KR20170002958A - Artificial Leather with Improved Abrasion and Rubbing Fastness, and Method for Manufacturing The Same - Google Patents
Artificial Leather with Improved Abrasion and Rubbing Fastness, and Method for Manufacturing The Same Download PDFInfo
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- KR20170002958A KR20170002958A KR1020150092947A KR20150092947A KR20170002958A KR 20170002958 A KR20170002958 A KR 20170002958A KR 1020150092947 A KR1020150092947 A KR 1020150092947A KR 20150092947 A KR20150092947 A KR 20150092947A KR 20170002958 A KR20170002958 A KR 20170002958A
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- South Korea
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- artificial leather
- polycarbonate
- polyurethane
- abrasion
- mol
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Links
- 239000002649 leather substitute Substances 0.000 title claims abstract description 65
- 238000005299 abrasion Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title description 23
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 63
- 239000004417 polycarbonate Substances 0.000 claims abstract description 63
- 229920002635 polyurethane Polymers 0.000 claims abstract description 62
- 239000004814 polyurethane Substances 0.000 claims abstract description 62
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 28
- 239000000835 fiber Substances 0.000 claims abstract description 20
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 239000000806 elastomer Substances 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 229920005862 polyol Polymers 0.000 claims description 28
- 150000003077 polyols Chemical class 0.000 claims description 28
- -1 methylene bisbenzene amine Chemical class 0.000 claims description 24
- 239000004698 Polyethylene Substances 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 239000004970 Chain extender Substances 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 14
- 239000000975 dye Substances 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 238000004043 dyeing Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 239000000986 disperse dye Substances 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000013013 elastic material Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920001410 Microfiber Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000003658 microfiber Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical group N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/32—Material containing basic nitrogen containing amide groups leather skins
-
- 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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
본 발명은 극세섬유 부직포에 고분자 탄성체로서 폴리카보네이트폴리우레탄을 함침시켜 상기 탄성체가 인공피혁 중에 10 ~ 40 중량% 함유된 우수한 마모 및 마찰견뢰도를 갖는 인공피혁 및 이의 제조방법에 관한 것이다.
본 발명에 따르면, 고분자 탄성체로 폴리카보네이트폴리우레탄을 적용함으로써 딱딱해지지 않으면서도 우수한 마모 및 마찰견뢰도의 인공피혁을 얻을 수 있어 우수한 표면 품위가 요구되는 제품에 용이하게 사용될 수 있다.The present invention relates to an artificial leather impregnated with a microfine fiber nonwoven fabric as a polymer elastomer and polycarbonate polyurethane as a polymer elastomer, and the elastomer is contained in an artificial leather in an amount of 10 to 40% by weight and has excellent abrasion resistance and friction fastness.
According to the present invention, by applying polycarbonate polyurethane as a polymeric elastomer, it is possible to obtain an artificial leather having excellent abrasion and friction fastness without being hardened, and can be easily used for a product requiring an excellent surface quality.
Description
본 발명은 마모 및 마찰견뢰도가 우수한 인공피혁 및 이의 제조방법에 관한 것으로서, 보다 구체적으로는, 인공피혁을 제조할 때에 탄성체 부여 단계에서 폴리카보네이트폴리우레탄 함침재를 이용하여 딱딱해지지 않으면서도 우수한 마모 및 마찰견뢰도를 갖는 것을 특징으로 하는 인공피혁 및 이의 제조방법에 관한 것이다.The present invention relates to an artificial leather excellent in abrasion and friction fastness and a method of manufacturing the same, and more particularly, to a method of manufacturing an artificial leather using a polycarbonate polyurethane impregnated material in the step of applying an elastic material, And a method of producing the same.
인공피혁은 극세섬유가 3차원적으로 교락되어 형성된 부직포에 고분자 탄성체가 함침되어 이루어진 것으로서, 천연피혁과 유사하게 부드러운 질감 및 독특한 외관을 보유하여, 신발, 의류, 장갑, 잡화, 가구, 및 자동차 내장재 등과 같은 다양한 분야에 널리 이용되고 있다.The artificial leather is made by impregnating a nonwoven fabric formed by three-dimensionally entangled microfine fibers into a polymer elastomer, and has a soft texture and a unique appearance similar to natural leather and is used in shoes, clothes, gloves, And the like.
종래 인공피혁 제조시 고분자 탄성체로서 폴리우레탄이 함침재로 주로 사용되어 왔다. 이는 우수한 탄성과 물성이 인공피혁의 소재로써 적합하였기 때문이다.Conventionally, polyurethane as a polymer elastomer has been mainly used as an impregnation material in the artificial leather production. This is because excellent elasticity and physical properties are suitable as materials for artificial leather.
폴리우레탄을 함침한 인공피혁에 대한 특허로서 대한민국등록특허공보 제0588596호(발명의 명칭: 저 이염(移染)성 폴리우레탄함침 스웨이드조 인공피혁의 제조방법(Preparation of suede-like artificial polyurethane impregnated leather having low migration))가 있다.A patent for artificial leather impregnated with polyurethane is disclosed in Korean Patent Publication No. 0588596 entitled " Preparation of suede-like artificial polyurethane impregnated leather with low permeability (polyurethane impregnated suede) having low migration).
폴리우레탄 함침 인공피혁의 제조에 있어서, 폴리우레탄 함침공정은 디메틸포름아마이드와 같은 유기용매하에 우레탄 원료인 폴리올, 이소시아네이트, 사슬연장제를 중합하여 함침액을 준비하는 단계, 부직포를 상기 함침액에 침지하는 단계, 폴리우레탄을 응고시키는 응고단계, 수세단계 및 건조단계를 거쳐 이루어지는데, 이를 일반적으로 습식법이라 한다.In the production of the polyurethane-impregnated artificial leather, the polyurethane impregnation step is a step of preparing an impregnating solution by polymerizing polyol, isocyanate and chain extender, which are urethane raw materials, in an organic solvent such as dimethylformamide, , A coagulation step of coagulating the polyurethane, a washing step and a drying step, which are generally referred to as a wet method.
폴리우레탄을 함침한 후에 다양한 색상으로 염색하여 색상을 지닌 인공피혁을 제조하게 되는데, 이러한 인공피혁은 색상에 따라 - 예를 들면, 농색과 담색에 따라 - 견뢰도의 차이가 발생하는 문제점이 있다.After impregnation with polyurethane, artificial leather having a color is produced by dyeing in various colors. Such artificial leather has a problem in that there is a difference in fastness depending on color - for example, depending on color and color.
이는 인공피혁이 극세사 부직포에서 극세섬유의 교락으로 구성되어 있어서 마모강도가 우수하지 못하며, 염색 후 폴리우레탄 탄성체의 염료 오염으로 견뢰도가 취약해지는 것이 하나의 문제점이다.This is a problem in that the artificial leather is composed of microfiber interlocking in microfiber nonwoven fabric so that the abrasion strength is not excellent and the fastness after dyeing becomes poor due to dye contamination of the polyurethane elastomer.
이러한 문제점을 해결하기 위해 섬유밀도를 높여 마모강도를 향상시키려는 기술이 개발되고 있다.In order to solve these problems, a technique for improving the abrasion strength by increasing the fiber density has been developed.
또한, 폴리우레탄 탄성체 내에 염료가 적게 잔존할 수 있도록 인공피혁의 공정 중 염색공정에서 염색 후 세정할 때에 염료를 용이하게 제거하여 마찰견뢰도를 향상시키려는 개발이 진행되고 있다.Further, development is progressing to improve the fastness to rubbing by easily removing the dye when washing after dyeing in the dyeing process of the artificial leather so that a small amount of dye can remain in the polyurethane elastic body.
그러나, 상기 마모강도를 향상시키려는 기술은, 통상제품과 비교하여 고가로 되어 경제성이 저하되며, 극세사의 마모 저항성 향상에 한계가 있는 또 다른 문제점이 있다.However, the technique for improving the abrasion strength is costly compared with a normal product, resulting in lowering of economic efficiency, and there is a further problem in that there is a limit to improvement of micro wear resistance.
또한, 잔존 염료를 용이하게 제거하는 방법을 성능이 우수한 염료를 사용하게 되는 경우, 염료 제거 후 폴리우레탄 탄성체의 색상과 염색된 섬유의 색상 차이가 발생하여 품위가 저하되고 마찰에 의한 섬유의 낙모로 견뢰도가 저하되는 또 다른 문제점이 있다.Further, when a dye having excellent performance is used as a method of easily removing residual dyes, there is a difference in hue between the color of the polyurethane elastic body and the stained fiber after dye removal, There is another problem that the fastness is lowered.
일본 공개특허 2001-214376에는 염색한 시트물 표면에 고분자 수지를 코팅하는 방법이 게재되어있다Japanese Patent Application Laid-Open No. 2001-214376 discloses a method of coating a polymeric resin on the surface of a dyed sheet
마모강도를 개선하기 위하여 표면에 고분자 수지를 코팅하는 상기 방법은 마모강도는 우수하지만 표면에 스웨드 효과가 없고 코팅된 고분자 수지 자체의 특성으로 인해 촉감이 딱딱하여 용도에 제한을 받고, 또한 코팅에 사용되는 고분자 수지가 용제형으로 되어 있기 때문에 표면 코팅시 용제에 의하여 인공피혁에 존재하는 염료의 용해로 인해 이차적인 오염문제가 발생할 수 있고, 인체에 유해한 단점이 있다.The above method of coating a polymer resin on the surface in order to improve the abrasion strength has excellent abrasion strength but has no suede effect on the surface and has a limited use due to its hard feel due to the properties of the coated polymer resin itself, Since the polymer resin is in the form of a solvent, there is a problem of secondary contamination due to the dissolution of the dye present in the artificial leather by the solvent during the surface coating, which is harmful to the human body.
본 발명은 상기 문제점을 해결하기 위하여, 인공피혁의 마모 및 마찰견뢰도를 향상시켜 염색된 색상의 견뢰도가 향상되는 인공피혁 및 이의 제조방법을 제공하는 것을 목적으로 한다.The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an artificial leather and a method of manufacturing the artificial leather, wherein the color fastness of the dyed color is improved by improving the abrasion and friction fastness of the artificial leather.
상기 과제를 해결하기 위해 본 발명은, 해도형 극세섬유로 이루어진 부직포에 고분자 탄성체가 함침되고 염색되어 이루어지는 인공피혁에 있어서, 상기 고분자 탄성체는, 폴리카보네이트디올; 이소시아네티트; 및 사슬 연장제로서 에틸렌글리콜 및 메틸렌비스벤젠아민;을 포함한 원료로 중합된 폴리카보네이트폴리우레탄으로서, 상기 폴리카보네이트폴리우레탄이 상기 인공피혁에서 10~40 중량% 함유되는 것을 특징으로 하는 마모 및 마찰견뢰도가 우수한 인공피혁을 제공한다.In order to solve the above problems, the present invention provides an artificial leather comprising a nonwoven fabric made of sea-island microfine fibers impregnated with a polymeric elastomer and dyed, wherein the polymeric elastomer comprises a polycarbonate diol; Isocyanat; And polycarbonate polyurethane polymerized with a raw material containing ethylene glycol and methylene bisbenzene amine as a chain extender, wherein the polycarbonate polyurethane is contained in an amount of 10 to 40% by weight in the artificial leather. Provides excellent artificial leather.
본 발명에 따르면 고분자 탄성체로서 개질된 폴리카보네이트폴리우레탄을 함침시켜 제조된 인공피혁이 딱딱해지지 않고 유연성을 가지면서도 마모 및 마찰견뢰도가 향상되는 것이 가능해진다.According to the present invention, an artificial leather produced by impregnating a modified polycarbonate polyurethane as a polymer elastomer is not hardened, and it becomes possible to improve wear and friction fastness while having flexibility.
본 발명에 의한 인공피혁은 염색물의 마찰견뢰도가 증진되는데, 특히 습마찰 견뢰도가 향상되어 사람의 접촉이 빈번한 차량용 내장재로 활용할 수 있다.The artificial leather according to the present invention improves the fastness to rubbing of the dyed material, and particularly the wet fastness to rubbing is improved, so that it can be utilized as a vehicle interior material having frequent human contact.
본 발명의 기술적 사상 및 범위를 벗어나지 않는 범위 내에서 본 발명의 다양한 변경 및 변형이 가능하다는 점은 당업자에게 자명할 것이다. 따라서, 본 발명은 특허청구범위에 기재된 발명 및 그 균등물의 범위 내에 드는 변경 및 변형을 모두 포함한다.It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. Therefore, the present invention encompasses all changes and modifications that come within the scope of the invention as defined in the appended claims and equivalents thereof.
이하, 본 발명의 바람직한 실시예들에 대해서 상세히 설명하기로 한다.Hereinafter, preferred embodiments of the present invention will be described in detail.
본 발명은 0.001 내지 0.3 데니어의 섬도를 갖고 서로 교락되어 있는 해도형 극세섬유들을 포함하는 부직포에 탄성체로서 폴리카보네이트폴리우레탄을 함침시켜 이루어진 인공피혁에 있어서, 상기 폴리카보네이트폴리우레탄이 10~40 중량% 함유되고 상기 인공피혁은 염료로 염색된 염색물이며, 10,000 사이클 이상의 마모강도(Taber 마모 C5-10, 파열시점)와 4급 이상의 마찰견뢰도를 갖는 것을 특징으로 한다.The present invention provides an artificial leather impregnated with a polycarbonate polyurethane as an elastic material in a nonwoven fabric containing sea-island microfine fibers having a fineness of 0.001 to 0.3 denier and being entangled with each other, wherein the polycarbonate polyurethane is 10 to 40% And the artificial leather is a dye which is dyed with a dye and has a wear strength of at least 10,000 cycles (Taber abrasion C5-10, rupture time) and a rub fastness of 4 or more.
일반적으로 인공피혁용 폴리우레탄을 제조할 때에 연성 세그먼트(soft segment)로 작용하는 폴리올로서 폴리테트라메틸렌글리콜(PTMG)을 사용하는데, 이 경우에 인공피혁에서 소프트니스(softness)는 매우 우수해지나 열안정성과 내후성이 크게 저하되는 문제점이 있다. In general, polytetramethylene glycol (PTMG) is used as a polyol acting as a soft segment in the production of polyurethane for artificial leather. In this case, softness in artificial leather is excellent, There is a problem that the stability and the weather resistance are significantly deteriorated.
또한, 폴리올로서 아디페이트나 폴리카프로락톤을 사용할 수 있지만 내가수분해성이 크게 저하되고 인장강도를 제외한 인공피혁에서 요구하는 탄성과 같은 여러 다른 물성(예를 들면, 탄성, 열안정성, 저온특성, 항균성 등)은 향상되지 않는다. Adipate or polycaprolactone may be used as the polyol, but the hydrolysis resistance is significantly lowered and various physical properties such as elasticity required in artificial leather excluding tensile strength (for example, elasticity, thermal stability, low temperature characteristics, antibacterial properties Etc.) are not improved.
또한, 폴리올로서 폴리카보네이트디올(PCDL)을 사용할 경우에 내약품성, 내수성, 내열성 및 강도 측면에서 매우 우수한 물성을 발현하나 강직성이 높아서 인공피혁에서 연질감과 탄성을 부여하는데 한계가 있다. In addition, when polycarbonate diol (PCDL) is used as a polyol, it exhibits excellent physical properties in terms of chemical resistance, water resistance, heat resistance, and strength, but has a limitation in giving softness and elasticity in artificial leather because of its high rigidity.
이에 따라 본 발명에서는 분자 사슬의 길이가 증대된 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올을 사용하여 연질감이 저하되지 않으면서도 인공피혁에서 요구하는 각종 요구 특성을 만족하고 특히 탄성, 마모 및 마찰 특성이 우수한 인공피혁을 제공하는 것이다. Accordingly, in the present invention, the use of a linear aliphatic polycarbonate / polyethylene polyol having an increased molecular chain length satisfies various required properties required in artificial leather without deteriorating the soft texture, and in particular, the artificial leather having excellent elasticity, Leather.
본 발명의 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올는 하기 화학식 1로 표시된다. The linear aliphatic polycarbonate / polyethylene polyol of the present invention is represented by the following formula (1).
[화학식 1][Chemical Formula 1]
폴리카보네이트디올의 알킬기 사슬길이의 경우 분자길이가 짧게 형성되어 경직한 구조를 가지고 있으나, 상기 화학식 1의 경우 알킬기의 길이를 공중합체 형태로 전체 사슬길이를 증가시켜 유연성이 증대되면서도 폴리카보네이트디올의 고유 특성인 기계적 강도의 우수성이 발현될 수 있다. In the case of the alkyl chain length of the polycarbonate diol, the length of the alkyl chain is short and rigid. However, in the case of the formula (1), the length of the alkyl chain is increased in the form of a copolymer to increase the total chain length, Excellent mechanical strength can be achieved.
이때, 상기 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올는 중량평균분자량이 500~3,000인 것이 바람직한데, 중량평균분자량이 500 미만이면 인공피혁에서 유연성이 저하될 수 있고, 3,000을 초과하면 마모강도를 향상시킬 수 없어 바람직하지 못하다.The linear aliphatic polycarbonate / polyethylene polyol preferably has a weight average molecular weight of 500 to 3,000. If the weight average molecular weight is less than 500, the flexibility of the artificial leather may be deteriorated. If the weight average molecular weight is more than 3,000, It is not desirable.
상기 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올의 상업화된 제품의 예로는 일본 우베(UBE Industries, Ltd.)의 ETERNACOLL® UH-50, UH-100, UH-200, UH-300 등이 있다.Examples of commercialized products of the linear aliphatic polycarbonate / polyethylene polyols and the like Japan Ube (UBE Industries, Ltd.) of ETERNACOLL ® UH-50, UH- 100, UH-200, UH-300.
한편, 본 발명에서는 폴리올로서 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올를 사용하는 것만으로는 인공피혁에서 탄성체로서 폴리우레탄의 개질 특성이 충분하지 않은 것을 보완하기 위해, 사슬 연장제로서 메틸렌비스벤젠아민(MBA)과 에틸렌글리콜(EG)을 동시에 사용하여 중합된 폴리우레탄을 탄성체로 사용한다. On the other hand, in the present invention, in order to compensate for the insufficient modification properties of polyurethane as an elastic material in artificial leather by using a linear aliphatic polycarbonate / polyethylene polyol as the polyol, methylene bisbenzene amine (MBA) and Polyurethane polymerized by using ethylene glycol (EG) at the same time is used as an elastic material.
본 발명의 폴리카보네이트폴리우레탄은, 폴리올 및 사슬연장제에 대해 이소시아네이트를 등몰의 비율로 반응시키되, 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올 0.4 ~ 0.6 몰, 사슬 연장제로서 에틸렌글리콜 0.2 ~ 0.3 몰 및 메틸렌비스벤젠아민 0.2 ~ 0.3몰의 비율로 중합되어 제조되는 중합물이다. The polycarbonate polyurethane of the present invention is obtained by reacting an isocyanate with a polyol and a chain extender at an equivalent molar ratio, wherein 0.4 to 0.6 mol of a linear aliphatic polycarbonate / polyethylene polyol, 0.2 to 0.3 mol of ethylene glycol as a chain extender, Benzene amine in a proportion of 0.2 to 0.3 mol.
상기 폴리카보네이트폴리우레탄을 사용하게 되면 인공피혁에서 충진감을 부여하고, 에틸렌글리콜이 사슬 연장제로 사용되어 유연성을 향상시키고, 아민과 이소시아네이트의 우레아 반응에 의해 강하고 경직된(Rigid) 결합을 이루어 내열 특성이 우수해진다. When the polycarbonate polyurethane is used, a feeling of filling is imparted in artificial leather, ethylene glycol is used as a chain extender to improve flexibility, and a strong and rigid bond is formed due to the urea reaction between amine and isocyanate, It becomes.
또한, MBA, MDI의 경우에 안정된 아로마틱 구조를 가지고 있고, 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올 또한 카보네이트 구조로 분자사슬의 강직성이 높기 때문에 다른 물질에 비하여 기계적 물성이 매우 우수해진다. In addition, MBA and MDI have a stable aromatic structure, and since the linear aliphatic polycarbonate / polyethylene polyol also has a carbonate structure, the rigidity of the molecular chains is high, so that the mechanical properties are remarkably improved as compared with other materials.
상기한, 폴리올로서 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올; 사슬 연장제로서 에틸렌글리콜(EG) 및 메틸렌비스벤젠아민(MBA); 및 이소시아네이트의 조합에 의한 폴리카보네이트폴리우레탄은, 인공피혁에서 기계적 물성과 견뢰도 향상이 가능해진다. As the above-mentioned polyol, a linear aliphatic polycarbonate / polyethylene polyol; Ethylene glycol (EG) and methylene bisbenzeneamine (MBA) as chain extenders; And polycarbonate polyurethane by combination of isocyanate can improve mechanical properties and fastness in artificial leather.
이때, 본 발명의 인공피혁에서 상기 폴리카보네이트폴리우레탄의 함량이 10 중량% 미만이면 탄성체의 역할을 하기 어려워 염색한 후에 섬유의 감성이 발현되어 스웨이드 감성이 나타나기 어렵고 탄성, 내구성 및 견뢰도가 저하되며, 40 중량%를 초과하면 인공피혁이 너무 딱딱해져서 표면가공이 어려워지고 이로 인하여 고감성의 스웨이드 인공피혁이 구현되기 어려워 바람직하지 못하다.If the content of the polycarbonate polyurethane in the artificial leather of the present invention is less than 10% by weight, it is difficult to serve as an elastic body, so that after the dyeing, the sensibility of the fiber is developed, and suede feeling is difficult to be exhibited and the elasticity, durability, If it exceeds 40% by weight, the artificial leather becomes too hard and the surface processing becomes difficult, which makes it difficult to realize high-sensitivity suede artificial leather.
본 발명의 인공피혁을 구성하는 부직포 및 염료는 통상적으로 인공피혁을 제조할 수 있는 것이라면 제한 없이 사용될 수 있다.The nonwoven fabric and the dye constituting the artificial leather of the present invention can be used without limitation as long as they are capable of producing artificial leather.
이하에서는, 본 발명의 인공피혁 제조방법을 구체적으로 설명한다.Hereinafter, the artificial leather manufacturing method of the present invention will be described in detail.
본 발명의 인공피혁 제조방법은 폴리카보네이트폴리우레탄이 함침된 부직포를 제조하는 단계, 염료를 준비하는 단계 및 상기 폴리카보네이트폴리우레탄이 함침된 부직포를 상기 염료로 염색하는 단계를 포함한다. 이하, 각 단계별로 구체적으로 설명한다.The artificial leather manufacturing method of the present invention includes the steps of producing a nonwoven fabric impregnated with polycarbonate polyurethane, preparing a dye, and dyeing the nonwoven fabric impregnated with the polycarbonate polyurethane with the dye. Hereinafter, each step will be described in detail.
본 발명의 일 실시예에 의하면, 상기 폴리카보네이트폴리우레탄이 함침된 부직포를 제조하는 단계는, 복합방사공정을 통해 해도형(island in a sea type) 섬유를 제조하는 단계, 상기 해도형 섬유를 이용하여 부직포를 제조하는 단계, 상기 부직포에 폴리카보네이트폴리우레탄을 함침시키는 탄성체 부여 단계, 및 상기 폴리카보네이트폴리우레탄이 함침된 부직포에서 상기 해도형 섬유의 해성분을 제거하는 용출 공정을 포함한 극세섬유화 단계를 포함한다.According to an embodiment of the present invention, the step of fabricating the nonwoven fabric impregnated with the polycarbonate polyurethane may include the steps of preparing an island in a sea type fiber through a composite spinning process, A microfibre step including an elongation step of impregnating the nonwoven fabric with polycarbonate polyurethane and an elution step of removing the sea component of the sea-island fiber from the nonwoven fabric impregnated with the polycarbonate polyurethane, .
이때, 상기 극세섬유화 단계는 상기 탄성체 부여 단계의 이전 또는 이후에 수행할 수 있다.At this time, the microfiberization step may be performed before or after the elastomer application step.
상기 해도형 섬유를 제조하는 단계는, 용제에 용해되어 용출되는 해(sea)성분의 제1폴리머와 용제에 용해되지 않고 잔존하는 도(island)성분의 제2폴리머를 이용하여 복합방사하는 공정을 포함한다.The step of producing the sea-island fiber includes a step of composite spinning using a first polymer of a sea component dissolved and dissolved in a solvent and a second polymer of an island component remaining unresolved in a solvent .
상기 부직포를 제조하는 단계는, 스테이플 섬유(staple fiber) 상태의 해도형 섬유를 카딩(carding) 공정 및 크로스 래핑(cross lapping) 공정을 통해 웹(Web)을 형성하는 공정 및 상기 형성한 웹을 니들 펀치 또는 워터젯 펀치하는 공정을 포함한다.The step of fabricating the nonwoven fabric may include a step of forming a web through a carding process and a cross lapping process in the form of staple fibers in a staple fiber state, Punching or water jet punching.
선택적으로, 필라멘트 섬유 상태의 해도형 섬유를 스판 본딩(span bonding) 공정을 통해 웹(Web)을 형성한 후 니들펀치 또는 워터젯펀치 등을 이용하여 부직포를 제조할 수도 있다.Optionally, the nonwoven fabric may be manufactured using a needle punch or a waterjet punch after a web is formed through a span bonding process in a filament fiber state.
상기 폴리카보네이트폴리우레탄을 함침시키는 탄성체 부여 단계는 상기 제조된 부직포를 상기 폴리카보네이트폴리우레탄의 함침액에 침지시킨 후 패딩(Padding)을 하고, 응고조에서 물과 디메틸포름아미드(DiMethyl Formamide, DMF)의 치환반응을 통해 폴리우레탄을 응고시켜 이루어지는 함침공정으로서, 부직포에 탄성체가 함침된 함침포가 만들어진다. In the step of applying the elastomer to impregnate the polycarbonate polyurethane, the produced nonwoven fabric is immersed in the impregnation solution of the polycarbonate polyurethane, followed by padding, and water and dimethylformamide (DMF) In which the polyurethane is solidified through a substitution reaction of the nonwoven fabric with the elastomer impregnated into the nonwoven fabric.
이때, 상기 함침액으로 사용되는 폴리카보네이트폴리우레탄은, 폴리올로서 상기 화학식 1로 표시되는 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올 0.4 ~ 0.6 몰, 사슬 연장제로서 에틸렌글리콜(EG) 0.2 ~ 0.3 몰 및 메틸렌비스벤젠아민(MBA) 0.2 ~ 0.3몰로 이루어진 폴리올 및 사슬연장제에 대해 이소시아네이트를 등몰로 반응시켜 중합되어 제조되는 중합물이다. The polycarbonate polyurethane used as the impregnating solution is prepared by mixing 0.4 to 0.6 mol of a linear aliphatic polycarbonate / polyethylene polyol represented by the formula (1), 0.2 to 0.3 mol of ethylene glycol (EG) as a chain extender, Is a polymer prepared by reacting an isocyanate with an isocyanate to a polyol and a chain extender comprising 0.2 to 0.3 mol of benzene amine (MBA).
이때, 상기 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올는 중량평균분자량이 500~3,000인 것이 인공피혁에서 마모강도를 저하시키지 않으면서도 유연성을 향상할 수 있어 바람직하다.The linear aliphatic polycarbonate / polyethylene polyol preferably has a weight average molecular weight of 500 to 3,000 because it can improve flexibility without reducing the abrasion strength in artificial leather.
통상 함침액은 디메틸포름아미드에 상기 폴리카보네이트폴리우레탄 고형분이 15 ~ 35 중량%로 희석용해된 상태이다. Usually, the impregnating solution is in a state in which the solid content of the polycarbonate polyurethane is diluted to 15 to 35% by weight in dimethylformamide.
상기 해도형 섬유의 해성분을 제거하는 용출 공정을 포함한 극세섬유화 단계는, 가성소다 수용액과 같은 알칼리 용제를 이용하여 해성분인 제1폴리머를 용출시키는 공정을 포함한다.The microfiberization step including an elution step for removing the sea component of the sea-island fiber includes a step of eluting the first polymer as a sea component by using an alkali solvent such as caustic soda aqueous solution.
본 발명의 다른 실시예에 의하면, 부직포 제조 단계는, 복합방사공정을 통해 해도형 섬유를 제조하는 단계, 상기 해도형 섬유를 이용하여 부직포를 제조하는 단계, 상기 부직포에서 상기 해도형 섬유의 해성분을 제거하는 용출 공정을 포함한 극세섬유화 단계 및 상기 해성분이 제거된 부직포에 폴리카보네이트폴리우레탄을 함침시키는 탄성체 부여 단계를 포함한다.According to another embodiment of the present invention, the nonwoven fabric manufacturing step includes a step of producing sea-island fibers through a composite spinning process, a step of producing a nonwoven fabric using the sea-island fibers, And an elastic body applying step of impregnating the nonwoven fabric from which the sea component has been removed with polycarbonate polyurethane.
본 발명의 또 다른 실시예에 의하면, 부직포 제조 단계는, 복합방사를 통해 0.001 내지 0.3 데니어의 섬도를 갖는 극세섬유를 제조하는 단계, 상기 극세섬유를 이용하여 부직포를 제조하는 단계 및 상기 부직포에 폴리카보네이트폴리우레탄을 함침시키는 탄성체 부여 단계를 포함한다.According to another embodiment of the present invention, the step of producing a nonwoven fabric comprises the steps of: preparing microfine fibers having a fineness of 0.001 to 0.3 denier through composite spinning; preparing a nonwoven fabric using the microfine fibers; And an elastomer-imparting step of impregnating the carbonate polyurethane.
본 발명에서는 상기 부직포를 열수 수축하여 고밀도화 하는 단계가 상기 극세섬유화 단계 이후에 더 실시될 수 있다. In the present invention, the step of heat-shrinking and densifying the nonwoven fabric may be further performed after the microfibrous step.
상기 열수 수축에 의해 부직포의 밀도를 향상시킬 수 있고, 이로 인하여 최종제품인 인공피혁에서 표면의 입모 밀도가 높이 증가하여, 표면 외관 품질을 개선하고, 유연성과 부드러운 감촉의 감성품질을 향상시킬 수 있다.The density of the nonwoven fabric can be improved by the above-mentioned heat shrinkage shrinkage, thereby increasing the napped density of the surface of artificial leather as a final product, thereby improving the surface appearance quality and improving the quality of sensibility of softness and softness.
상기 고밀도화 단계는 부직포를 80 ℃ 이상의 열탕에 1분 이상 체류하도록 통과시키고 열 캘린더로 압착하여 실시할 수 있다. In the densification step, the nonwoven fabric may be allowed to stay in hot water at 80 ° C or more for 1 minute or more and compressed by a thermal calender.
상기 염료를 준비하는 단계는 황색, 적색 및 청색 분산 염료들을 혼합하는 단계를 포함한다.The step of preparing the dye comprises mixing yellow, red and blue disperse dyes.
상기 분산 염료는 벤젠 아조계 분산 염료, 헤테로환 아조계 분산 염료, 안트라퀴논계 분산 염료, 축합계 분산 염료 중에서 선택된 어느 하나 이상의 염료로 이루어진 것을 이용할 수 있다.The dispersion dye may be one comprising at least one dye selected from benzene azo based dispersion dyes, heterocyclic azo based dispersion dyes, anthraquinone based dispersion dyes and condensed dispersion dyes.
상기 고분자 탄성체가 함침된 부직포를 상기 분산 염료로 염색하는 단계는 상기 분산 염료 및 조제를 첨가한 염액을 이용하여 수행될 수 있다.The step of dyeing the polymeric elastomer-impregnated nonwoven fabric with the disperse dye may be carried out using a salt solution to which the disperse dye and the additive are added.
상기 염액은 1 내지 20 % o.w.f.(on the weight of fiber, 대섬유 중량)의 황색 분산 염료, 1 내지 20 % o.w.f.의 적색 분산 염료 및 1 내지 20 % o.w.f.의 청색 분산 염료를 포함함으로써 흑색 계통의 컬러를 발현하며, 상기 분산 염료의 총 함량은 3 내지 60 % o.w.f.일 수 있다.The saline solution contains a yellow disperse dye of 1 to 20% owf (on the weight of fiber), a red disperse dye of 1 to 20% owf and a blue disperse dye of 1 to 20% owf, , And the total content of the disperse dye may be 3 to 60% owf.
상기 염색하는 단계에서 상기 염액의 온도를 80 ~ 140 ℃로 유지하고, 20 ~ 60분 동안 염색을 수행할 수 있다. 상기 염액의 온도가 140 ℃를 초과하거나 상기 염색을 60 분 초과하여 수행할 경우에는 비용이 증가할 수 있어 바람직하지 못하다.In the dyeing step, the temperature of the saline solution may be maintained at 80 to 140 DEG C and dyeing may be performed for 20 to 60 minutes. If the temperature of the saline solution exceeds 140 ° C or the dyeing is performed for more than 60 minutes, the cost may increase, which is not preferable.
염색된 인공피혁의 표면상의 미고착염료나 불순물을 제거하는 환원세정 공정이 더 수행될 수 있다. 상기 환원세정 공정은 40 ~ 100 ℃에서 10~30 분 동안 수행될 수 있다. 상기 환원세정 공정을 통해, 인공피혁의 색상이 더욱 선명해질 수 있다.A reduction washing process for removing unfixed dyes or impurities on the surface of the dyed artificial leather can be further performed. The reduction washing process may be performed at 40 to 100 ° C for 10 to 30 minutes. Through the reduction washing process, the color of the artificial leather can be made clearer.
이하, 제조예, 실시예 및 비교예를 통하여 본 발명을 더욱 구체적으로 살펴본다.Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples.
[제조예 1] (폴리카보네이트폴리우레탄의 제조방법)[Production Example 1] (Production method of polycarbonate polyurethane)
통상의 폴리우레탄 중합방법을 사용하여, 폴리올로서 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올 0.6 mol(ETERNACOLL® UH-200, UBE Industries, Ltd., 일본, 중량평균분자: 2,000); 에틸렌글리콜 0.2 mol 및 4,4'-메틸렌비스벤젠아민 0.2 mol; 및 4,4'-디페닐메탄 디이소시아네이트 1.0 mol을 부가반응시켜 중합하고, 이렇게 중합된 중합물의 전체 고형분이 30 중량%가 되도록 디메틸포름아미드에 희석용해하여 중량평균분자량이 250,000인 반응종결형 폴리카보네이트폴리우레탄 화합물을 제조하였다.Using a conventional polyurethane polymerization method, a linear aliphatic polycarbonate / polyethylene polyol 0.6 mol as the polyol (ETERNACOLL UH-200 ®, UBE Industries, Ltd., Japan, average molecular weight: 2,000); 0.2 mol of ethylene glycol and 0.2 mol of 4,4'-methylene bisbenzene amine; And 1.0 mol of 4,4'-diphenylmethane diisocyanate were subjected to an addition reaction to polymerize. The thus polymerized polymer was diluted with dimethylformamide to have a total solid content of 30% by weight to obtain a reaction-terminated polycarbonate having a weight average molecular weight of 250,000 To prepare a polyurethane compound.
[제조예 2] (폴리카보네이트폴리우레탄의 제조방법)[Production Example 2] (Production method of polycarbonate polyurethane)
상기 제조예 1에서 폴리올로서 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올 0.4 mol(ETERNACOLL® UH-200, UBE Industries, Ltd., 일본, 중량평균분자: 2,000); 에틸렌글리콜 0.3 mol 및 4,4'-메틸렌비스벤젠아민 0.3 mol; 및 4,4'-디페닐메탄 디이소시아네이트 1.0 mol을 사용한 것을 제외하고는, 제조예 1과 동일한 방법을 사용하여 중량평균분자량이 200,000인 반응종결형 폴리카보네이트폴리우레탄 화합물을 제조하였다. Preparation Example 1, a linear aliphatic polycarbonate / polyethylene polyol 0.4 mol as the polyol from (ETERNACOLL UH-200 ®, UBE Industries, Ltd., Japan, average molecular weight: 2,000); 0.3 mol of ethylene glycol and 0.3 mol of 4,4'-methylene bisbenzene amine; And 1.0 mol of 4,4'-diphenylmethane diisocyanate were used in place of the polyisocyanate compound of Preparation Example 1, a reaction-terminated polycarbonate polyurethane compound having a weight average molecular weight of 200,000 was prepared.
[제조예 3] (폴리카보네이트폴리우레탄의 제조방법)[Production Example 3] (Production method of polycarbonate polyurethane)
상기 제조예 1에서 상기 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올을 ETERNACOLL® UH-100(중량평균분자: 1,000)을 사용한 것을 제외하고는, 제조예 1과 동일한 방법을 사용하여 중량평균분자량이 180,000인 반응종결형 폴리카보네이트폴리우레탄 화합물을 제조하였다. The linear aliphatic polycarbonate / polyethylene polyol in Preparative Example 1 ETERNACOLL ® UH-100 (weight average molecular 1,000) and is, in Production Example 1 and the reaction using the same method having a weight average molecular weight of 180,000 jonggyeolhyeong, except for using To prepare a polycarbonate polyurethane compound.
[실시예 1][Example 1]
단사섬도가 0.3 데니어인 부직포에 고분자 탄성체로서 제조예 1의 폴리카보네이트폴리우레탄을 함침시키고 부직포 두께의 80%로 짜준 후, 디메틸포름아미드 20 중량%의 수용액에서 응고시키고 수세하여 폴리카보네이트폴리우레탄이 10 중량% 함유된 함침포를 얻도록 가공하였다. A nonwoven fabric having a monofilament fineness of 0.3 denier was impregnated with a polycarbonate polyurethane of Production Example 1 as a polymeric elastomer and sieved to 80% of the thickness of the nonwoven fabric, then coagulated in an aqueous solution of 20% by weight of dimethylformamide and washed with water to obtain a polycarbonate polyurethane And processed so as to obtain the impregnation containing the weight%.
이후에 버핑기를 사용하여 상기 함침포의 표면을 샌드페이퍼 320 메시로 버핑하여 표면에 입모가 형성된 1.0 mm 두께의 인공피혁으로 제조하였고, 하기 염색조건 및 환원세정조건으로 염색 및 환원세정을 하였다.Thereafter, the surface of the impregnation was buffered with a sandpaper 320 mesh to prepare a 1.0 mm thick artificial leather having a nap on the surface, and dyeing and reduction washing were performed under the following dyeing conditions and reducing washing conditions.
<염색조건><Conditions for dyeing>
1) 염료 비율1) Dye ratio
- 황색 분산 염료(Huntsman사 제품) 8.0 % o.w.f.Yellow disperse dye (Huntsman) 8.0% o.w.f.
- 적색 분산 염료(Huntsman사 제품) 6.5 % o.w.f.- Red disperse dye (Huntsman) 6.5% o.w.f.
- 청색 분산 염료(Huntsman사 제품) 6.5 % o.w.f.Blue disperse dye (Huntsman) 6.5% o.w.f.
2) 균염제 : PEO Alkyl Amine Sulfate Type 화합물 배합품 3.0% o.w.f.2) Leveling agent: PEO Alkyl Amine Sulfate Type Compound compound 3.0% o.w.f.
3) 욕중유연제(D-1500) : 3 g/l3) Bath softener (D-1500): 3 g / l
4) 산 : 아세트산 1 g/l4) Acid: 1 g / l of acetic acid
5) 욕비(첨가물 중량:용매 중량) : 1:255) Bath (additive weight: solvent weight): 1:25
6) 염색온도 및 시간 : 120 ℃ 및 60 분6) Dyeing temperature and time: 120 占 폚 and 60 minutes
상기 조건으로 염색과정을 완료한 후, 아래 같은 조건으로 2회 환원세정하였다.After completion of the dyeing process under the above conditions, the mixture was subjected to reduction washing twice under the following conditions.
<환원세정조건><Reduction Cleaning Conditions>
1) 수산화나트륨 : 4 g/l1) Sodium hydroxide: 4 g / l
2) 소듐하이드로설파이트 : 8 g/l2) Sodium hydrosulfite: 8 g / l
3) 욕비(첨가물 중량:용매 중량) : 1:253) Bath (additive weight: solvent weight): 1:25
4) 세정온도 및 시간 : 80 ℃ 및 20분4) Cleaning temperature and time: 80 ° C and 20 minutes
상기 조건의 세정을 완료한 후 인공피혁을 회수하고 열풍건조기 내에서 120 ℃에서 10 분간 건조하여 흑색 컬러의 인공피혁을 제조하였다.After completion of washing under the above conditions, the artificial leather was recovered and dried in a hot air dryer at 120 ° C for 10 minutes to prepare artificial leather of black color.
[실시예 2][Example 2]
상기 실시예 1에서 상기 폴리카보네이트폴리우레탄이 25 중량% 함유된 함침포를 얻도록 가공한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 사용하여 흑색 컬러의 인공피혁을 제조하였다.A black colored artificial leather was produced in the same manner as in Example 1, except that the polycarbonate polyurethane in Example 1 was processed so as to obtain an impregnation containing 25% by weight of the polycarbonate polyurethane.
[실시예 3][Example 3]
상기 실시예 1에서 상기 제조예 2의 폴리카보네이트폴리우레탄이 20 중량% 함유된 함침포를 얻도록 가공한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 사용하여 흑색 컬러의 인공피혁을 제조하였다.A black colored artificial leather was produced in the same manner as in Example 1, except that in Example 1, the polycarbonate polyurethane of Production Example 2 was processed so as to obtain an impregnation containing 20% by weight of the polycarbonate polyurethane .
[실시예 4][Example 4]
상기 실시예 1에서 상기 제조예 3의 폴리카보네이트폴리우레탄이 20 중량% 함유된 함침포를 얻도록 가공한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 사용하여 흑색 컬러의 인공피혁을 제조하였다.Black colored artificial leather was produced in the same manner as in Example 1, except that the polycarbonate polyurethane of Production Example 3 was processed so as to obtain an impregnation containing 20% by weight of the polycarbonate polyurethane .
[비교예 1][Comparative Example 1]
상기 실시예 1에서 상기 제조예 1의 폴리카보네이트폴리우레탄 대신에 폴리올로서 PTMG를 이용하여 제조된 폴리우레탄 고분자가 10 중량% 함유된 함침포를 얻도록 가공한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 사용하여 흑색 컬러의 인공피혁을 제조하였다.The procedure of Example 1 was repeated except that the polycarbonate polyurethane of Production Example 1 was replaced with the polyurethane polymer prepared by using PTMG as a polyol to obtain a dipping cloth containing 10% by weight of the polyurethane polymer. Artificial leather of black color was produced using the same method.
[비교예 2][Comparative Example 2]
상기 실시예 1에서 상기 제조예 1의 폴리카보네이트폴리우레탄 대신에 폴리올로서 PTMG를 이용하여 제조된 폴리우레탄 고분자가 25 중량% 함유된 함침포를 얻도록 가공한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 사용하여 흑색 컬러의 인공피혁을 제조하였다.The procedure of Example 1 was repeated except that the polycarbonate polyurethane of Production Example 1 was replaced with the polyurethane polymer prepared by using PTMG as a polyol to obtain a dipping cloth containing 25% by weight of a polyurethane polymer. Artificial leather of black color was produced using the same method.
상기 실시예 및 비교예에서 제조된 인공피혁에 대하여 하기의 평가방법으로 물성을 측정하고 그 결과를 표 3에 나타내었다.The properties of the artificial leather prepared in the above Examples and Comparative Examples were measured by the following evaluation methods, and the results are shown in Table 3.
<평가방법><Evaluation method>
본 발명에서 '인공피혁의 마찰견뢰도'는 ISO 105법에 의하여 측정한다.In the present invention, the 'fastness to friction of artificial leather' is measured according to ISO 105 method.
건마찰 견뢰도 평가는 폭 25 mm, 길이 220 mm의 시험 편을 세로방향에 평행으로 2 매 취하여 마찰시험기의 시험대에 고정하고, 세로, 가로 각각 50 mm의 백면포로 시험기의 마찰자를 덮어 고정한다. 마찰자에는 4.9 N(500 gf)의 하중을 건 후, 왕복속도 30 회/분, 이행 거리 100 mm로 시험편의 표면을 100 회 왕복시킨 후 백면포를 벗겨 백면포의 오염 정도를 오염용 그레이 스케일로 판정한 등급을 구한다.In the evaluation of the dry friction resistance, two test specimens with a width of 25 mm and a length of 220 mm are taken parallel to the longitudinal direction, fixed on the test stand of the friction tester, and the rubbers of the test rollers of 50 mm in length and 50 mm in width are fixed. After a load of 4.9 N (500 gf) was applied to the rubbing member, the surface of the test piece was reciprocated 100 times at a reciprocating speed of 30 times / min and a transfer distance of 100 mm. Then, the white cotton cloth was peeled off, Is obtained.
습마찰 견뢰도 평가는 폭 25 mm, 길이 220 mm의 시험편을 세로방향에 평행으로 2 매 취하여 마찰시험기의 시험대에 고정하고, 세로, 가로 각각 50 mm의 백면포로 인공 땀액에 10 분간 침적한 후 가볍게 짜서 시험기의 마찰자를 덮어 고정한다. 마찰자에는 4.9 N(500 gf)의 하중을 건 후, 왕복속도 30 회/분, 이행 거리 100 mm로 시험편의 표면을 100 회 왕복시킨 후 백면포를 벗겨 백면포의 오염 정도를 오염용 그레이 스케일로 판정한 등급을 구한다.The wet rubbing fastness test was carried out by taking two parallel test specimens having a width of 25 mm and a length of 220 mm and fixing them on a test stand of a friction tester and immersing them in a 50 mm long, Cover and fix the rubbers of the testing machine. After a load of 4.9 N (500 gf) was applied to the rubbing member, the surface of the test piece was reciprocated 100 times at a reciprocating speed of 30 times / min and a transfer distance of 100 mm. Then, the white cotton cloth was peeled off, Is obtained.
본 발명에서 '인공피혁의 마모강도'는 MS320-19법에 의하여 측정한다.In the present invention, the 'abrasion strength of artificial leather' is measured by the MS320-19 method.
직경이 약 150 mm의 시험 편을 취하여 그 중앙부에 직경 약 6 mm의 구멍을 뚫고, 마모시험기(JIS L 1096(일반직물 시험방법)으로 규정한 Taber형 마모시험기)에 설치하여 하기 표 1의 조건에 따라서 시험을 행한다. 시험을 행한 후의 표면마모 상태를 하기 표 2의 등급으로 나타내거나, 또는 별도로 정한 표준시료와 비교 판정하는 것도 가능하다. A test piece having a diameter of about 150 mm was drilled and a hole having a diameter of about 6 mm was drilled in the center thereof. The test piece was placed in an abrasion tester (Taber type abrasion tester specified by JIS L 1096 The test is carried out. The state of surface abrasion after the test is performed can be indicated by the grade in Table 2 or can be compared with a standard specimen determined separately.
본 발명에서 중량평균분자량(Mw)은, 시료를 겔 투과 크로마토그래피(GPC)(RI-8000, Tosoh사)를 이용하여, 테트라하이드로퓨란(tetrahydrofuran)을 이동상(유속 1 mL/min)으로 하고 TSKgel super HM-L, TSKgel super HM-M, TSKgel super HM-N(Tosoh사)을 직렬로 연결한 칼럼을 통과시키되, 칼럼오븐의 온도를 40 ℃로 한 조건에서 측정한다.In the present invention, the weight average molecular weight (Mw) of the sample is measured by using tetrahydrofuran as a mobile phase (flow rate: 1 mL / min) using gel permeation chromatography (GPC) (RI- pass through a column in which a super HM-L, a TSKgel super HM-M and a TSKgel super HM-N (Tosoh) are connected in series, and the temperature of the column oven is set to 40 ° C.
상기 표 3으로부터 본 발명에 따른 폴리카보네이트폴리우레탄을 함침시킨 인공피혁이, 마찰견뢰도와 마모강도에서, 통상의 폴리우레탄을 함침시킨 인공피혁보다 우수한 특성을 나타냄을 확인할 수 있다. From the above Table 3, it can be seen that the artificial leather impregnated with the polycarbonate polyurethane according to the present invention shows better characteristics than the artificial leather impregnated with ordinary polyurethane in the friction fastness and the abrasion strength.
Claims (6)
상기 고분자 탄성체는, 폴리카보네이트디올; 이소시아네티트; 및 사슬 연장제로서 에틸렌글리콜 및 메틸렌비스벤젠아민;을 포함한 원료로 중합된 폴리카보네이트폴리우레탄으로서,
상기 폴리카보네이트폴리우레탄이 상기 인공피혁에서 10~40 중량% 함유되는 것을 특징으로 하는 마모 및 마찰견뢰도가 우수한 인공피혁.An artificial leather comprising a nonwoven fabric made of sea-island microfine fibers impregnated with a polymeric elastomer and dyed,
The polymeric elastomer includes polycarbonate diol; Isocyanat; And polycarbonate polyurethane polymerized with a raw material containing ethylene glycol and methylene bisbenzene amine as a chain extender,
Wherein the polycarbonate polyurethane is contained in the artificial leather in an amount of 10 to 40% by weight.
상기 인공피혁은 ISO 105법에 의한 건마찰 견뢰도가 4급 이상이며, 습마찰 견뢰도가 4급 이상인 것을 특징으로 하는 마모 및 마찰견뢰도가 우수한 인공피혁.The method according to claim 1,
Wherein the artificial leather has a dry friction resistance of not less than grade 4 according to the ISO 105 method, and a wet friction fastness of not less than grade 4, which is excellent in wear and friction fastness.
상기 인공피혁은 마모강도가 10,000 사이클(Taber 마모 C5-10, 파열시점) 이상인 것을 특징으로 하는 마모 및 마찰견뢰도가 우수한 인공피혁.The method according to claim 1,
Wherein the artificial leather has an abrasion strength of 10,000 cycles (Taber abrasion C5-10, rupture time) or more, and is excellent in abrasion and friction fastness.
상기 폴리카보네이트디올은 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올로서, 하기 화학식 1로 표시되는 화합물인 것을 특징으로 하는 마모 및 마찰견뢰도가 우수한 인공피혁.
[화학식 1]
Wherein the polycarbonate diol is a linear aliphatic polycarbonate / polyethylene polyol, and is a compound represented by the following formula (1).
[Chemical Formula 1]
상기 선형 지방족 폴리카보네이트/폴리에틸렌 폴리올은 중량평균분자량이 500 ~ 3,000인 것을 특징으로 하는 마모 및 마찰견뢰도가 우수한 인공피혁.5. The method of claim 4,
The linear aliphatic polycarbonate / polyethylene polyol has a weight average molecular weight of 500 to 3,000. The artificial leather excellent in abrasion and friction fastness.
상기 폴리카보네이트폴리우레탄은, 폴리올 및 사슬연장제에 대해 이소시아네이트를 등몰의 비율로 반응시키되,
상기 폴리카보네이트디올 0.4 ~ 0.6 몰, 사슬 연장제로서 에틸렌글리콜 0.2 ~ 0.3 몰 및 메틸렌비스벤젠아민 0.2 ~ 0.3몰의 비율인 것을 특징으로 하는 마모 및 마찰견뢰도가 우수한 인공피혁.The method according to claim 1,
The polycarbonate polyurethane is produced by reacting an isocyanate with a polyol and a chain extender at an equivalent molar ratio,
0.4 to 0.6 mol of the polycarbonate diol, 0.2 to 0.3 mol of ethylene glycol as a chain extender, and 0.2 to 0.3 mol of methylene bisbenzene amine.
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