KR101744487B1 - Polyurethane resin compositions for a non-swelling permeable waterproof cloth used surface activated nano-silica particles - Google Patents
Polyurethane resin compositions for a non-swelling permeable waterproof cloth used surface activated nano-silica particles Download PDFInfo
- Publication number
- KR101744487B1 KR101744487B1 KR1020150158570A KR20150158570A KR101744487B1 KR 101744487 B1 KR101744487 B1 KR 101744487B1 KR 1020150158570 A KR1020150158570 A KR 1020150158570A KR 20150158570 A KR20150158570 A KR 20150158570A KR 101744487 B1 KR101744487 B1 KR 101744487B1
- Authority
- KR
- South Korea
- Prior art keywords
- polyurethane resin
- moisture
- weight
- resin composition
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 66
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- 230000008961 swelling Effects 0.000 title claims abstract description 20
- 239000004744 fabric Substances 0.000 title description 12
- 230000035699 permeability Effects 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 silane compound Chemical class 0.000 claims abstract description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 26
- 238000004078 waterproofing Methods 0.000 claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 22
- 229910000077 silane Inorganic materials 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 7
- DUDCYUDPBRJVLG-UHFFFAOYSA-N ethoxyethane methyl 2-methylprop-2-enoate Chemical compound CCOCC.COC(=O)C(C)=C DUDCYUDPBRJVLG-UHFFFAOYSA-N 0.000 claims description 6
- 229920001427 mPEG Polymers 0.000 claims description 6
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 4
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 27
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 239000012528 membrane Substances 0.000 abstract description 5
- 239000006260 foam Substances 0.000 abstract description 3
- 230000002940 repellent Effects 0.000 abstract description 2
- 239000005871 repellent Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 45
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000544 Gore-Tex Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 230000008451 emotion Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/36—Silica
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
본 발명은 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물에 관한 것으로, 소수성 폴리우레탄 수지 100중량부를 기준으로, 입자크기가 10 ~ 1,000nm인 나노실리카 표면에 실란화합물(Silane compound)과 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)가 커플링된 실리케이트(Silicate) 10 ~ 15 중량부가 균일하게 혼합되어 이루어지는 것을 특징으로 한다.
본 발명의 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물은 소수성 폴리우레탄 수지에 첨가되는 나노실리카 입자의 표면에 실란화합물(Silane compound)과 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)가 커플링된 실리케이트(Silicate)를 함유함으로써 폴리우레탄 수지 및 용매와의 상용성이 양호하며, 수분침투로 인한 팽윤현상(swelling)이 발생되지 않으면서도 투습성이 우수하게 되는 효과가 있다.
또한, 본 발명의 폴리우레탄 수지조성물이 두께 10 ~ 30㎛ 정도의 필름형태로 형성되어 이루어지는 투습 방수포는 투습성 발현시 나타나는 팽윤현상이 현저히 저감되어 미관이 양호하며, 소재의 밀도가 높고 소재의 표면이 소수성(hydrophobic)을 띠기 때문에 습기에 대한 내가수분해성이 우수할 뿐만 아니라 내구성이 양호하게 되는 효과가 있다.The present invention relates to a polyurethane resin composition for a non-swellable moisture-permeable and waterproofing membrane using surface-treated nanosilica particles, and more particularly, to a polyurethane resin composition for surface-treated nanosilica particles, which comprises a hydrophobic polyurethane resin and a silane compound having a particle size of 10 to 1,000 nm 10 to 15 parts by weight of silicate coupled with a polyethylene glycol macromer is uniformly mixed.
The polyurethane resin composition for a non-swellable moisture-permeable and waterproofing sheet using the surface-treated nanosilica particles of the present invention comprises a silane compound and a polyethylene glycol macromer on the surface of the nanosilica particles added to the hydrophobic polyurethane resin, Is highly compatible with the polyurethane resin and the solvent and is excellent in the moisture permeability without causing swelling due to moisture permeation.
Further, the moisture-permeable and water repellent foam formed by the polyurethane resin composition of the present invention in the form of a film having a thickness of about 10 to 30 탆 has a remarkably reduced swelling phenomenon in the appearance of moisture permeability and has a good aesthetic appearance, Hydrophobicity, so that the hydrolysis resistance against moisture is excellent, and the durability is improved.
Description
본 발명은 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물에 관한 것으로, 더욱 상세하게는 소수성 폴리우레탄 수지에 첨가되는 나노실리카의 입자 표면에 실란화합물(Silane compound)과 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)가 커플링된 실리케이트(Silicate)를 함유함으로써, 폴리우레탄 수지 및 용매와의 상용성이 좋고 소재의 밀도가 높으면서 소수성(hydrophobic)을 띠기 때문에 이를 필름형태의 투습 방수포로 제조할 경우, 습기에 대한 내가수분해성이 우수하고 수분침투로 인한 팽윤현상(swelling)이 발생되지 않아 우수한 내구성과 미관, 그리고 양호한 투습성을 부여할 수 있는 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물에 관한 것이다.The present invention relates to a polyurethane resin composition for surface-treated nanosilica particles, and more particularly to a polyurethane resin composition for a non-swellable moisture-permeable and waterproofing polyurethane resin, which comprises a silane compound and a polyethylene glycol Polyethylene glycol macromer contains silicate which is coupled with polyurethane resin and solvent so that it has hydrophilic property while having high density of material. Therefore, it is made into a moisture permeable film of film type Non-swellable moisture-permeable waterproofing using surface-treated nanosilica particles that can impart excellent durability, aesthetic appearance, and good moisture permeability due to excellent hydrolysis resistance to moisture and swelling caused by moisture penetration Containing polyurethane resin composition.
투습방수소재는 다공질막 코팅법에 의한 가공법이 등장하기 이전부터 개발이 진행되어 왔는데, 1960년대 중순부터 코팅수지에 염화칼슘의 미세분말을 혼입하여 직물에 코팅한 수분흡수형 마이크로포어스(micropores) 피막제품이 개발되었다. 이 제품은 투습성이 우수하였으나 핀홀(pin-hole)에 의한 누수와 한냉시 촉감의 경화, 제품의 중후감 등의 원인으로 정착되지 못하였다. 선진국에서는 1970년대 중반부터 스포츠 붐이 일기 시작하여 투습방수성에 대한 수요가 강하게 요구되어 왔고, 이 시기 등장한 것이 다공질막 코팅법에 의한 투습방수포로서 당시 학계 및 업계를 포함한 모든 제조업자에 강한 충격을 주었다.The moisture permeable waterproof material has been developed before the process of the porous film coating method, and since the middle of the 1960s, a microporous coating of water-absorbing micropores The product was developed. This product was excellent in moisture permeability but it could not be fixed due to pinhole leakage, hardening of the feeling due to cold, and heavy feeling of the product. In developed countries, since the mid-1970s, the sports boom has started and demand for breathable and waterproof has been strongly demanded. At this time, moisture permeation defoamer by porous film coating method has strongly impacted all manufacturers including academia and industry at that time .
위와 같이, 방수가공 제품은 이미 개발되었으나 결로에 의한 끈적거림의 문제를 해결할 수 없어 투습성을 어떻게 부여할 것인가 하는 것이 당시 큰 문제로 대두되고 있었고, 미다공질막을 직물에 형성하는 투습방수소재의 기본원리는 코팅에 의해 제안됨에 따라 업계에서는 이것을 중심으로 하여 연구개발이 활성화하게 되었다. 그 결과, 다공질 막을 갖는 코팅제품이 개발되었는데, 이때 개발된 방법은 폴리우레탄의 습식코팅이 있으며, 1980년부터는 건식에 의한 아크릴수지의 미다공질 코팅이 개발되었고 그 후로 우레탄계, 아크릴계 및 습식, 건식코팅 미다공질 가공기술도 출현하였다.As described above, the waterproofing product has already been developed, but the problem of stickiness due to condensation can not be solved, and how to impart moisture permeability has been a major problem at the time. The basic principle of the moisture permeable and waterproofing material forming the microporous membrane Has been proposed by coatings, and research and development has become active in the industry. As a result, a coating product having a porous film was developed, in which a wet coating of polyurethane was developed, and a microporous coating of a dry acrylic resin was developed from 1980, and thereafter a urethane, acrylic and wet, Microporous machining technology has also appeared.
1977년에 시판된 고어텍스(Goretex, 제1세대)는 유지에 의한 오염, 계면활성제에 의한 방수성 저하 등의 문제가 지적되었으며, 1979년에는 이를 개량한 불소필름을 사용하여 수지를 얇게 도포한 투습방수소재(제2세대)도 개발되었다. 이들 후가공제품에 대하여 1981년에는 분리분할형 복합섬유에 의한 고밀도직물과 1983년도에는 극세섬유의 고혼섬사에 의한 폴리에스터 고밀도직물, 즉 논코팅(non-coating) 투습방수포도 개발되었다. 이들 고밀도직물은 일부에서 후가공제품과 경합하면서 투습방수소재의 한 분야를 확립하게 되었는데, 기능에서는 후가공, 감성에서는 고밀도직물로 대비되고 있다.Goretex (first generation) sold in 1977 pointed out problems such as oil contamination due to oil retention and deterioration of water resistance due to surfactants. In 1979, a modified fluorine film was used to apply a thin layer of resin Waterproof material (2nd generation) was also developed. For these post-processing products, high-density fabrics made of split-type composite fibers in 1981 and high-density polyester fabrics made of microfibers in 1983, non-coating moisture-proof fabrics, were also developed. These high-density fabrics compete with post-processing products in some parts and establish a field of breathable and waterproof material, which is prepared with high-density fabric in post-processing and emotion.
1980년대 전반은 내수압, 투습도 등 기본기능의 향상과 보온성, 스트레치성 등 신기능 부가가 진행되어 왔으며, 후반이 되면서 감성에 대한 요구가 강하게 되었다. 기능면은 결로 억제가 테마로 되었고, 고투습화 및 천연고분자 원료를 응용한 흡방습성의 부여 등이 진전되었으며, 보온성에서도 태양광선을 흡수한 축열방열형이 개발되었다. 1990년대에 들어서는 단가 저하가 주된 요인으로 소비자의 사용목적에 적합한 수준을 적재적소에 사용하고 지나친 과잉기능은 오히려 단가를 상승시키는 요인이 되기 때문에 회피하게 되었다. 이에 따라 현재에 이르기까지 고투습성을 유지하면서 내수압 향상, 그리고 세탁에 의한 내수압 저하와 바스락거리는 소리가 없고 높은 박리강도, 피막의 극막화(極膜化)에 의한 촉감향상 등 기능성 소재의 기본성능과 착용 쾌적성을 향상시키는 것이 주된 테마로 되고 있다.In the first half of 1980s, improvement of basic functions such as water pressure, moisture permeability, warmth, stretch and other new functions have been progressed. The functional surface has been dewatered to prevent condensation, and high moisture permeability and moisture absorption and deodorization imparted by using natural polymer materials have been advanced, and a heat storage type that absorbs sunlight has been developed even in warmth. In the 1990s, the decline in unit price was the main factor, and consumers were avoided because they used the appropriate level for the purpose of use and excessively excessive function was a factor that raised the unit price. Accordingly, the basic performance of functional materials such as improvement of water pressure while maintaining high moisture permeability up to the present, low water pressure due to washing, no rustling sound, high peeling strength, and improvement of touch by polar membrane The main theme is to improve wearing comfort.
현재, 투습방수소재의 개발에서 가장 큰 부류를 형성하고 있는 것이 내수압 향상일 것이다. 내수압 향상은 투습성과의 균형이 중요하고 투습성을 유지하면서 내수압을 증대시키는 방향으로 개발해야 되는데, 실제로 양 기능을 동시에 향상시키는 것은 어려운 점이 많다. 고내수압의 기준은 대략 5,000mmH2O 이상을 대상으로 하는데, 내수압만을 한정하면 코팅에 비해 라미네이팅하는 방법이 고성능이어야 하며, 무공질 필름으로 하면 20,000mmH2O 정도, 적어도 10,000mmH2O 이상의 내수압을 얻을 수 있다. 코팅은 라미네이트에 비해 내수압이 상대적으로 낮아 약 5,000mmH2O부터 10,000mmH2O 정도로서, 높은 것은 20,000mmH2O에 달하는 것도 있으나 2,000mmH2O 정도면 의류용으로 사용하는데 지장을 주지 않을 것으로 추정된다.At present, the most important class in the development of moisture permeable and waterproof materials is the improvement of the water pressure. The improvement of the water pressure should be developed in the direction of increasing the water pressure while maintaining the balance with the moisture permeability and maintaining the moisture permeability. In fact, it is difficult to improve both functions at the same time. Based on a high water pressure resistance is in the target substantially 5,000mmH 2 O or more, when the water pressure must be limited to only this method than the lamination coating and high performance, the 20,000mmH 2 O level, water pressure resistance of at least 10,000mmH 2 O When the imperforate film quality Can be obtained. The coating is estimated to be compared with the water pressure laminate is from about 2 O 5,000mmH relatively low degree 10,000mmH 2 O, it is high up to 20,000mmH 2 O, but does not prevent to use for clothing in about 2,000mmH 2 O .
그리고 투습성은 정해진 규정은 없으나 통상 4,000g/㎡24hrs 이상의 고투습도를 요구하고 있는 경우가 많은데, 요즘은 8,000g/㎡24hrs까지 향상시킨 제품도 개발되고 있다. 투습도를 향상시키기 위해서는 피막층을 얇게 하여 피막의 기공율을 높이는 것이 많이 사용되고 있고, 이는 역으로 내수압을 저하시킨다. 이 때문에 친수성 수지로 복층구조로 피막하기도 하고 천연고분자 원료를 이용하는 등의 연구도 진행되고 있다. 또 W/O형 에멀젼을 이용한 선택증발법도 얇은 고투습성의 피막이 얻어진다. 투습성을 높이려면 결로 억제효과를 높여야 하는데 결로 발생을 완전히 차단하기는 불가능하다. 일반적으로 의류의 투습도는 3,000g/㎠·24hrs 이상이면 충분하다고 말할 수 있으나 외기온도가 고온이면 일시적으로 다량의 발한이 따르는 경우도 있기 때문에 투습도는 높은 편이 좋다.Although there is no prescribed regulation for moisture permeability, it is often required to have a high humidity of 4,000g / ㎡24hrs or more. Nowadays, a product improved to 8,000g / ㎡24hrs is being developed. In order to improve the moisture permeability, it is often used to make the coating layer thinner to increase the porosity of the coating, which in turn decreases the water pressure. For this reason, researches are being conducted such as coating a multilayer structure with a hydrophilic resin and using a natural polymer material. In addition, a selective evaporation method using a W / O type emulsion also provides a thin film having a high moisture permeability. In order to increase the moisture permeability, it is necessary to increase the condensation suppression effect, and it is impossible to completely prevent condensation from occurring. Generally, it can be said that the water vapor permeability of the clothes is more than 3,000 g / cm 2 24 hrs. However, when the outside temperature is high, a large amount of perspiration may be followed temporarily.
위와 같이, 의류용 투습방수소재의 경우에는 내수압과 투습도 등과 같은 기능성을 가장 중요시하고 있기 때문에 모든 연구개발이 고기능성에 집중되고 있으나 투습도를 향상시키기 위해 피막층을 얇게 하여 피막의 기공율(氣孔率)을 높인 제품은 역으로 내수압을 저하시킨다. 또한, 투습도를 높이기 위해 지나치게 친수성 소재를 도입하게 되면 실제 의류용으로 사용할 경우 내수압과 투습도는 뛰어나지만 눈이나 비, 땀 등과 같은 수분에 장기간 노출시 친수성 필름층이 팽윤(swelling)하여 의복이 쉽게 뒤틀어져 외관을 크게 훼손하는 문제점이 발생되고 있다. 그리고 투습방수소재로 된 의류를 세탁함으로 인해 발수성이 저하되면 이러한 현상은 더욱 심하게 일어나게 되며, 상기 필름층이 팽윤된 상태의 경우 모든 강도와 물성이 약해지기 때문에 이 상태로 장시간 착용을 하게 되면 필름이 손상되어 기능성이 크게 저하되는 문제점이 있다.As described above, in the case of the moisture permeable and waterproof material for clothes, since the functions such as water pressure and moisture permeability are most important, all research and development are concentrated on high functionality, but in order to improve the moisture permeability, the film thickness is decreased to decrease the porosity Increased products adversely affect water pressure. In addition, when an excessively hydrophilic material is introduced to increase the moisture permeability, the waterproofing and moisture permeability is excellent when used for actual clothing, but when exposed to water such as snow, rain or sweat for a long time, the hydrophilic film layer swells, And thus the appearance is greatly damaged. When the water repellency of the clothes is deteriorated due to washing of the moisture permeable and waterproof clothing, such a phenomenon occurs more severely. When the film layer is swollen, all the strength and physical properties are weakened. There is a problem that the functionality is greatly deteriorated.
이러한 문제점을 해결하기 위해, 대한민국 등록특허공보 제10-0909677호에서는 투습방수필름 및 상기 투습방수필름의 적어도 일 표면에 친수성 폴리우레탄수지와 비점이 상이한 3종 이상의 용제로 이루어지는 친수성 폴리우레탄 조성물을 캐스트하여 상기 친수성 폴리우레탄 조성물에 함유된 용제들의 비점 온도로 열처리하되, 가장 비점이 낮은 용제로부터 비점이 높아지는 용제의 순서대로 다단 열처리를 실시하여 형성되는 모노리스 멤브레인을 포함하는 비팽윤성 적층필름 및 그 제조방법을 개시하고 있으나, 상기 적층필름은 다단 열처리를 실시하여 모노리스 멤브레인을 제조한다는 공정상의 어려움이 있다.In order to solve such a problem, Korean Patent Registration No. 10-0909677 discloses a hydrophilic polyurethane composition comprising at least one surface of a moisture permeable waterproof film and a moisture permeable waterproof film, wherein the hydrophilic polyurethane composition is composed of at least three solvents different in boiling point from the hydrophilic polyurethane resin Swellable film comprising a monolithic membrane formed by subjecting a solvent contained in the hydrophilic polyurethane composition to a heat treatment at a boiling point temperature and a solvent having a boiling point higher than that of the solvent having the lowest boiling point, However, there is a difficulty in the process of manufacturing a monolithic membrane by performing a multi-stage heat treatment on the laminated film.
또한, 대한민국 공개특허공보 제10-2014-0082161호를 보면, 투습성과 내수압이 우수하고 촉감이 부드러우며 박리강도 및 세탁 내구성이 우수한 고기능성 투습방수포를 제공하기 위해, 소수성 폴리우레탄 피막을 적용하여 친수성 필름층의 팽윤(swelling)에 따른 문제를 해결하고 고투습성을 부여하기 위해 흡습성이 우수한 나노 상태의 미립자 성분을 투입하며, 나노 사이즈의 미세기공을 형성할 수 있는 첨가제를 투입함으로써 고감성과 고투습성이 우수한 고기능성의 라미네이팅 투습방수포 및 그 제조방법에 대한 것으로, 상기 고기능성의 라미네이팅 투습방수포의 제조방법은 이형지 상에 소수성이 높은 수지, 나노 상태의 미립자 및 첨가제로 구성된 수지 조성물을 코팅한 후 건조하여 다공성(Micorporous) 필름층을 형성하는 단계; 및 상기 필름 층에 폴리우레탄 접착제를 이용 전면 접착하거나 도트 접착을 하여 원단과 결합시켜 라미네이팅하는 단계로 구성됨을 특징으로 하고 있다.Korean Patent Laid-Open Publication No. 10-2014-0082161 discloses a hydrophilic polyurethane film which is excellent in moisture permeability, water pressure, smooth touch, excellent in peel strength and durability, In order to solve the problem caused by the swelling of the film layer and to impart high moisture permeability, a nano-state fine particulate component having excellent hygroscopicity is introduced, and an additive capable of forming nano- The present invention relates to a highly functional laminating moisture-proofing protective film and a method of manufacturing the same. In the method of manufacturing the highly functional laminating moisture-proofing protective film, a resin composition comprising a highly hydrophobic resin, nano- To form a microporous film layer; And a step of laminating the film layer by bonding the entire surface of the film layer with a polyurethane adhesive or by bonding the layer with the fabric.
그 외에도, 대한민국 공개특허공보 제10-2014-0090259호(출원인 : 쓰리엠 이노베이티브 프로퍼티즈 컴파니, 미국)에 기재되어 있는 나노실리카 함유 폴리시아네이트 에스테르 조성물을 보면, 경화성 폴리시아네이트 에스테르 수지 및 30중량% 이상의 본질적으로 휘발성 물질이 없는, 실질적으로 구형인 표면-개질된 실리카 나노입자의 콜로이드성 분산물을 갖는 경화성 수지 졸이 제공되며, 여기서 경화성 수지 졸은 실리카 나노입자 및 경화성 폴리시아네이트 에스테르 수지의 총 중량을 기준으로 200중량 백만분율 이하의 알칼리 금속 및 알칼리 토금속 이온을 포함한다. 이러한 경화성 수지 졸 및 보강 섬유를 포함하는 조성물, 이러한 조성물의 제조 공정, 및 이러한 경화성 수지 졸 및 조성물을 사용하여 제조한 다양한 용품 또한 제공된다.In addition, in the nanosilica-containing polycyanate ester composition described in Korean Patent Laid-Open Publication No. 10-2014-0090259 (Applicant: 3M Innovative Properties Company, USA), the curable polycyanate ester resin and There is provided a curable resin sol having a colloidal dispersion of substantially spherical surface-modified silica nanoparticles, wherein the curable resin sol is a mixture of silica nanoparticles and a hardenable poly cyanate ester Based on the total weight of the resin, of up to 200 weight percent of alkali and alkaline earth metal ions. Compositions comprising such curable resin sols and reinforcing fibers, processes for making such compositions, and various articles made using such curable resin sols and compositions are also provided.
한편, 본 발명에서는 우레탄 수지에 투습성을 갖는 폴리에틸렌글리콜 등을 붙여 투습성을 부여하는 것이 아니라, 첨가제인 나노실리카 입자의 표면에 실란화합물과 폴리에틸렌글리콜 마이크로머가 커플링된 실리케이트를 혼합함으로써 팽윤현상 저감은 물론 투습성을 부여할 수 있는 투습 방수포용 폴리우레탄 수지조성물을 개발하여 본 발명을 완성한 것이다.On the other hand, in the present invention, rather than imparting moisture permeability to a polyurethane resin having moisture permeability to a urethane resin, a silane compound and a silicate coupling with a polyethylene glycol micro- The present invention has been completed by developing a polyurethane resin composition for breathable waterproofing which can impart moisture permeability.
본 발명의 목적은 소수성 폴리우레탄 수지에 첨가되는 나노실리카 입자의 표면에 실란화합물(Silane compound)과 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)가 커플링된 실리케이트(Silicate)를 함유함으로써, 폴리우레탄 수지 및 용매와의 상용성이 좋고 소재의 밀도가 높으면서 소수성(hydrophobic)을 띠기 때문에 이를 필름형태의 투습 방수포로 제조할 경우, 습기에 대한 내가수분해성이 우수하고 수분침투로 인한 팽윤현상(swelling)이 발생되지 않아 우수한 내구성과 미관, 그리고 양호한 투습성을 부여할 수 있는 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물을 제공하는 것이다.It is an object of the present invention to provide a hydrophobic polyurethane resin composition which contains a silicate compound and a polyethylene glycol macromer-linked silicate on the surface of a nanosilica particle added to a hydrophobic polyurethane resin, When the film is formed into a moisture-permeable tarpaulin in the form of a film because it has good compatibility with a solvent and has a high density of material and is hydrophobic, swellability due to moisture penetration is excellent due to excellent hydrolysis resistance against moisture Swellable waterproof breathable polyurethane resin composition using surface-treated nanosilica particles which can provide excellent durability, aesthetic appearance, and good moisture permeability.
본 발명에 의한 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물은 소수성 폴리우레탄 수지 100중량부를 기준으로, 입자크기가 10 ~ 1,000nm인 나노실리카 표면에 실란화합물(Silane compound)과 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)가 커플링된 실리케이트(Silicate) 10 ~ 15 중량부가 균일하게 혼합되어 이루어지는 것을 특징으로 한다.The polyurethane resin composition for a non-swellable moisture-permeable and waterproofing sheet using the surface-treated nanosilica particles according to the present invention comprises a silane compound on the surface of a nanosilica having a particle size of 10 to 1,000 nm based on 100 parts by weight of a hydrophobic polyurethane resin. And 10-15 parts by weight of silicate coupled with a polyethylene glycol macromer are uniformly mixed with each other.
본 발명의 바람직한 실시예에 따르면, 상기 실란화합물(Silane compound)은 3-메타 아크릴록시 프로필 트리에톡시 실란{3-methacryloxypropyl triethoxysilane}, 3-메타 아크릴록시 프로필 메틸디메톡시 실란{3-Methacryloxypropylmethyldimethoxysilane}, 3-아크릴록시 프로필 트리메톡시 실란{3-acryloxy propyl trimethoxysilane} 중에서 선택되는 어느 1종 이상의 물질이며, 상기 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)는 수평균분자량 950, 1500, 4,000 중에서 선택되는 어느 1종 이상의 폴리(에틸렌 글리콜) 메틸 에테르 메타아크릴레이트{Poly(ethylene glycol) methyl ether methacrylate}를 사용하는 것을 특징으로 하고 있다.According to a preferred embodiment of the present invention, the silane compound may include 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxy propyl trimethoxysilane, and the polyethylene glycol macromer is any one selected from the group consisting of a number average molecular weight of 950, 1500 and 4,000. Poly (ethylene glycol) methyl ether methacrylate (poly (ethylene glycol) methyl ether methacrylate} is used.
또한, 상기 폴리우레탄 수지조성물은 소수성 폴리우레탄 수지 100중량부에 대하여 디메틸포름아미드(Dimethylformamide, DMF) 5 ~ 15중량부; 톨루엔(Toluene) 15 ~ 25중량부; 메틸에틸케톤(Methylethylketone, MEK) 15 ~ 25중량부로 이루어지는 용매를 포함함으로써 점도가 3,000 ~ 3,200cps(25℃) 정도로 형성된다.The polyurethane resin composition may further comprise 5 to 15 parts by weight of dimethylformamide (DMF) relative to 100 parts by weight of the hydrophobic polyurethane resin; 15 to 25 parts by weight of toluene (Toluene); And 15 to 25 parts by weight of methylethylketone (MEK), so that the viscosity is about 3,000 to 3,200 cps (25 캜).
그리고 상기 폴리우레탄 수지조성물을 이형지 상에 코팅하여 두께 10 ~ 30㎛인 필름형태의 투습 방수포로 형성될 수 있으며, 상기 필름형태의 투습 방수포는 내수압 10,000mmH20(ISO 0811) 이상이고, 투습도 7,700g/㎡24hrs(JIS L 1099A-1법) 이상인 것을 특징으로 하고 있다.And by coating the polyurethane resin composition on a release liner may be formed from a breathable tarpaulin of a film thickness of 10 ~ 30㎛ form, and moisture-permeable film of the tarpaulin type water pressure 10,000mmH 2 0 (ISO 0811) or more, the moisture permeability 7700 g / m < 2 > 24hrs (JIS L 1099A-1 method).
본 발명의 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물은 소수성 폴리우레탄 수지에 첨가되는 나노실리카 입자의 표면에 실란화합물(Silane compound)과 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)가 커플링된 실리케이트(Silicate)를 함유함으로써 폴리우레탄 수지 및 용매와의 상용성이 양호하며, 수분침투로 인한 팽윤현상(swelling)이 발생되지 않으면서도 투습성이 우수하게 되는 효과가 있다.The polyurethane resin composition for a non-swellable moisture-permeable and waterproofing sheet using the surface-treated nanosilica particles of the present invention comprises a silane compound and a polyethylene glycol macromer on the surface of the nanosilica particles added to the hydrophobic polyurethane resin, Is highly compatible with the polyurethane resin and the solvent and is excellent in the moisture permeability without causing swelling due to moisture permeation.
또한, 본 발명의 폴리우레탄 수지조성물이 두께 10 ~ 30㎛ 정도의 필름형태로 형성되어 이루어지는 투습 방수포는 투습성 발현시 나타나는 팽윤현상이 현저히 저감되어 미관이 양호하며, 소재의 밀도가 높고 소재의 표면이 소수성(hydrophobic)을 띠기 때문에 습기에 대한 내가수분해성이 우수할 뿐만 아니라 내구성이 양호하게 되는 효과가 있다.Further, the moisture-permeable and water repellent foam formed by the polyurethane resin composition of the present invention in the form of a film having a thickness of about 10 to 30 탆 has a remarkably reduced swelling phenomenon in the appearance of moisture permeability and has a good aesthetic appearance, Hydrophobicity, so that the hydrolysis resistance against moisture is excellent, and the durability is improved.
이하에서는 본 발명에 의한 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물의 제조방법에 대하여 상세하게 설명하기로 하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 예시하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, a method for preparing a polyurethane resin composition for a non-swellable moisture-permeable and waterproofing membrane using the surface-treated nanosilica particles according to the present invention will be described in detail. So as not to imply that the technical idea and scope of the present invention are limited.
일반적으로, 폴리우레탄 수지는 중합체 중에 이소시아네이트기(-NCO)와 수산기(-OH)의 반응에 의해서 생성된 우레탄결합을 기본으로 하여 생성된 수지이고 그 원료로서 폴리올, 이소시아네이트, 체인확장제 등이 있으며, 각종 용제가 첨가되어 용액중합방법으로 제조된다. 폴리우레탄 수지의 특징은 피막강도, 접착강도가 크기 때문에 얇은 코팅막의 제조가 가능하고 코팅피막의 탄력성이 풍부하여 촉감이 부드러우며, 다공질막 필름으로 제조할 수 있어 투습성, 통기성을 부여할 수 있고 내한성이 우수하며, 가소제를 사용하지 않고 가공하기 때문에 가소제로 인하여 발생되는 작업성 문제가 적다.Generally, a polyurethane resin is a resin produced on the basis of a urethane bond formed by the reaction of an isocyanate group (-NCO) with a hydroxyl group (-OH) in a polymer, and a polyol, isocyanate, Various solvents are added to prepare a solution polymerization method. The characteristics of the polyurethane resin are that it is possible to produce a thin coating film because of its large film strength and high adhesive strength, and it is possible to produce a porous film film by softening the feel by abundant elasticity of the coating film and providing moisture permeability and breathability, And since it is processed without using a plasticizer, there is little workability problem caused by the plasticizer.
폴리우레탄 수지는 사용되는 원재료에 따라 친수성 타입(Hydrophilic type)과 소수성 타입(Hydrophobic type)으로 나눌 수 있는데, 친수성 폴리우레탄 수지는 폴리에틸렌글리콜(Polytethylene glycol, PEG)을 원료로 사용함으로써 투습성이 우수한 친수성 수지를 합성할 수 있다. 그러나 PEG를 사용한 친수성 폴리우레탄의 경우, 팽윤현상(swelling)이 발생하여 미관상 좋지 않을 뿐만 아니라 내가수분해성이 나쁘기 때문에 물이나 땀 등에 쉽게 분해될 우려가 있다. 한편, 소수성 폴리우레탄 수지는 폴리테트라메틸렌 에테르 글리콜(Polytetramethylene ether glycol, PTMG), 폴리프로필렌글리콜 (Polypropylene glycol, PPG), 폴리에스테르폴리올(Polyester polyol), 폴리카보네이트폴리올(Polycarbonate polyol) 등을 사용함으로써 내수압이 우수한 소수성 수지를 제조할 수 있는데, 소수성 우레탄수지는 물과 섞이지 않고 내구성이 우수하며, 완전경화 시에 내수성 및 내유성이 강하다.The polyurethane resin can be divided into a hydrophilic type and a hydrophobic type according to raw materials used. The hydrophilic polyurethane resin is made of polyethylene glycol (PEG) as a raw material, Can be synthesized. However, in the case of hydrophilic polyurethane using PEG, swelling occurs, which is not good for cosmetics, and is easily degraded to water or sweat because of poor hydrolysis resistance. On the other hand, the hydrophobic polyurethane resin can be manufactured by using a polytetramethylene ether glycol (PTMG), a polypropylene glycol (PPG), a polyester polyol, a polycarbonate polyol, This hydrophobic resin can be produced. The hydrophobic urethane resin is excellent in durability without mixing with water, and has high water resistance and oil resistance when fully cured.
종래기술에 의하면, 라미네이팅 투습방수포의 제조방법에 있어 원단에 대한 고투습성을 부여하기 위해 폴리우레탄 접착제에 실리카(silica) 또는 실리케이트(silicate) 등과 같은 흡습성이 우수한 나노 상태의 미립자 성분을 5 내지 30중량부 정도 투입함으로써 나노 사이즈의 미세기공을 형성할 수 있다고 알려져 있으나, 이는 투습성을 양호하게 하기 위하여 다공성 및 흡수성을 갖는 다량의 미립자 성분을 투입하는데 따르는 입자의 분산성 불량, 필름강도 약화 등으로 인하여 제품에 심각한 부작용을 초래할 우려가 있다.According to the prior art, in order to impart high moisture permeability to a fabric in a manufacturing method of a laminating moisture-proofing and defoaming agent, a nano-state fine particle component having excellent hygroscopicity such as silica or silicate is added to a polyurethane adhesive in an amount of 5 to 30 wt. It is known that nano-sized fine pores can be formed by injecting a large amount of fine particles having a porosity and an absorbency in order to improve the moisture permeability. However, due to poor dispersibility of particles and weakness of the film, Which can cause serious side effects.
또한, 현재 시중에 판매되고 있는 기능성 투습방수용 폴리우레탄 소재는 투습성을 발현하기 위해 폴리에틸렌글리콜이라는 폴리올을 원재료로 사용하여 제조되는 경우가 대부분인데, 이 원재료가 투습성을 발현하는 역할을 하지만, 이는 물(가수분해) 또는 땀에 닿을 경우 팽윤현상이 일어나고 내구성 또한 좋지 않으며, 팽윤현상이 일어나지 않는 소재의 경우 어플리케이션이 어렵고 고가인 경우가 대부분이다.In order to develop moisture permeability, the polyurethane material for functional breathable waterproofing which is currently on the market is mostly produced by using a polyol such as polyethylene glycol as a raw material. This raw material plays a role of expressing the moisture permeability, Hydrolysis) or sweat, swelling occurs and the durability is not good. In the case of a material which does not cause swelling, the application is often difficult and expensive.
이를 개선하기 위해, 본 발명에서는 우레탄 수지에 투습성을 가지는 폴리에틸렌글리콜을 붙여 투습성을 부여하는 것이 아니라, 첨가제인 나노실리카 입자의 표면에 실란화합물과 폴리에틸렌글리콜 마이크로머가 커플링된 실리케이트를 혼합함으로써 팽윤현상 저감은 물론 투습성을 부여할 수 있는 투습 방수포용 폴리우레탄 수지조성물을 제공하고자 한다.In order to solve this problem, in the present invention, the polyurethane glycol having moisture permeability is bonded to the urethane resin to impart moisture permeability, and a silane compound and a polyethylene glycol micromer-linked silicate are mixed on the surface of the nanosilica particles as an additive to reduce swelling Waterproofing polyurethane resin composition capable of imparting moisture permeability as well as moisture permeability to water.
본 발명은 우레탄수지를 이용하여 팽윤현상이 현저히 저감되었으면서도 투습성을 발현하기 위해, 소수성 폴리우레탄 수지 100중량부에 입자크기가 10 ~ 1,000nm인 나노실리카 표면에 실란화합물(Silane compound)과 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)가 커플링된 실리케이트(Silicate) 10 ~ 15 중량부가 균일하게 혼합되어 이루어지는 것을 특징으로 한다.The present invention relates to a process for producing a polyurethane resin composition, which comprises using a urethane resin to silane compound (s) on the surface of a nanosilica having a particle size of 10 to 1,000 nm and 100 g / m < 2 > of a hydrophobic polyurethane resin in order to exhibit moisture permeability while remarkably reducing swelling, And 10-15 parts by weight of silicate (Polyethylene glycol macromer) -coupled silicate is uniformly mixed.
즉, 상기 나노실리카 입자의 표면 처리는 나노실리카에 실란화합물을 커플링시키고 투습성 부여가 가능한 폴리에틸렌글리콜 마크로머를 넣어 반응시키는 공정으로, 실란화합물과 폴리에틸렌글리콜 마크로머가 결합된 실리케이트로 나노실리카를 표면 처리함으로써 폴리우레탄 수지의 팽윤현상이 현저히 저감되었으면서도 투습성을 발현할 수 있게 되는 것이다.That is, the surface treatment of the nanosilica particles is a step of coupling the silane compound to the nanosilica and adding the polyethylene glycol macromer capable of imparting the moisture permeability to the nanosilica particle. The nanosilica surface treatment is performed with a silicate combined with a silane compound and a polyethylene glycol macromer The swelling phenomenon of the polyurethane resin can be remarkably reduced and the moisture permeability can be exhibited.
상기 실란화합물(Silane compound)의 경우 이중결합을 가진 실란커플링제(Silane coupling agent)를 사용할 수 있으며, 3-메타 아크릴록시 프로필 트리에톡시 실란{3-methacryloxypropyl triethoxysilane}, 3-메타 아크릴록시 프로필 메틸디메톡시 실란{3-Methacryloxypropylmethyldimethoxysilane}, 3-아크릴록시 프로필 트리메톡시 실란{3-acryloxy propyl trimethoxysilane} 중에서 선택되는 어느 1종 이상의 물질을 이용하여 나노실리카의 표면을 처리하였으며, 상기 실란화합물이 나노실리카가 가지고 있는 친수성을 완전히 블로킹(blocking)하게 되거나 나노실리카 표면에 강한 소수성을 띠게 되면 투습성이 제대로 안 나올 가능성이 있으므로 이를 고려해서 가장 적합한 종류의 실란화합물을 선택하였음을 밝혀두고자 한다.In the case of the silane compound, a silane coupling agent having a double bond may be used. Examples of the silane coupling agent include 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl methyl The surface of the nanosilica is treated with at least one material selected from among dimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and 3-acryloxypropyl trimethoxysilane, The hydrophilicity of the nanosilica is blocked completely or the nanosilica surface has strong hydrophobicity, the moisture permeability may not be satisfactory. Therefore, the most suitable type of silane compound is selected.
실리카 입자와 3-메타 아크릴록시 프로필 트리에톡시 실란과의 화학구조는 하기 반응식 1과 같다.The chemical structure of the silica particles and the 3-methacryloxypropyltriethoxysilane is shown in the following Reaction Scheme 1.
<반응식 1><Reaction Scheme 1>
상기 반응 이후, 투습성 발현을 위해 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)를 넣고 라디칼반응을 진행하게 되면 최종적으로 하기 반응식 2와 같은 화학구조의 투습성을 가진 표면 처리된 나노실리카를 얻을 수 있게 된다.After the reaction, if a polyethylene glycol macromer is added for the moisture-permeable development and the radical reaction proceeds, the surface treated nanosilica having the chemical structure as shown in the following reaction formula 2 can be obtained.
<반응식 2><Reaction Scheme 2>
상기 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)는 수평균분자량 950, 1500, 4,000 중에서 선택되는 어느 1종 이상의 폴리(에틸렌 글리콜) 메틸 에테르 메타아크릴레이트{Poly(ethylene glycol) methyl ether methacrylate}를 사용하는 것이 바람직하며, 상기 폴리에틸렌글리콜 마크로머의 분자량은 상기 제시된 범위에 벗어난 종류를 사용하면 실란화합물과의 반응성이 저하되는 것으로 분석되었다. 일반적으로 마크로머(Macromer)는 중합체사슬의 말단에 중합가능한 기를 가진 중합체인 말단반응성고분자로서 기능성 그룹을 도입하기 위해 설계되어 높은 반응성을 가진 중합체에 해당된다.The polyethylene glycol macromer may be any one selected from the group consisting of poly (ethylene glycol) methyl ether methacrylate having a number average molecular weight of 950, 1500 and 4,000 And it is analyzed that the reactivity with the silane compound is lowered when the molecular weight of the polyethylene glycol macromer is out of the above range. In general, macromers are polymers with high reactivity designed to introduce functional groups as terminal reactive macromolecules that are polymers with polymerizable groups at the ends of the polymer chains.
또한, 본 발명에서는 나노실리카 표면처리시 반응의 균일성과 편의를 위하여 톨루엔을 용매로 사용하였으며, 이때 나노실리카와 톨루엔의 비율을 1/5 ~ 1/20의 중량비로 조절하는 것이 바람직하다. 상기 반응에 있어서 반응종료 후 사용된 용매와 미반응 실란은 감압여과를 통하여 제거할 수 있으며, 감압여과 후에 얻은 실리케이트는 에탄올을 이용하여 5회(3 ~ 7회) 정도 세척하고 100℃(90 ~ 110℃)의 드라이오븐에서 약 10시간(5 ~ 15시간) 동안 건조 처리하면 나노실리카 표면에 실란화합물과 폴리에틸렌글리콜 마크로머가 적합하게 커플링된 실리케이트를 안정적으로 형성할 수 있다.Also, in the present invention, toluene is used as a solvent for the uniformity and convenience of the reaction in the surface treatment of the nanosilica, and it is preferable to adjust the ratio of the nanosilica and toluene to a weight ratio of 1/5 to 1/20. After the completion of the reaction, the solvent and the unreacted silane can be removed by filtration under reduced pressure. After the filtration under reduced pressure, the obtained silicate is washed 5 times (3 to 7 times) with ethanol, 110 ° C) in a dry oven for about 10 hours (5 to 15 hours) can stably form a silicate compound suitably coupled to the surface of the nanosilica with a silane compound and a polyethylene glycol macromer.
본 발명에 의한 폴리우레탄 수지조성물은 입자크기가 10 ~ 1,000nm인 나노실리카를 실란화합물과 폴리에틸렌글리콜 마크로머로 표면 처리한 나노상태의 흡수성 미립자인 실리케이트를 형성한 후 이를 소수성 폴리우레탄 수지 100중량부를 기준으로 10 ~ 15중량부 정도로 첨가되고 균일하게 혼합되는바, 상기 나노상태의 실리케이트는 비표면적이 양호하여 상기 폴리우레탄 수지조성물로 제조된 투습 방수포에 수분에 대한 팽윤현상이 현저히 저감되었으면서도 우수한 투습기능을 부여하는 역할을 한다.The polyurethane resin composition according to the present invention is a nano-state absorbent microparticle obtained by surface-treating nano silica having a particle size of 10 to 1,000 nm with a silane compound and a polyethylene glycol macromer, and then adding 100 parts by weight of the hydrophobic polyurethane resin The nano-state silicate has a good specific surface area, so that the moisture permeation protection fabric made of the polyurethane resin composition is remarkably reduced in swelling with respect to moisture, Function.
만일 상기 실리케이트를 10중량부 미만으로 함유할 경우 팽윤현상과 내수압은 우수하나 투습성이 불량하게 되며, 15중량부를 초과할 경우에는 팽윤현상과 투습성은 우수하나 내수압이 불량하게 될 우려가 있다. 그리고 폴리우레탄 수지에 혼입되는 실리케이트는 혼합 및 분산성이 제품의 품질에 매우 중요한 요소임을 고려할 때, 상기 폴리우레탄 수지조성물의 점도는 약 3,000 ~ 3,200cps(25℃ 기준) 정도로 형성하는 것이 좋다.If the silicate is contained in an amount of less than 10 parts by weight, the swelling phenomenon and the water pressure are excellent but the moisture permeability is poor. If the silicate is more than 15 parts by weight, the swelling phenomenon and the moisture permeability are excellent, but the water pressure may be poor. The viscosity of the polyurethane resin composition is preferably about 3,000 to 3,200 cps (based on 25 ° C), considering that the mixing and dispersing properties of the silicate incorporated in the polyurethane resin are very important factors for the quality of the product.
상기 나노상태의 실리케이트는 입자크기가 10 ~ 1,000nm로서, 통상의 나노실리카와 달리 폴리우레탄 수지 및 용매와의 상용성이 좋기 때문에 이를 포함하는 폴리우레탄 수지조성물은 밀도가 높으면서도 점도가 낮고 소수성(hydrophobic)을 띠고 있어 이를 필름형태의 투습 방수포로 제조할 경우, 내수성 및 내유성은 물론 내구성이 우수할 뿐만 아니라 수분침투로 인한 팽윤현상(swelling)이 거의 발생되지 않는다.Since the nano-state silicate has a particle size of 10 to 1,000 nm, the polyurethane resin composition containing the nano-state silicate has good compatibility with the polyurethane resin and the solvent unlike the conventional nanosilica. Therefore, the polyurethane resin composition containing the silicate has a low density, hydrophobic), and when it is manufactured as a moisture permeable waterproof film of film type, not only water resistance and oil resistance but also durability are excellent, and swelling due to moisture penetration hardly occurs.
그리고 상기 폴리우레탄 수지조성물은 용매를 포함함으로써 코팅할 수 있는 상태로 되는데, 상기 용매는 폴리우레탄 수지와 상용성이 있는 것이라면 그 구체적인 종류에 특별한 제한이 없지만, 본 발명에서는 소수성 폴리우레탄 수지 100중량부 및 실리케이트 10 ~ 15중량부로 구성될 경우, 용매를 35 ~ 65중량부 범위로 혼합하여 사용하게 되면 점도가 3,000 ~ 3,200cps(25℃ 기준) 정도로 밀도가 높고 투습방수효과가 우수한 필름을 형성하기에 적합할 뿐만 아니라 제품의 내구성도 탁월한 것으로 연구되었다.The polyurethane resin composition can be coated by including a solvent. The solvent is not particularly limited as long as it is compatible with the polyurethane resin. In the present invention, 100 parts by weight of the hydrophobic polyurethane resin And 10 to 15 parts by weight of silicate, when the solvent is mixed in the range of 35 to 65 parts by weight, a film having a high viscosity of about 3,000 to 3,200 cps (based on 25 ° C) and excellent moisture permeability is formed It has been studied not only that it is suitable but also that the durability of the product is excellent.
특히, 본 발명에서 사용하는 용매는 디메틸포름아미드(Dimethylformamide, DMF) 5 ~ 15중량부, 톨루엔(Toluene) 15 ~ 25중량부, 메틸에틸케톤(Methylethylketone, MEK) 15 ~ 25중량부로 이루어지는 복합용매를 사용하는 것이 폴리우레탄 수지에 대한 용해성을 극대화할 수 있어 코팅필름의 내구성과 기밀성을 오랫동안 유지하기에 바람직하다.In particular, the solvent used in the present invention is a complex solvent comprising 5 to 15 parts by weight of dimethylformamide (DMF), 15 to 25 parts by weight of toluene (toluene) and 15 to 25 parts by weight of methylethylketone (MEK) It is possible to maximize the solubility in the polyurethane resin, so that the durability and the airtightness of the coating film are maintained for a long time.
또한, 상기 폴리우레탄 수지조성물을 이형지 상에 코팅하여 두께 10 ~ 30㎛인 필름형태의 투습 방수포로 형성될 수도 있으며, 상기 필름형태로 형성되는 투습 방수포는 두께가 얇게 형성됨에 따라 촉감이 부드러우면서도 내수압이 약 10,000mmH20(ISO 0811), 투습도는 약 8,000g/㎡24hrs(JIS L 1099A-1법) 정도의 고기능성 제품에 사용될 수 있다.Also, the polyurethane resin composition may be coated on a release paper to form a moisture-permeable waterproofing film having a thickness of 10 to 30 占 퐉. The moisture permeable waterproofing foam formed in the film form has a thin thickness, It can be used for high-performance products with a water pressure of about 10,000 mmH 2 0 (ISO 0811) and a moisture permeability of about 8,000 g / ㎡ 24 hrs (JIS L 1099A-1 method).
그러나 종래 투습이 되는 기능성 제품의 경우, 기공형은 필름강도가 떨어지고 공정이 까다로운 단점이 있으며, 무공형은 친수성으로 내가수분해성이 취약하고 팽윤현상(swelling)이 발생되기 때문에 미관상 좋지 않았으나, 본 발명에 따른 투습 방수포는 제조공정이 쉽고 장시간 수분에 노출되더라도 팽윤현상이 거의 발생되지 않으며, 또 필름의 강도 및 내가수분해성이 매우 높아 내구성도 좋고 미관도 우수하다.However, in the case of the functional product which is conventionally permeable to moisture, the pore type has a disadvantage in that the film strength is low and the process is difficult, and the non-porous type is hydrophilic and poor in hydrolysis resistance and swell, The waterproofing fabric according to the present invention is easy to manufacture and does not cause swelling even when it is exposed to water for a long period of time, and has high strength and hydrolysis resistance of the film.
이하에서는 본 발명에 의한 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물을 실험한 실시예를 살펴보기로 하되, 당업자가 용이하게 이해하고 실시할 수 있을 정도의 바람직한 실시예를 통하여 본 발명을 설명한다.Hereinafter, a polyurethane resin composition for a non-swellable moisture-permeable and waterproofing sheet using the surface-treated nanosilica particles according to the present invention will be described. However, it should be understood that the present invention is not limited to the specific examples The present invention will be described.
[실시예 1][Example 1]
2리터 3구 환류 반응기에 나노실리카 100g과 톨루엔 1ℓ를 넣고 잘 교반하여 준다. 이후 3-메타 아크릴록시 프로필 트리에톡시 실란 {3-methacryloxypropyl triethoxysilane} 62.08g을 넣고 천천히 승온하여 60℃에서 4시간 동안 반응시킨다. 이후 반응기 온도를 40℃ 이하로 냉각시킨 다음, 폴리(에틸렌글리콜) 메틸에테르 메타아크릴레이트{Poly(ethylene glycol) methyl ether methacrylate} 237g(분자량: 950)을 천천히 적하하여 반응시킨다(약 3hr).100 g of nano silica and 1 L of toluene are put into a 2-liter three-neck reflux reactor and stirred well. Then, 62.08 g of 3-methacryloxypropyl triethoxysilane was added, and the temperature was slowly raised, and the reaction was carried out at 60 ° C for 4 hours. After the temperature of the reactor was lowered to 40 ° C or less, 237 g of poly (ethylene glycol) methyl ether methacrylate (molecular weight: 950) was slowly added dropwise to the reaction system (about 3 hours).
상기 반응물은 감압여과를 통해 톨루엔을 제거한 다음, 에탄올을 이용하여 5회 세척한다. 이후 100℃ 정도의 드라이오븐에서 24시간 동안 건조하여 나노실리카에 실란화합물과 폴리에틸렌글리콜 마크로머가 커플링된 실리케이트를 최종물질로 합성하였다.The reaction product is filtered through reduced pressure to remove toluene, and then washed five times with ethanol. Thereafter, the resultant was dried in a dry oven at about 100 ° C. for 24 hours to synthesize a silicate in which a silane compound and a polyethylene glycol macromer were coupled to the nanosilica as a final material.
[실시예 2][Example 2]
2리터 3구 환류 반응기에 나노실리카 100g과 톨루엔 1ℓ를 넣고 잘 교반하여 준다. 이후 3-메타 아크릴록시 프로필 트리에톡시 실란 {3-methacryloxypropyl triethoxysilane} 62.08g을 넣고 천천히 승온하며 60℃에서 4시간 동안 반응시킨다. 이후 반응기 온도를 40℃ 이하로 냉각시킨 다음, 폴리(에틸렌글리콜) 메틸에테르 메타아크릴레이트{Poly(ethylene glycol) methyl ether methacrylate} 375g(분자량: 1500)을 천천히 적하하여 반응시킨다(약 3hr).100 g of nano silica and 1 L of toluene are put into a 2-liter three-neck reflux reactor and stirred well. Then, 62.08 g of 3-methacryloxypropyl triethoxysilane was added thereto, and the mixture was slowly heated and reacted at 60 ° C for 4 hours. After the reactor temperature is lowered to 40 ° C or less, 375 g of poly (ethylene glycol) methyl ether methacrylate (molecular weight: 1500) is slowly added dropwise (about 3 hours).
상기 반응물은 감압여과를 통해 톨루엔을 제거한 다음, 에탄올을 이용하여 5회 세척한다. 이후 100℃ 정도의 드라이오븐에서 24시간 동안 건조하여 나노실리카에 실란화합물과 폴리에틸렌글리콜 마크로머가 커플링된 실리케이트를 최종물질로 합성하였다.The reaction product is filtered through reduced pressure to remove toluene, and then washed five times with ethanol. Thereafter, the resultant was dried in a dry oven at about 100 ° C. for 24 hours to synthesize a silicate in which a silane compound and a polyethylene glycol macromer were coupled to the nanosilica as a final material.
[실시예 3][Example 3]
소수성 폴리우레탄 수지 100중량부에 대하여 실시예 1에서 합성한 실리케이트 15중량부와 DMF 10중량부, Toluene 20중량부, MEK 20중량부를 넣은 후, 호모믹서를 이용해 15분간 분산시켜 코팅액을 준비한다(점도 3,000 ~ 3,200cps at 25℃). 준비된 코팅액을 이형지 상에 콤마나이프로 두께 20㎛가 되도록 필름을 형성하고 약 120℃에서 1분 30초간 건조하여 필름을 제조하였다.15 parts by weight of the silicate synthesized in Example 1, 10 parts by weight of DMF, 20 parts by weight of Toluene and 20 parts by weight of MEK were added to 100 parts by weight of the hydrophobic polyurethane resin and dispersed for 15 minutes using a homomixer to prepare a coating solution Viscosity 3,000 to 3,200 cps at 25 ° C). The prepared coating solution was formed into a film having a thickness of 20 μm with a comma knife on a release paper and dried at about 120 ° C. for 1 minute and 30 seconds to prepare a film.
[실시예 4][Example 4]
소수성 폴리우레탄 수지 100중량부에 대하여 실시예 2에서 합성한 실리케이트 15중량부와 DMF 10중량부, Toluene 20중량부, MEK 20중량부를 넣은 후, 호모믹서를 이용해 15분간 분산시켜 코팅액을 준비한다(점도 3,000 ~ 3,200cps at 25℃). 준비된 코팅액을 이형지 상에 콤마나이프로 두께 20㎛가 되도록 필름을 형성하고 약 120℃에서 1분 30초간 건조하여 필름을 제조하였다.15 parts by weight of the silicate synthesized in Example 2, 10 parts by weight of DMF, 20 parts by weight of Toluene and 20 parts by weight of MEK were added to 100 parts by weight of the hydrophobic polyurethane resin and dispersed for 15 minutes using a homomixer to prepare a coating solution Viscosity 3,000 to 3,200 cps at 25 ° C). The prepared coating solution was formed into a film having a thickness of 20 μm with a comma knife on a release paper and dried at about 120 ° C. for 1 minute and 30 seconds to prepare a film.
[비교예 1][Comparative Example 1]
2리터 3구 환류 반응기에 나노실리카 100g과 톨루엔 1ℓ를 넣고 잘 교반하여 준다. 이후 3-메타 아크릴록시 프로필 트리에톡시 실란 {3-methacryloxypropyl triethoxysilane} 62.08g을 넣고 넣고 천천히 승온하며 60℃에서 4시간 동안 반응시킨다. 이후 반응물은 감압여과를 통해 톨루엔을 제거한 다음, 에탄올을 이용하여 5회 세척한다. 이후 100℃ 드라이오븐에서 24시간 건조하여 나노실리카에 실란화합물이 커플링된 실리케이트를 합성하였다.100 g of nano silica and 1 L of toluene are put into a 2-liter three-neck reflux reactor and stirred well. Then, 62.08 g of 3-methacryloxypropyl triethoxysilane was added thereto, and the mixture was slowly heated and reacted at 60 ° C for 4 hours. Thereafter, the reaction product is subjected to filtration under reduced pressure to remove toluene and then washed five times with ethanol. Then, it was dried in a 100 ° C dry oven for 24 hours to synthesize a silicate in which a silane compound was coupled to nano silica.
[비교예 2][Comparative Example 2]
소수성 폴리우레탄 수지 100중량부에 대하여 비교예 1에서 합성된 실리케이트15중량부와 DMF 10중량부, Toluene 20중량부, MEK 20중량부를 넣은 후, 호모믹서를 이용하여 15분간 분산시켜 코팅액을 준비한다(점도 3,000 ~ 3,200cps at 25℃). 준비된 코팅액을 이형지 상에 콤마나이프로 두께 20㎛가 되도록 필름을 형성하고 약 120℃에서 1분 30초간 건조하여 필름을 제조하였다.15 parts by weight of the silicate synthesized in Comparative Example 1, 10 parts by weight of DMF, 20 parts by weight of Toluene and 20 parts by weight of MEK were added to 100 parts by weight of the hydrophobic polyurethane resin and dispersed for 15 minutes using a homomixer to prepare a coating solution (Viscosity 3,000 to 3,200 cps at 25 ° C). The prepared coating solution was formed into a film having a thickness of 20 μm with a comma knife on a release paper and dried at about 120 ° C. for 1 minute and 30 seconds to prepare a film.
[실험예][Experimental Example]
실시예 1, 2, 비교예 1에서 합성된 실리케이트의 중량부를 달리하여 실시예 3, 4, 비교예 2와 같은 방법으로 제조된 필름에 대하여 각각의 투습도와 내수압을 측정하고 그 결과를 [표 1]에 나타내었다.The moisture permeability and water pressure of each of the films prepared in the same manner as in Examples 3 and 4 and Comparative Example 2 were measured by varying the weight of the silicate synthesized in Examples 1 and 2 and Comparative Example 1, ].
비교예 2
Comparative Example 2
(g/㎡24hr)Moisture permeability
(g / m224hr)
1,000
1,000
2,200
2,200
2,500
2,500
(mmH2O)Water pressure
(mmH 2 O)
10,000
10,000
10,000
10,000
10,000
10,000
실시예 3
Example 3
(g/㎡24hr)Moisture permeability
(g / m224hr)
4,300
4,300
7,700
7,700
9,300
9,300
(mmH2O)Water pressure
(mmH 2 O)
10,000
10,000
10,000
10,000
10,000
10,000
실시예 4
Example 4
(g/㎡24hr)Moisture permeability
(g / m224hr)
4,600
4,600
7,800
7,800
10,000
10,000
(mmH2O)Water pressure
(mmH 2 O)
10,000
10,000
10,000
10,000
10,000
10,000
상기 [표 1]에서와 같이, 본 발명에 의한 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물로 제조된 투습 방수포는 내수압이 10,000mmH20(ISO 0811) 이상이고 투습도 7,700g/㎡24hrs(JIS L 1099A-1법) 이상으로서, 기존 고기능성 투습 방수포에 비해 강한 내수압과 우수한 투습성을 그대로 유지하면서도 수분흡수에 따르는 팽윤현상(swelling)이 발생되지 않고 촉감, 신축성 및 박리강도 등 모든 평가항목에서 보다 월등한 특성을 보였는바, 본 발명의 폴리우레탄 수지조성물은 등산복이나 스포츠웨어, 캐주얼웨어, 작업복, 특수복 등과 같은 의복이나 장갑, 양말, 모자, 신발, 천막 등과 용품에 사용되어 외기 수분침투를 억제하고 발한 및 수분응결에 의한 수분을 외기로 발산하여 결로현상을 방지하는데 탁월한 효과를 기대할 수 있다.As shown in Table 1, the moisture-permeable tarpaulin made of the polyurethane resin composition for non-swellable moisture-permeable and waterproofing using the surface-treated nanosilica particles according to the present invention has a water pressure of 10,000 mmH 2 O (ISO 0811) or more and a moisture permeability of 7,700 The present invention relates to a high moisture permeable waterproofing cloth which is superior in water resistance and moisture permeability to a conventional high moisture permeable waterproofing cloth and which does not cause swelling due to moisture absorption, , The polyurethane resin composition of the present invention is used in clothing, gloves, socks, hats, shoes, tents, and other articles such as mountaineering clothes, sportswear, casual wear, work clothes, Superior effect can be expected in suppressing moisture penetration into the outside air and preventing moisture from condensation by sweating and moisture condensation to the outside. All.
따라서 본 발명의 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물은 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지로 치환, 변형 및 변경이 가능한 것으로, 투습방수포는 물론 각종 섬유제품의 표면에 코팅되거나 필름형태로 접합되는 등 다양한 용도와 형태로 사용되어 질 수 있다.Therefore, the polyurethane resin composition for non-swellable moisture-permeable and waterproofing polyurethane resin using the surface-treated nanosilica particles of the present invention can be variously substituted, modified and changed without departing from the technical idea of the present invention. Can be used in various applications and forms such as being coated on the surface of a textile product or bonded in a film form.
Claims (7)
상기 실란화합물(Silane compound)은 3-메타 아크릴록시 프로필 트리에톡시 실란{3-methacryloxypropyl triethoxysilane}, 3-메타 아크릴록시 프로필 메틸디메톡시 실란{3-Methacryloxypropylmethyldimethoxysilane}, 3-아크릴록시 프로필 트리메톡시 실란{3-acryloxy propyl trimethoxysilane} 중에서 선택되는 어느 1종 이상의 물질이고,
상기 폴리에틸렌글리콜 마크로머(Polyethylene glycol macromer)는 수평균분자량 950, 1500, 4,000 중에서 선택되는 어느 1종 이상의 폴리(에틸렌 글리콜) 메틸 에테르 메타아크릴레이트{Poly(ethylene glycol) methyl ether methacrylate}를 사용하며,
상기 소수성 폴리우레탄 수지 100중량부를 기준으로, 디메틸포름아미드(Dimethylformamide, DMF) 5 ~ 15중량부; 톨루엔(Toluene) 15 ~ 25중량부; 메틸에틸케톤(Methylethylketone, MEK) 15 ~ 25중량부로 이루어지는 용매를 포함함으로써 점도가 3,000 ~ 3,200cps(25℃ 기준)인 것을 특징으로 하는 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물.Based on 100 parts by weight of a hydrophobic polyurethane resin, 10 to 15 weight parts of a silicate compound having a silane compound and a polyethylene glycol macromer coupled to the surface of nanosilica having a particle size of 10 to 1,000 nm In the polyurethane resin composition obtained by uniformly mixing the components,
The silane compound may be selected from the group consisting of 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, {3-acryloxy propyl trimethoxysilane}, and more preferably,
The polyethylene glycol macromer uses at least one poly (ethylene glycol) methyl ether methacrylate selected from the group consisting of number average molecular weights of 950, 1500 and 4,000,
5 to 15 parts by weight of dimethylformamide (DMF) based on 100 parts by weight of the hydrophobic polyurethane resin; 15 to 25 parts by weight of toluene (Toluene); And a solvent comprising 15 to 25 parts by weight of methylethylketone (MEK), and having a viscosity of 3,000 to 3,200 cps (based on 25 DEG C). The non-swellable polyurethane resin for moisture- Composition.
상기 폴리우레탄 수지조성물을 이형지 상에 코팅하여 두께 10 ~ 30㎛인 필름형태의 투습 방수포로 형성되는 것을 특징으로 하는 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물.The method according to claim 1,
Wherein the polyurethane resin composition is coated on a release paper to form a moisture permeable waterproofing film having a thickness of 10 to 30 占 퐉. The polyurethane resin composition for non-swelling waterproofing and moistureproofing waterproofing using the surface treated nanosilica particles.
상기 필름형태의 투습 방수포는 내수압 10,000mmH20(ISO 0811) 이상이고, 투습도 7,700g/㎡24hrs(JIS L 1099A-1법) 이상인 것을 특징으로 하는 표면 처리된 나노실리카 입자를 이용한 비팽윤성 투습 방수포용 폴리우레탄 수지조성물The method according to claim 6,
Wherein the moisture permeable protective film of the film type has a water pressure of 10,000 mmH 2 O (ISO 0811) or higher and a moisture permeability of 7,700 g / m 2 24 hrs (JIS L 1099A-1 method) Embedded polyurethane resin composition
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150158570A KR101744487B1 (en) | 2015-11-12 | 2015-11-12 | Polyurethane resin compositions for a non-swelling permeable waterproof cloth used surface activated nano-silica particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150158570A KR101744487B1 (en) | 2015-11-12 | 2015-11-12 | Polyurethane resin compositions for a non-swelling permeable waterproof cloth used surface activated nano-silica particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170055651A KR20170055651A (en) | 2017-05-22 |
| KR101744487B1 true KR101744487B1 (en) | 2017-06-20 |
Family
ID=59050089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150158570A Active KR101744487B1 (en) | 2015-11-12 | 2015-11-12 | Polyurethane resin compositions for a non-swelling permeable waterproof cloth used surface activated nano-silica particles |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101744487B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102007392B1 (en) * | 2018-04-27 | 2019-08-05 | 서용성 | Waterborne resin composition containing silicone-modified polyurethane and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102728859B1 (en) * | 2021-11-24 | 2024-11-13 | 주식회사 세양 | Method for manufacturing a film for fabric protective coating and moisture-permeable waterproof zipper manufactured by using the film for fabric protective coating produced thereby |
| CN119685965B (en) * | 2025-02-21 | 2025-08-01 | 绍兴惠群新材料科技有限公司 | Fiber capable of rapidly guiding moisture as well as preparation method and application thereof |
| CN120574376A (en) * | 2025-08-04 | 2025-09-02 | 吴江市汉塔纺织整理有限公司 | A dry preparation method for a polyurethane nanofilm with high water pressure resistance and dynamic controllable moisture permeability |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100909677B1 (en) * | 2008-10-20 | 2009-07-29 | 주식회사 비 에스 지 | Manufacturing method of non-swellable laminated film |
-
2015
- 2015-11-12 KR KR1020150158570A patent/KR101744487B1/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100909677B1 (en) * | 2008-10-20 | 2009-07-29 | 주식회사 비 에스 지 | Manufacturing method of non-swellable laminated film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102007392B1 (en) * | 2018-04-27 | 2019-08-05 | 서용성 | Waterborne resin composition containing silicone-modified polyurethane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170055651A (en) | 2017-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101744487B1 (en) | Polyurethane resin compositions for a non-swelling permeable waterproof cloth used surface activated nano-silica particles | |
| KR101638772B1 (en) | High-hydraulic pressure and high-permeable polyurethane resin compositions containing surface activated nano-silica | |
| KR101402783B1 (en) | Synthetic leather and preparing method thereof | |
| EP2247441A1 (en) | Multi-layer composite material, production and use thereof | |
| EP2436724B1 (en) | Process for producing porous object, and porous object, layered product, and leather-like sheet each obtained thereby | |
| CN101705617A (en) | Water-based PU high solid resin combination for synthetic leather | |
| KR101421660B1 (en) | the coat composite with nano Zinc Oxide the outdoor fabric with both resin coated coat composite and coated porous resin and the manufacturing method of outdoor fabric | |
| KR101434154B1 (en) | Permeable and waterproof coating fabric and prepairing process thereof | |
| CN112208177A (en) | High-breathability PE composite fabric and preparation method thereof | |
| KR20200002272A (en) | Water Proof Breathable Outdoor knit Fabric and manufacturing method thereof | |
| KR101234048B1 (en) | Ultraviolet-curable type waterproof and berathable fabric having deodrant and antistatic, and a method of fabricating the same | |
| WO2015119037A1 (en) | Waterproof fabric and textile product employing same | |
| CN113789672B (en) | Polyurethane synthetic leather for outdoor sport casual shoes and preparation method thereof | |
| KR101049257B1 (en) | Coating composition for moisture-permeable waterproof, moisture-permeable waterproof fabric and manufacturing method thereof | |
| CN114714720A (en) | Washing-resistant waterproof moisture-permeable composite fabric and preparation method thereof | |
| JP5596564B2 (en) | Highly flexible sheet-like composite material | |
| JP5396010B2 (en) | Moisture permeable waterproof fabric and method for producing the same | |
| JP2009161898A (en) | Glove insert made of plant-originated component | |
| WO2009106501A1 (en) | Multi-layer composite material, production and use thereof | |
| KR100612294B1 (en) | Foam moisture-permeable tarpaulin and its manufacturing method | |
| KR101598856B1 (en) | Method for Manufacturing Artificial Leather Using Aqueous Polyurethane | |
| KR101965583B1 (en) | Permeable waterproof resin compositions for fabric coating and coating fabric using the same | |
| KR20140045490A (en) | The coat composite with nano zinc oxide the outdoor fabric with both resin coated coat composite and coated porous resin and the manufacturing method of outdoor fabric | |
| US20230092011A1 (en) | Eco-friendly automotive interior part and method of manufacturing same | |
| JP5183980B2 (en) | Waterproof fabric and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| PA0109 | Patent application |
Patent event code: PA01091R01D Comment text: Patent Application Patent event date: 20151112 |
|
| PA0201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 20161021 Patent event code: PE09021S01D |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
Patent event code: PE07011S01D Comment text: Decision to Grant Registration Patent event date: 20170522 |
|
| PG1501 | Laying open of application | ||
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 20170601 Patent event code: PR07011E01D |
|
| PR1002 | Payment of registration fee |
Payment date: 20170602 End annual number: 3 Start annual number: 1 |
|
| PG1601 | Publication of registration | ||
| PR1001 | Payment of annual fee |
Payment date: 20200428 Start annual number: 4 End annual number: 4 |
|
| PR1001 | Payment of annual fee |
Payment date: 20210429 Start annual number: 5 End annual number: 5 |
|
| PR1001 | Payment of annual fee |
Payment date: 20220428 Start annual number: 6 End annual number: 6 |
|
| PR1001 | Payment of annual fee |
Payment date: 20230405 Start annual number: 7 End annual number: 7 |
|
| PR1001 | Payment of annual fee |
Payment date: 20240521 Start annual number: 8 End annual number: 8 |
|
| PR1001 | Payment of annual fee |
Payment date: 20250407 Start annual number: 9 End annual number: 9 |