KR20020032796A - Method for the preparation of the polymer membrane having water-proof and gas permeable properties - Google Patents
Method for the preparation of the polymer membrane having water-proof and gas permeable properties Download PDFInfo
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/24—Rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/54—Polyureas; Polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
- B29C67/202—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored comprising elimination of a solid or a liquid ingredient
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/10—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
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Abstract
본 발명은 필름형태나 섬유상에 직접 적층된 형태로 제조되는 통기 방수성 고분자 막의 제조방법에 관한 것으로서, 특히 종래의 방법에 비해 통기 방수효과가 우수하고 제조방법이 단순하여 제조비용의 절감을 도모할 수 있는 새로운 제조방법을 제공하는데 그 목적이 있는 것이다.The present invention relates to a method of manufacturing a breathable waterproof polymer membrane prepared in the form of a film or directly laminated on a fiber, in particular, compared to the conventional method is excellent in breathable waterproof effect and simple manufacturing method can reduce the manufacturing cost The purpose is to provide a new manufacturing method.
본 발명은 상기와 같은 목적을 달성하는 일방법으로, 고분자 재료에 산용액 또는 알카리 용액에 용해 가능한 무기 입자를 첨가하여 막상으로 성형한 후, 이 성형물을 산용액 또는 알카리 용액에 침적시켜 무기 입자를 용출 제거 시키는 것을 특징으로 한 통기 방수성 고분자 막 제조법을 개시한다.According to one aspect of the present invention, an inorganic particle soluble in an acid solution or an alkali solution is added to a polymer material to form a film, and then the molded product is deposited in an acid solution or an alkali solution to form an inorganic particle. Disclosed is a method for producing a breathable waterproof polymer membrane, which is eluted and removed.
Description
본 발명은 필름형태나 또는 섬유상에 직접 적층된 형태로 여성용 생리대, 유아용 기저귀, 낚시복, 등산복 등에 사용되는 통기 방수성 고분자 막 제조방법에 관한 것으로서, 특히 산이나 알카리 용액을 사용하여 통기 방수성의 고분자 막을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a breathable waterproof polymer membrane used in women's sanitary napkins, baby diapers, fishing clothes, mountaineering clothes, etc. in the form of a film or directly laminated on a fiber, in particular using a acid or alkaline solution to produce a waterproof breathable polymer membrane It is about how to.
통기 방수성 고분자 막은 습기와 같은 기체 상태의 물질은 통과시키는 대신에 액상이나 고상의 물질은 통과시키지 않는 특성을 지닌 막으로서, 이와 같은 특성을 지닌 고분자 막을 제조하는 종래의 대표적인 방법으로는 막의 재료인 고분자를 극성 용제에 용해시킨 후 DMF(N,N-디메틸 포름아미드)등을 넣고 필름형태로 습식성형시킨후 수용액에 침적시켜 상기 필름에 함유되어 있는 극성 용제를 추출시켜 다공막을 형성시키는 방법(A), 연신율이 큰 고분자 재료에 함유 수분을 조절한 무기질 충전제를 혼합하여 압출성형 등으로 필름화 한 후 이를 연신시켜 기공을 형성시키는 방법(B), 수용성의 무기염 또는 수용성 고분자를 해당 고분자 소재에 혼합한 후 압출성형 등으로 필름화 한 후 이를 물에 넣어 상기 수용성 물질을 용해시켜 제거함에 의해 기공을 형성시키는 방법(C) 등이 알려져 있다.The breathable waterproof polymer membrane is a membrane having a property of passing a gaseous substance such as moisture but not a liquid or solid substance. A conventional representative method of manufacturing a polymer membrane having such a characteristic is a polymer of a membrane. Is dissolved in a polar solvent, DMF (N, N-dimethyl formamide) and the like is wet molded in the form of a film, and then immersed in an aqueous solution to extract the polar solvent contained in the film to form a porous membrane (A) , A method of mixing the water-modified inorganic filler into a polymer material having a high elongation rate and film-forming it by extrusion molding, and then stretching it to form pores (B), mixing a water-soluble inorganic salt or a water-soluble polymer into the polymer material After the film is formed by extrusion molding, it is placed in water to dissolve and remove the water-soluble substance. It is known, such as methods of property (C).
그러나, (A)방법의 경우는 극성 용매에 용해될 수 있는 고분자를 막의 소재로 사용해야 하는 재료 선택의 한계가 있고, 또한 기공의 크기나 양을 임의로 조정하기가 어려운 문제점이 있으며, (B)방법의 경우는 기공의 크기를 조절하기가 용이하나 연신율이 큰 고분자 소재를 사용해야만 하는 문제점이 있으며, (C)방법의 경우는 사용가능한 무기염의 경우가 수용성 염이므로 상온에서 수분과 반응하여 입자가 응집하는 특징이 있어서 작업성이 떨어지고, 또 수용성 고분자의 경우는 폴리머 매트릭스 내에서 물로 용해시 고분자가 스웰링(swelling)되며 추출될때까지의 시간이 오래 걸리는 등의 문제점을 지닌다.However, in the case of the method (A), there is a limitation in selecting a material in which a polymer that can be dissolved in a polar solvent is used as the material of the membrane, and in addition, it is difficult to arbitrarily adjust the size or amount of the pores. In the case of, it is easy to control the size of the pores, but there is a problem that a polymer material having a high elongation must be used.In the case of the (C) method, the available inorganic salts are water-soluble salts, so that the particles react with moisture at room temperature to aggregate. In the case of water-soluble polymers, the water-soluble polymers have problems such as swelling and long time for extraction when dissolved in water in the polymer matrix.
일반적으로 통기 방수성 고분자막의 수증기 투과량(Q)은 표면적(A), 투과시간(T)및 접액면의 온도차에 기인한 증기의 분압차(ㅿP)에 비례하고 두께(L)에 반비례하며, 다음과 같은 식으로 나타낼수 있다.In general, the water vapor permeability (Q) of the water-permeable waterproof polymer membrane is proportional to the partial pressure difference (ㅿ P) of steam due to the surface area (A), the permeation time (T), and the temperature difference of the contact surface, and inversely proportional to the thickness (L). It can be expressed as
Q = K·A·T·ㅿP/LQ = K, A, T, ㅿ P / L
상기 식에서 비례상수 K는 투과계수로서, 고분자 막의 수증기의 물 분자의 이동도를 나타내는 확산계수와 고분자내의 수증기 용해성을 나타내는 용해도 계수의 적(積)으로서, 기체 투과를 지배하는 값이다.In the above formula, the proportional constant K is a value that governs gas permeation as the permeability coefficient, the product of the diffusion coefficient indicating the mobility of water molecules in the water vapor of the polymer membrane and the solubility coefficient indicating water solubility in the polymer.
따라서 특히 방수성이 우수한 고분자 막을 제조하기 위해서는 확산계수를 크게 할 필요가 있다. 이러한 확산계수는 물리적으로 기공의 크기를 증대시키면 증가하나 기공의 크기가 큰 경우는 물의 응집에너지에 의해 삼투현상이 발생하므로 통기 방수성 고분자 막은 물의 삼투현상이 일어나지 않는 범위내로 기공의 크기를 제한하고 기공수를 많게 하는 것이 필요하다.Therefore, it is necessary to increase the diffusion coefficient especially in order to produce a polymer membrane having excellent waterproofness. This diffusion coefficient increases when the pore size is physically increased, but when the pore size is large, osmotic phenomena are generated by the cohesive energy of water. Therefore, the waterproof air-permeable polymer membrane restricts the pore size within the range where water osmosis does not occur, It is necessary to increase the number.
본 발명은 전술한 바와 같은 종래의 통기 방수성 고분자 막의 문제점을 해결하기 위해 안출된 것으로서, 특히 기공의 크기나 양의 조절이 가능하고 투기 방수효과가 우수한 고분자 막의 제조가 가능하고, 제조공정이 단순하여 제조비용의 절감을 도모할 수 있는 새로운 통기 방수성 고분자 막 제조법을 제공하는데 그 목적이 있는 것이다.The present invention has been made to solve the problems of the conventional air-permeable waterproof polymer membrane as described above, in particular, it is possible to control the size or amount of pores and to produce a polymer membrane excellent in the air permeability waterproof effect, the manufacturing process is simple It is an object of the present invention to provide a new breathable waterproof polymer membrane manufacturing method that can reduce the manufacturing cost.
본 발명은 이와 같은 발명의 목적을 달성하는 일 방법으로, 막의 소재인 고분자에 산용액 또는 알카리 용액에 용해가 가능한 무기입자를 적당량 첨가 혼합하고 막상으로 성형한 후, 상기 성형물을 산용액 또는 알카리 용액에 침적시켜 고분자 막중에 함유된 무기입자를 용출 제거시키는 것을 특징으로 한 고분자 막 제조법을 개시한다.The present invention is one method to achieve the object of the invention, by adding an appropriate amount of inorganic particles soluble in an acid solution or an alkali solution to the polymer material of the membrane, and then molded into a film, the molded product is an acid solution or an alkali solution Disclosed is a method for producing a polymer membrane, characterized in that the inorganic particles contained in the polymer membrane are eluted and removed by evaporation.
이하에서 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 전술한 바와 같이 산 또는 알카리에 쉽게 용해되는 무기 입자를 막의 소재인 고분자에 혼합시키고 막상으로 성형한 후, 이를 산용액 또는 알카리 용액에 침적시켜 화학반응에 의해 상기 무기입자을 제거함으로써 원하는 통기방수성의 고분자 막을 제조하며 이때, 사용되는 무기입자는 산이나 알카리에 용해되는 것이면 특별히 한정되지 않고 어느것이나 사용 가능한데, 예를 들어, 산화아연, 산화마그네슘 등의 금속산화물, 철분말, 알루미늄 분말과 같은 금속 분말, 탄산칼슘, 탄산마그네슘 등이 있다. 또한, 막의 소재로 사용되는 고분자 재료의 경우에는 막으로 성형이 가능한 고분자는 열가소성이나 열경화성 소재를 구분하지 않고 모두 사용가능하다.In the present invention, as described above, the inorganic particles that are easily dissolved in acid or alkali are mixed with the polymer, which is the material of the membrane, and molded into a membrane, and then deposited in an acid solution or an alkali solution to remove the inorganic particles by chemical reaction, thereby providing a desired aeration. In this case, the inorganic particles used are not particularly limited as long as they are dissolved in acid or alkali. For example, metal oxides such as zinc oxide and magnesium oxide, iron powder, and aluminum powder may be used. Metal powder, calcium carbonate, magnesium carbonate and the like. In addition, in the case of the polymer material used as the material of the membrane, any polymer that can be molded into a membrane can be used without distinguishing a thermoplastic or thermosetting material.
한편, 고분자에 무기입자를 첨가하여 투기 방수성 막을 제조하는 방법으로는, 고분자를 가용 용매에 용해시킨 다음 여기에 무기입자를 첨가하여 균일하게 혼합한 후, 상기 혼합 용액을 유리판이나 스테인레스 스틸판과 같은 기재에 적당한 두께로 코팅, 건조, 박리 공정을 거쳐 얻어진 필름상의 막 또는 상기혼합용액을 고분자 막으로 피복시키고자 하는 섬유재나 종이재의 원자재에 직접 코팅 시키고 건조시켜 생성된 막을 산용액이나 알카리 용액에 침적시켜 무기입자를 제거시킴에 의해 통기 방수성 막을 얻는 방법과, 열가소성 고분자의 경우 펠레트상이나 분말상의 고분자 재료와 무기입자를 혼합하여 가열 유동화 시켜며 압출가공 또는 캘린더 가공등의 가공법을 이용해 필름상으로 성형한 것을 산용액이나 알카리 용액에 침적시켜 무기 입자를 제거시킴에 의해 통기 방수성 막을 얻는 방법 등이 있다.On the other hand, as a method of producing an air permeable waterproof membrane by adding inorganic particles to the polymer, the polymer is dissolved in a soluble solvent and then the inorganic particles are added and mixed uniformly, and then the mixed solution is mixed with a glass plate or a stainless steel plate. The film formed by coating, drying, or peeling the substrate to a suitable thickness or the mixed solution is directly coated on the raw material of the fiber or paper material to be coated with a polymer film and dried to deposit the resulting film in an acid solution or an alkaline solution. To obtain a breathable waterproof membrane by removing the inorganic particles, and in the case of the thermoplastic polymer, a pelletized or powdered polymer material and inorganic particles are mixed and heated to be fluidized, and formed into a film using a processing method such as extrusion processing or calender processing. The inorganic particles are deposited in an acid solution or an alkali solution. By going Sikkim and a method for obtaining breathable waterproof membrane.
본 발명에서 무기입자의 입자크기와 그 사용량은 최종 제품의 기공의 크기, 투기도 등을 결정하는 중요한 요소로서, 입자의 크기는 대략 평균입경이 0.1∼20㎛범위, 사용량은 고분자 100중량부에 대하여 대략 60∼800중량부 범위가 바람직하나, 상기 범위들에 의해 본 발명이 한정되는 것은 아니다.In the present invention, the particle size and the amount of the inorganic particles are an important factor for determining the pore size, air permeability, etc. of the final product, the size of the particles is approximately 0.1 ~ 20㎛ range of average particle diameter, the amount is 100 parts by weight of the polymer A range of about 60 to 800 parts by weight is preferred, but the present invention is not limited by the above ranges.
이하에서 실시예를 들어 본 발명을 좀 더 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예 1]Example 1
천연고무 100중량부, 산화아연 5중량부, 스테아린산 2.5중량부, 고무용 황 2.5중량부, 디벤조티아질 디설파이드(Dibenzothiazyl disulfide) 2.5중량부 및 BZ(Zinc di-n-butyldithiocarbamate) 0.5 중량부를 오픈 롤(Open Roll)상에서 혼련하여 얻어진 고무 조성물을 톨루엔 500중량부에 넣어 용해시킨 후, 탄산칼슘(유진실업주식회사제, 평균 입자경 6.05㎛)을 하기 표 1과 같이 변량 첨가하였다.100 parts by weight of natural rubber, 5 parts by weight of zinc oxide, 2.5 parts by weight of stearic acid, 2.5 parts by weight of rubber sulfur, 2.5 parts by weight of dibenzothiazyl disulfide and 0.5 parts by weight of zinc di-n-butyldithiocarbamate (BZ) After dissolving the rubber composition obtained by kneading on an open roll in 500 parts by weight of toluene and dissolving, calcium carbonate (Eujin Industry Co., Ltd., average particle size: 6.05 mu m) was added in a variable amount as shown in Table 1 below.
상기와 같이 배합된 고무 조성물들을 각각 직경이 50㎝ 이고 뚜껑이 없는 스텐인레스제 용기에 건조 후 두께가 대략 2㎜ 정도가 되도록 도포한 다음 진공 챔버에서 750㎜Hg ×40℃의 조건으로 2일간 방치하여 톨루엔을 완전히 제거하였다.Each of the rubber compositions blended as described above was applied to a stainless steel container having a diameter of 50 cm without a lid, and then dried to a thickness of about 2 mm, and then left in a vacuum chamber for 2 days under conditions of 750 mm Hg × 40 ° C. Toluene was completely removed.
톨루엔이 제거된 상기 시편들을 철재 금형에 넣고 200kg/㎠×150℃의 조건하에서 10분간 가황하였다. 이어서 가황된 시편들을 폭 5㎝ ×길이 5㎝ x 두께 2㎜의 판상으로 절단한 후, 이들을 각각 5% 묽은 염삼 용액에 침적시키고 24시간 상온에서 방치시킨 후 꺼내서 세척 및 건조공정을 거친 다음 CaCO3배합량에 따른 기공의 형성 정도를 관찰하기 위하여 염산 침적전의 시료들의 무게와 염산 침적후 세척, 건조 공정을 거친 시료들의 무게를 측정하여 하기 표 2에 나타내었다.The toluene-free specimens were placed in an iron mold and vulcanized for 10 minutes under conditions of 200 kg / cm 2 × 150 ° C. Subsequently, the vulcanized specimens were cut into plates having a width of 5 cm x 5 cm x 2 mm, and then they were respectively immersed in a 5% diluted saline solution, left at room temperature for 24 hours, removed, washed and dried before CaCO 3 In order to observe the degree of formation of pores according to the blending amount, the weight of the samples before hydrochloric acid deposition and the weight of the samples after washing and drying after hydrochloric acid deposition were measured and shown in Table 2 below.
상기 표 2 및 육안에 의한 관찰에 따르면, (1), (2)의 시편은 대략 막의 표피층에 존재하는 CaCO3만 용출 되었고, (3)의 경우는 대략 절반 정도가 용출되었으며, (4)∼(10)은 거의 또는 완전히 CaCO3가 용출된 것을 확인 할 수 있었다.According to the observation of Table 2 and the naked eye, the specimens of (1) and (2) were eluted only with CaCO 3 present in the epidermal layer of the membrane, and in (3), about half were eluted. (10) confirmed that CaCO 3 eluted almost or completely.
[실시예 2]Example 2
네오프렌 고무(Neoprene AD) 100중량부에 MgO 8중량부, ZnO 5중량부, 페놀수지 40중량부가 함유된 고무 조성물을 고형분 농도가 10중량% 되도록 톨루엔 용액에 용해시킨 후 CaCO3를 70중량부 투입하여 균일하게 분산시킨 혼합물을 나일론 섬유로 제직한 직포에 나이프 코터를 사용하여 20g/㎡의 양으로 도포한 후 상온에서 10분간 건조시키고, 이어서 150℃에서 열공기로 5분간 가황하고, 상기 가황된 시료를상온에서 5%염산 용액에 10분간 침적하여 CaCO3를 완전히 용출시킨 후 세척, 건조공정을 거쳐 통기 방수성 고분자 막을 나일론 직포상에 적층시켰다.After dissolving the rubber composition containing 8 parts by weight of MgO, 5 parts by weight of ZnO, and 40 parts by weight of phenol resin in 100 parts by weight of neoprene rubber in a toluene solution to add a solid content of 10% by weight, 70 parts by weight of CaCO 3 was added. The uniformly dispersed mixture was applied to a woven fabric made of nylon fiber using a knife coater in an amount of 20 g / m 2, dried at room temperature for 10 minutes, and then vulcanized with hot air at 150 ° C. for 5 minutes. After evaporating CaCO 3 completely by dipping in a 5% hydrochloric acid solution at room temperature for 10 minutes, a breathable waterproof polymer membrane was laminated on a nylon woven fabric by washing and drying.
이와 같이 하여 얻어진 고분자 막의 투습도 시험을 JISL-1099(A-1)법에 의해 실시하였는바, 투습도가 9800g/㎡·24hrs이었다.Thus, the moisture permeability test of the obtained polymer membrane was performed by JISL-1099 (A-1) method, and the water vapor transmission rate was 9800 g / m <2> * 24hrs.
[실시예 3]Example 3
CaCO3대신에 금속 알루미늄 분말을 사용하고, 5% 염산용액 대신에 30% 가성소다 용액을 사용한 것 이외에는 실시예 2와 동일하게 실시하여 통기 방수성 막을 나일론 직포상에 적층시켰으며, 얻어진 고분자 막의 투습도를 실시예 2와 동일한 방법으로 측정한 결과 8700g/㎡·24hrs이었다.Except for using the metal aluminum powder instead of CaCO 3 and 30% caustic soda solution instead of 5% hydrochloric acid solution was carried out in the same manner as in Example 2 to laminate a breathable waterproof membrane on a nylon woven fabric, the moisture permeability of the obtained polymer membrane The measurement in the same manner as in Example 2 resulted in 8700 g / m 2 · 24 hrs.
[실시예 4]Example 4
우레탄 프레폴리머(미국 유니로얄사제, L-83)를 MEK에 용해시켜 20% 용액으로 만들고, 경화제로 MOCA(4, 4'-methylene-bis-ortho-chloro aniline)를 MEK에 용해시켜 20%용액으로 만들었다. 상기 프레폴리머 용액 100중량부에 경화제 3중량부를 섞은 용액에 CaCO370중량부를 투입하여 균일하게 분산된 혼합물을 나이프 코터를 사용하여 28g/㎡ 의 양으로 나일론 직포상에 도포한 후, 상온에서 10분간 건조시키고 이어서 120℃ 가열공기로 10시간 경화시켰다. 상기 시료는 5% 염산 용액에 상온에서 15분간 침적시킨 후 꺼내어 세척 및 건조공정을 거쳐 통기방수성의 고분자막을 나일론 직포상에 적층시켰으며, 얻어진 고분자 막의 투습도 시험을 실시예 2와 동일한 방법으로 행하였는 바, 투습도가 9100g/㎡·24hrs로 나타났다.Dissolve urethane prepolymer (L-83, manufactured by U.S. Uni-Royal) in MEK to make 20% solution, and dissolve MOCA (4, 4'-methylene-bis-ortho-chloro aniline) in MEK with 20% solution with curing agent. Made with. 70 parts by weight of CaCO 3 was added to a solution mixed with 3 parts by weight of a curing agent to 100 parts by weight of the prepolymer solution, and then a uniformly dispersed mixture was coated on a nylon woven fabric in an amount of 28 g / m 2 using a knife coater, and then at room temperature. Drying was followed by curing for 10 hours with 120 DEG C heated air. The sample was immersed in a 5% hydrochloric acid solution at room temperature for 15 minutes, taken out, and washed and dried to laminate a breathable waterproof polymer membrane on a nylon woven fabric. , Water vapor transmission rate was 9100g / m 2 · 24hrs.
상기 실시예에서도 확인되듯이 본 발명에 따른 방법을 사용하여 투기 방수성의 고분자 막을 제조하는 경우, 통기 방수 효과가 우수한 고분자 막의 제조가 가능하고 또 종래에 비해 제조 공정이 단순하여 제조비용의 절감을 이룰 수 있는 등의 유용성을 얻을 수 있다.As can be seen from the above embodiment, when manufacturing the air permeable waterproof polymer membrane using the method according to the present invention, it is possible to manufacture a polymer membrane having excellent air permeability waterproof effect, and the manufacturing process is simple compared to the prior art to reduce the manufacturing cost Availability can be obtained.
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| KR1020000063458A KR20020032796A (en) | 2000-10-27 | 2000-10-27 | Method for the preparation of the polymer membrane having water-proof and gas permeable properties |
| PCT/KR2001/000608 WO2002034819A1 (en) | 2000-10-27 | 2001-04-11 | Method for the preparation of the polymer membrane having water-proof and gas permeable properties |
| AU2001250651A AU2001250651A1 (en) | 2000-10-27 | 2001-04-11 | Method for the preparation of the polymer membrane having water-proof and gas permeable properties |
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| EP2411129A4 (en) * | 2009-03-25 | 2013-04-10 | Univ Nanyang Tech | FILTERED |
| EP3178873A1 (en) | 2015-12-08 | 2017-06-14 | ETH Zurich | Waterproof and breathable, porous membranes |
| EP3858471A1 (en) * | 2020-01-31 | 2021-08-04 | Novamem AG | Solvent-free production of porous polymer structures |
| EP3875521A1 (en) * | 2020-03-06 | 2021-09-08 | ETH Zurich | Solvent free process for manufacturing membranes |
| EP3936658A1 (en) * | 2020-07-06 | 2022-01-12 | Dimpora AG | 3-dimensional manufacture of porous and waterproof membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62167332A (en) * | 1986-01-21 | 1987-07-23 | Mitsui Toatsu Chem Inc | Polyolefin porous film and its manufacturing method |
| JPH07118429A (en) * | 1993-10-26 | 1995-05-09 | Tonen Chem Corp | Manufacturing method of polypropylene porous film |
| KR960002226A (en) * | 1994-06-28 | 1996-01-26 | 조동식 | Sleep method of sound equipment |
| JPH0931228A (en) * | 1995-07-21 | 1997-02-04 | Tokuyama Corp | Porous film |
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| JPH0236938A (en) * | 1988-07-27 | 1990-02-06 | Mitsubishi Kasei Corp | Laminated material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62167332A (en) * | 1986-01-21 | 1987-07-23 | Mitsui Toatsu Chem Inc | Polyolefin porous film and its manufacturing method |
| JPH07118429A (en) * | 1993-10-26 | 1995-05-09 | Tonen Chem Corp | Manufacturing method of polypropylene porous film |
| KR960002226A (en) * | 1994-06-28 | 1996-01-26 | 조동식 | Sleep method of sound equipment |
| JPH0931228A (en) * | 1995-07-21 | 1997-02-04 | Tokuyama Corp | Porous film |
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| KR200454317Y1 (en) * | 2011-02-23 | 2011-06-28 | 신경임 | Medicine cabinet assembly |
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