Examples.
[실시예 1]Example 1
70데니어 210T나일론 평직물을 정련 염색한 후 여기에 폴리우레탄수지 100중량부(고형분기준), 강산인 염산으로 비등 처리하여 실리카/알루미나비를 22로 조절하고 이온교환법으로 은이온을 0.04% 담지시킨 후 평균입자크기를 2.0㎛로 조절한 모더나이트를 20중량부, 유효성분이 100%인 비이온 계면활성제를 10중량부, 고형분이 75%인 폴리이소시아네이트 12.5중량부를 혼합하고 디메틸포름아마이드로 점도를 조절하여 이루어진 코팅액을 100g/㎡로 도포한 후, 응고·수세공정을 거쳐 120℃에서 1분간 건조시키고 150℃에서 3분간 경화(curing)하였다.After refining and dyeing 70 denier 210T nylon plain fabric, it was boiled with 100 parts by weight of polyurethane resin (based on solids) and hydrochloric acid as a strong acid to adjust the silica / alumina ratio to 22 and carry 0.04% of silver ions by ion exchange. 20 parts by weight of mordenite having an average particle size of 2.0 μm, 10 parts by weight of a nonionic surfactant having 100% of an active ingredient, and 12.5 parts by weight of a polyisocyanate having a solid content of 75% were mixed, and the viscosity was adjusted with dimethylformamide. The coating solution was then applied at 100 g / m 2, dried at 120 ° C. for 1 minute through a coagulation and washing step, and cured at 150 ° C. for 3 minutes.
다음에 불소계 발수제를 5% 수용액으로 희석하여 30% 부착(pick-up)양으로 압착(padding)후 120℃에서 1분간 건조하고 160℃에서 3분간 경화(curing)하여 물성을 평가하였다. 그 결과는 표 1, 2와 같다.Next, the fluorine-based water repellent was diluted with a 5% aqueous solution, and then padded with 30% pick-up amount, dried at 120 ° C. for 1 minute, and cured at 160 ° C. for 3 minutes to evaluate physical properties. The results are shown in Tables 1 and 2.
[비교 실시예 1]Comparative Example 1
사용 모너나이트의 실리카/알루미나비가 5인 것을 사용하여 실시예 1과 동일하게 실시하였다. 그 결과는 표 1, 2와 같다.It carried out similarly to Example 1 using the thing of silica / alumina ratio of the used mordenite. The results are shown in Tables 1 and 2.
[비교 실시예 2]Comparative Example 2
사용 모더나이트의 실리카/알루미나비가 40인 것을 사용하여 실시예 1과 동일하게 실시하였다. 그 결과는 표 1, 2와 같다.It carried out similarly to Example 1 using the thing of silica / alumina ratio of used mordenite 40. The results are shown in Tables 1 and 2.
[비교 실시예 3]Comparative Example 3
사용 모더나이트의 살균성 금속인 은이온을 함유하지 않도록 하여 실시예 1과 동일하게 실시하였다. 그 결과는 표 1, 2와 같다.It carried out similarly to Example 1, containing no silver ion which is a disinfectant metal of the used mordenite. The results are shown in Tables 1 and 2.
[비교 실시예 4]Comparative Example 4
모더나이트의 입자크기를 평균 4㎛로 조절하여 실시예 1과 동일하게 실시하였다. 그 결과는 표 1, 2와 같다.The particle size of mordenite was adjusted to an average of 4㎛ was carried out in the same manner as in Example 1. The results are shown in Tables 1 and 2.
[비교 실시예 5]Comparative Example 5
모더나이트를 첨가하지 않고 실시예 1과 동일하게 실시하였다. 그 결과는 표 1, 2와 같다.It carried out similarly to Example 1, without adding mordenite. The results are shown in Tables 1 and 2.
[비교 실시예 6]Comparative Example 6
모더나이트의 첨가량을 폴리우레탄 수지의 유효성분을 기준하여 1중량부 사용하여 실시예 1과 동일하게 실시하였다.The addition amount of mordenite was carried out in the same manner as in Example 1 using 1 part by weight based on the active ingredient of the polyurethane resin.
그 결과는 표 1, 2와 같다.The results are shown in Tables 1 and 2.
[비교 실시예 7]Comparative Example 7
모더나이트의 첨가량을 폴리우레탄 수지의 유효성분을 기준하여 55중량부 사용하여 실시예 1과 동일하게 실시하였다. 그 결과는 표 1, 2와 같다.The addition amount of mordenite was carried out in the same manner as in Example 1 using 55 parts by weight based on the active ingredient of the polyurethane resin. The results are shown in Tables 1 and 2.
[표 1]TABLE 1
○ : 표면상태 우수○: Excellent surface condition
× : 표면상태 불량×: surface condition defective
Co. 암모니아가스 : 암모니아가스의 초기농도Co. Ammonia Gas: Initial concentration of ammonia gas
C : 4시간후의 암모니아가스 농도C: Ammonia gas concentration after 4 hours
C′o 황화수소가스 : 황화수소가스의 초기농도C′o hydrogen sulfide gas: Initial concentration of hydrogen sulfide gas
C′ : 4시간 후의 황화수소가스 농도C ′: hydrogen sulfide gas concentration after 4 hours
표 1에서 발수도는 KS K 0590(SPRAY법), 내수압은 KS K 0591(저수압법), 투습도는 KS K 6886(CUP법), 박리강도는 KS M 6664, 표면상태는 육안으로, 탈취효과는 시험 물질로서 암모니아가스(NH2)와 황화수소가스(H2S)를 사용하였으며, 암모니아가스의 경우는 초기농도를 85ppm 내지 105ppm으로 황화수소가스의 경우는 초기농도를 65ppm 내지 75ppm으로 조절한 후, 데시케이트(Desiccator)내에 시편을 15㎝×15㎝크기로 잘라넣고 4시간 후의 농도를 측정하여, 초기농도에 대한 4시간후의 농도비로 평가하였다.In Table 1, water repellency is KS K 0590 (SPRAY method), water pressure is KS K 0591 (low water pressure method), moisture permeability is KS K 6886 (CUP method), peeling strength is KS M 6664, surface condition is visual, deodorizing effect Ammonia gas (NH 2 ) and hydrogen sulfide gas (H 2 S) were used as test materials, and in the case of ammonia gas, the initial concentration was adjusted to 85 ppm to 105 ppm, and in the case of hydrogen sulfide gas, the initial concentration was adjusted to 65 ppm to 75 ppm, The specimen was cut into 15 cm x 15 cm size in a desiccator, and the concentration after 4 hours was measured, and the concentration ratio after 4 hours to the initial concentration was evaluated.
[표 2]TABLE 2
표 2에서 항균성 공시균(供試菌)인 스태필로코코스 아우레우스(Staphylococcus aureus American Type Culture Collection NO.6538)를 사용하여 셰이크 플라스크법(Shake Flask Method)으로 사용하였고, 세탁시험은 가정용 전기세탁기를 사용하여 다음과 같은 조건으로 실시하였고, 세탁탈수후는 자연건조시켜 성능평가를 하였다.Table 2 was used as the Shake Flask Method using the Staphylococcus aureus American Type Culture Collection NO.6538, an antimicrobial test bacterium. Using was carried out under the following conditions, and after washing and dehydration, the natural drying to evaluate the performance.
○ 세제 : 비이온합성세제 10g/5ℓ(물)○ Detergent: 10g / 5ℓ (water) of nonionic synthetic detergent
○ 세탁시간 : 5분○ Laundry time: 5 minutes
○ 탈수시간 : 1분○ Dehydration time: 1 minute
○ 재세탁시간 : 8분○ Rewashing time: 8 minutes
○ 탈수시간 : 2분○ Dehydration time: 2 minutes
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| KR1019890016545A KR910009948B1 (en) | 1989-11-15 | 1989-11-15 | The method of preparation of coated fabric having superior antibiosis,deodorizing property and hygroscopicity |
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| KR910009797A KR910009797A (en) | 1991-06-28 |
| KR910009948B1 true KR910009948B1 (en) | 1991-12-06 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1626118A3 (en) * | 2004-08-11 | 2006-03-08 | Formosa Taffeta Co.,Ltd. | Yarns and fabrics having long-lasting mosquito repellent or antibacterial effect and their preparation |
| FR3071421A1 (en) * | 2017-09-26 | 2019-03-29 | 3F Innovation | METHOD FOR MANUFACTURING ACTIVE MEDIUM AND SUPPORT THUS OBTAINED |
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1989
- 1989-11-15 KR KR1019890016545A patent/KR910009948B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1626118A3 (en) * | 2004-08-11 | 2006-03-08 | Formosa Taffeta Co.,Ltd. | Yarns and fabrics having long-lasting mosquito repellent or antibacterial effect and their preparation |
| FR3071421A1 (en) * | 2017-09-26 | 2019-03-29 | 3F Innovation | METHOD FOR MANUFACTURING ACTIVE MEDIUM AND SUPPORT THUS OBTAINED |
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| Publication number | Publication date |
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| KR910009797A (en) | 1991-06-28 |
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