KR101108766B1 - Artificial Leather for Interior Material of Automobile Having Silicon Coating Layer and Manufacturing Method Thereof - Google Patents
Artificial Leather for Interior Material of Automobile Having Silicon Coating Layer and Manufacturing Method Thereof Download PDFInfo
- Publication number
- KR101108766B1 KR101108766B1 KR1020090019897A KR20090019897A KR101108766B1 KR 101108766 B1 KR101108766 B1 KR 101108766B1 KR 1020090019897 A KR1020090019897 A KR 1020090019897A KR 20090019897 A KR20090019897 A KR 20090019897A KR 101108766 B1 KR101108766 B1 KR 101108766B1
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- South Korea
- Prior art keywords
- coating layer
- artificial leather
- polyurethane
- silicone
- coating
- Prior art date
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 28
- 239000010703 silicon Substances 0.000 title claims abstract description 28
- 239000011247 coating layer Substances 0.000 title claims abstract description 27
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- 229920002635 polyurethane Polymers 0.000 claims abstract description 49
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- 238000000576 coating method Methods 0.000 claims abstract description 48
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 24
- -1 automotive interior Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 23
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- 230000000052 comparative effect Effects 0.000 description 17
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
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- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
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- 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 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D06N2209/00—Properties of the materials
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- D06N2209/00—Properties of the materials
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- Chemical Kinetics & Catalysis (AREA)
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- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
본 발명은 실리콘 코팅층을 포함하는 자동차 내장재용 인공피혁 및 이것의 제조방법에 대한 것으로, 특히 부직포 원단의 일면에 실리콘 고무액으로 코팅되어 형성된 실리콘 코팅층; 및, 상기 실리콘 코팅층에 형성된 폴리우레탄 표면 코팅층;을 포함하는 것을 특징으로 한다. 이러한 본 발명은 부직포 원단과 폴리우레탄 표면 코팅층 사이에 실리콘 고무액을 코팅시킴으로서, 실리콘 고유 특성인 고 내광성, 고 내열성 및 난연성을 가지는 자동차 내장재용 인공피혁을 제공할 수 있다. The present invention relates to an artificial leather for automobile interior materials including a silicone coating layer and a method for manufacturing the same, in particular a silicone coating layer formed by coating a silicone rubber solution on one surface of a nonwoven fabric; And a polyurethane surface coating layer formed on the silicon coating layer. The present invention by coating the silicone rubber solution between the non-woven fabric and the polyurethane surface coating layer, it is possible to provide an artificial leather for automotive interior material having a high light resistance, high heat resistance and flame retardant properties of silicon.
인공피혁, 자동차 내장재, 실리콘 코팅층 Artificial leather, automotive interior, silicone coating layer
Description
본 발명은 자동차 내장재로 사용되는 인공피혁에 대한 것으로, 특히 실리콘 코팅층을 포함하는 자동차 내장재용 인공피혁 및 이것의 제조방법에 대한 것이며, 더욱 상세하게는 부직포 원단과 폴리우레탄 표면 코팅층 사이에 실리콘 코팅층을 가짐으로서, 실리콘 고유 특성인 고 내광성, 고 내열성 및 난연성을 가지는 자동차 내장재용 인공피혁에 대한 것이다. The present invention relates to artificial leather used as automotive interior materials, and more particularly to artificial leather for automobile interiors including a silicone coating layer and a method of manufacturing the same, and more particularly, a silicone coating layer between a nonwoven fabric and a polyurethane surface coating layer. The present invention relates to an artificial leather for automotive interior having high light resistance, high heat resistance, and flame retardancy, which are inherent to silicon.
자동차 내장재로서 폴리우레탄 인공피혁은 초기 PVC를 대체하는 소재로써 시트커버용, 기어 싸게용, 도어트림용 등의 용도로 사용 되어져 왔으나, 자동차 내장재중 IP 판넬 등의 용도로 확대 적용하기 위해서는 보다 높은 열안정성과, 내광성이 요구되어지게 되었다. Polyurethane artificial leather has been used for automobile seat cover, gear cheaper, door trim, etc. as a material to replace PVC in the early stages of automobile interior materials. Stability and light resistance were required.
자동차 내장재로서 폴리우레탄 인공피혁의 내열성은, 폴리우레탄 수지의 골격을 조절함으로서 함침 및 코팅 가공시 적용되는 폴리우레탄 수지의 내열성을 높이거나, 첨가제를 적용하여 내열성을 높이는 방법을 사용하고 있는데, 이와 같은 방법으로 내열성을 높이는 방법은 적용 수지의 Hardness 증가로 최종 제품의 감성과 물성이 저하되는 문제점이 있다. The heat resistance of polyurethane artificial leather as an automobile interior material is used to increase the heat resistance of the polyurethane resin applied during impregnation and coating processing by adjusting the skeleton of the polyurethane resin, or to increase the heat resistance by applying an additive. The method of increasing the heat resistance by the method has a problem that the sensitivity and physical properties of the final product is lowered by increasing the hardness of the applied resin.
그리고, 자동차 내장재의 내광성을 확보하기 위하여, 종래에는 표면 코팅제로 사용되는 폴리우레탄수지 합성시 내광성이 우수한 원료를 이용하거나, 표면 코팅제에 광안정제를 적용하는 방법이 이용되었는데, 완제품의 감성과 물성을 고려할때 보다 높은 열안정성과 내광성을 확보하기 위해서는 표면 코팅시 적용되는 폴리우레탄 수지의 개질 만으로는 한계가 있었다. In addition, in order to secure the light resistance of automobile interior materials, conventionally, a method using a material having excellent light resistance when synthesizing a polyurethane resin used as a surface coating agent or applying a light stabilizer to the surface coating agent was used. In consideration of the modification of the polyurethane resin applied to the surface coating in order to secure a higher thermal stability and light resistance there was a limit.
또한, 자동차 내장재의 난연성을 확보하기 위하여, 종래에는 부직포 함침가공 중에 난연제를 첨가하거나 스프레이 방식으로 난연제를 부직포 배면에 도포하는 방법이 일반적으로 사용되었는데, 상기 함침가공 중에 난연제를 첨가하는 방법은 이후 감량가공 공정 중에 사용되는 가성소다 및 이어지는 제조 공정 중에 사용되는 다양한 용제에 의해 앞서서 첨가된 난연제가 침해되거나 경시변화에 의한 난연제의 표면으로의 이행현상 또는 표면에 잔류하는 난연제가 대기중의 수분을 흡습하여 발생되는 표면 백분 현상 등의 표면 불량을 일으키는 문제점이 있고, 상기 스프레이 방식으로 난연제를 도포하는 방법은 완제품 상태에서 흡습에 의한 상품성 저하 현상 뿐만 아니라 폴리우레탄 인공피혁 고유의 감성물성 저하시키는 문제점이 있다. In addition, in order to secure the flame retardancy of the automotive interior, conventionally, a method of adding a flame retardant during nonwoven fabric impregnation processing or applying a flame retardant to the back surface of the nonwoven fabric by spray method has been generally used. The caustic soda used during processing and the various solvents used during the subsequent manufacturing process infringe on the flame retardant added to the surface or change the flame retardant to the surface due to changes over time, or the flame retardant remaining on the surface absorbs moisture in the air. There is a problem that causes surface defects such as surface powder phenomenon occurs, the method of applying the flame retardant by the spray method has a problem of reducing the intrinsic sensitivity of the polyurethane artificial leather as well as the deterioration of the merchandise by the moisture absorption in the finished product state.
상기한 문제점을 해결하기 위한 본 발명은 기존 인공피혁 제품의 감성과 물성을 유지하면서 기존의 방법으로는 구현이 어려운 내열성과 보다 안정적인 내광성 및 난연성을 가지는 자동차 내장재용 인공피혁을 제공하는 것이 목적이다. An object of the present invention for solving the above problems is to provide artificial leather for automotive interior materials having heat resistance and more stable light resistance and flame retardancy that is difficult to implement by the existing method while maintaining the sensitivity and physical properties of the existing artificial leather products.
또한, 종래와 같이 함침 가공 중에 난연제를 첨가하거나 난연제를 스프레이 형태로 코팅하는 경우 발생하는 난연제의 침해현상이나 경시변화에 의한 표면으로의 이행현상 및 표면 백분 현상을 방지하면서, 우수한 난연 효과를 가지는 자동차 내장재용 인공피혁의 제조방법을 제공하기 위한 것이다. In addition, a vehicle having an excellent flame retardant effect while preventing the transition to the surface due to the intrusion of the flame retardant or the change of the surface due to the change over time during the addition of a flame retardant during the impregnation processing or coating the flame retardant in the form of a spray It is to provide a method of manufacturing artificial leather for interior materials.
상기한 목적을 달성하기 위한 본 발명은, 부직포 원단의 일면에 실리콘 고무액을 코팅해서 실리콘 코팅층을 형성하는 단계; 및, 상기 형성된 실리콘 코팅층에 폴리우레탄 표면 코팅층을 형성하는 단계;를 포함하는 실리콘 코팅층을 포함하는 자동차 내장재용 인공피혁의 제조방법이다. The present invention for achieving the above object, the step of forming a silicone coating layer by coating a silicone rubber liquid on one side of the nonwoven fabric; And forming a polyurethane surface coating layer on the formed silicon coating layer. The method of manufacturing artificial leather for automobile interior material comprising a silicon coating layer.
여기서, 상기 실리콘 코팅층을 형성하는 단계는, 부직포 원단을 준비하는 단계; 비닐기(vinyl group)을 가지는 주쇄와 메틸하이드로젠기(Methylhydrogen group)를 가지는 경화제를 혼합하여 교반한 실리콘 고무액을 준비하는 단계; 및, 상기 준비된 부직포 원단의 일면에 상기 실리콘 고무액을 코팅기로 코팅하고, 건조 경화시키는 단계;를 포함하는 것이 바람직하다. Here, the step of forming the silicon coating layer, preparing a nonwoven fabric; Preparing a stirred silicone rubber liquid by mixing a main chain having a vinyl group and a curing agent having a methylhydrogen group; And coating the silicone rubber liquid with a coater on one surface of the prepared nonwoven fabric and drying and curing the same.
그리고, 상기 실리콘 고무액은 난연제로서, 예를 들면 알루미늄하이드레이트(Alumina hydrate), 티타늄다이옥사이드(Titanium dioxide) 및 실리카(silica)로 이루어진 군에서 하나 이상이 선택된 것을 더 포함하는 것이 더욱 바람직하다. In addition, the silicone rubber liquid may further include one or more selected from the group consisting of aluminum hydrate, titanium dioxide, and silica, for example, as a flame retardant.
본 발명의 다른 실시형태는 실리콘 코팅층을 포함하는 자동차 내장재용 인공피혁으로서, 부직포 원단; 상기 부직포 원단의 일면에 실리콘 고무액으로 코팅되어 형성된 실리콘 코팅층; 및, 상기 실리콘 코팅층에 형성된 폴리우레탄 표면 코팅층;을 포함하는 것이 특징이다. Another embodiment of the present invention is an artificial leather for automotive interior including a silicon coating layer, non-woven fabric; A silicon coating layer formed by coating a silicone rubber solution on one surface of the nonwoven fabric; And a polyurethane surface coating layer formed on the silicon coating layer.
여기서, 상기 실리콘 코팅층은, 비닐기(vinyl group)을 가지는 주쇄와 메틸하이드로젠기(Methylhydrogen group)를 가지는 경화제가 혼합된 실리콘 고무액이 경화되어 이루어진 것이 바람직하고, 상기한 바와 같이 난연제를 더 포함하는 것도 가능하다. Here, the silicone coating layer is preferably made of a silicone rubber liquid mixed with a main chain having a vinyl group and a curing agent having a methylhydrogen group, and further comprising a flame retardant as described above. It is also possible.
기타 실시예들의 구체적인 사항들은 상세한 설명 및 도면들에 포함되어 있다. Specific details of other embodiments are included in the detailed description and the drawings.
이러한 본 발명은 부직포 원단과 폴리우레탄 표면 코팅층 사이에 실리콘 코팅층을 가짐으로서, 기존 인공피혁 제품의 감성과 물성을 유지하면서 기존의 방법으로는 구현이 어려운 내열성과 보다 안정적인 내광성 및 난연성을 가지는 자동차 내장재용 인공피혁을 제공할 수 있는 효과가 있다. The present invention has a silicone coating layer between the non-woven fabric and the polyurethane surface coating layer, while maintaining the sensitivity and physical properties of the existing artificial leather products for automobile interior materials having heat resistance and more stable light resistance and flame resistance difficult to implement by conventional methods It is effective to provide artificial leather.
또한, 상기 실리콘 코팅층을 형성하기 위한 실리콘 고무액이 난연제를 더 포함하여, 상기 실리콘 코팅층의 형성과 함께 그 안에서 난연제가 안정적으로 보호됨으로서, 함침 가공 중에 난연제를 첨가하거나 난연제를 스프레이 형태로 코팅하는 경우 발생하는 난연제의 침해현상이나 경시변화에 의한 표면으로의 이행현상 및 표면 백분 현상을 방지할 수 있는 효과가 있다. In addition, the silicone rubber liquid for forming the silicone coating layer further comprises a flame retardant, and when the flame retardant is stably protected therein with the formation of the silicone coating layer, when adding a flame retardant during impregnation processing or coating the flame retardant in the form of a spray There is an effect that can prevent the phenomenon of intrusion of the flame retardant or transition to the surface due to the change over time and surface whitening phenomenon.
이하에서는 본 발명의 바람직한 하나의 실시형태를 첨부된 도면을 참조하여 상세하게 설명하기로 한다.Hereinafter, one preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명에 따른 자동차 내장재용 인공피혁(1)에 대한 구조의 일례를 나타내는 단면도이고, 여기에 도시된 바와 같이 본 발명은 부직포 원단(10); 실리콘 코팅층(20); 및 폴리우레탄 표면 코팅층(30);을 포함하고, 특히 실리콘 코팅층(20)을 포함하는 것이 특징이다. 1 is a cross-sectional view showing an example of a structure for the artificial leather 1 for automobile interior according to the present invention, as shown herein, the present invention is a
즉, 본 발명은 부직포 원단(10)과 폴리우레탄 표면 코팅층(30) 사이에 실리콘 코팅층(20)을 가짐으로서, 실리콘 고유 특성인 고 내광성, 고 내열성 및 난연성을 가지는 자동차 내장재용 인공피혁을 제공하는 것이다. That is, the present invention has a
종래에 자동차 내장재로 사용되는 인공피혁에 내열성을 부여하기 위해서는 부직포 원단으로 사용되는 폴리우레탄 수지의 골격을 조절하거나 첨가제를 적용해야 했고, 내광성을 부여하기 위해서는 내광성이 우수한 원료를 표면 코팅제로 사용하거나 광안정제를 첨가해야 했으며, 난연성을 부여하기 위해서는 부직포 원단의 함침 가공지 난연제를 첨가하거나 스프레이 방식으로 도포해야만 했다. Conventionally, in order to impart heat resistance to artificial leather used as automobile interior materials, it is necessary to adjust the skeleton of the polyurethane resin used as a nonwoven fabric or apply an additive.In order to impart light resistance, a raw material having excellent light resistance is used as a surface coating or Tablets had to be added, and impregnated paper impregnated paper flame retardants had to be added or spray applied to impart flame retardancy.
그러나, 본 발명자들은 부직포 원단(10)과 폴리우레탄 표면 코팅층(30) 사이에 실리콘 코팅층(20)을 구비시킴으로서, 기존 인공피혁 제품의 감성과 물성을 유지하면서 기존의 방법으로는 구현이 어려운 내열성과 보다 안정적인 내광성 및 난연성을 가지는 자동차 내장재용 인공피혁(1)을 제조할 수 있었다. However, the present inventors provided a
이에 따라, 상기 부직포 원단(10)은 자동차 내장재용으로 사용되는 모든 종류의 원단을 포함한다. 예를 들어, 나일론과 폴리에스테르로 이루어진 해도형 원사를 이용한 것뿐만 아니라, PET/PET 해도형 원사 등과 같이 이 기술분야에서 널리 알려진 다양한 형태의 원단이 사용될 수 있다. Accordingly, the
그리고, 본 발명은 상기와 같은 부직포 원단(10)의 일면에 실리콘 고무액으로 코팅되어 형성된 실리콘 코팅층(20)을 포함하는 것이 특징이다. 상기 실리콘 고무액이라함은 실리콘 고무(Silicone Rubber) 소재를 포함하는 배합액(Liquid Silicone Rubber : LSR), 즉 액상 실리콘 고무를 뜻하는 것으로, 본 발명은 이러한 LSR이 상기 부직포 원단(10)의 일면에 코팅기로 코팅된 것이 특징이다. And, the present invention is characterized in that it comprises a
상기 LSR은 이 기술분야에서 널리 알려진 다양한 형태의 액상 실리콘 고무를 포함하고, 예를 들면, 비닐기(vinyl group)을 가지는 주쇄와 메틸하이드로젠기(Methylhydrogen group)를 가지는 경화제가 혼합된 실리콘 고무액이 사용될 수 있으며, 이러한 실리콘 고무액은 코팅기를 이용한 가열 및 건조 경화 과정에서, 상기 비닐기와 메틸하이드로젠기가 부가 또는 축합반응으로 경화되어 실리콘 코팅층을 형성한다는 점에서 바람직하다. 이와 같은 부가 또는 축합반응에 의해 상기 주쇄와 경화제는 서로 가교 구조를 형성하고, 표면과 내부에서 함께 경화반응이 진행됨으로서 심부 경화성이 양호한 실리콘 소재의 안정적인 특성을 가지게 할 수 있다. 나아가, 상기 비닐기와 메틸하이드로젠기의 부가 또는 축합반응은 백금 촉매의 존재하에서 이루어지는 것이 부산물이 적어 더욱 바람직하다. The LSR includes various types of liquid silicone rubbers well known in the art, for example, a silicone rubber liquid in which a main chain having a vinyl group and a curing agent having a methylhydrogen group are mixed. This silicone rubber liquid is preferable in that the vinyl group and the methylhydrogen group are cured by addition or condensation reaction to form a silicone coating layer in a heating and dry curing process using a coating machine. By such an addition or condensation reaction, the main chain and the curing agent form a crosslinked structure with each other, and the curing reaction proceeds together on the surface and the inside thereof, thereby making it possible to have stable characteristics of a silicone material having good core hardenability. Further, the addition or condensation reaction of the vinyl group and the methylhydrogen group is more preferable because there are few by-products in the presence of a platinum catalyst.
그리고, 내열성, 내광성, 난연성 등의 물리적 특성을 더욱 강화하기 위해서는 상기 LSR이 알루미늄하이드레이트(Alumina hydrate), 티타늄다이옥사이드(Titanium dioxide), 실리카(silica) 등과 같은 난연제를 더 포함하는 것도 가능하다. In addition, the LSR may further include a flame retardant such as aluminum hydrate, titanium dioxide, silica, etc. in order to further enhance physical properties such as heat resistance, light resistance, and flame resistance.
또한, 상기 LSR을 부직포 원단(10)에 코팅시키는 방법은 특별히 제한되지 않으며, 예를 들면 그라비아 코팅 방법 또는 Direct Coating 가공 방법을 이용할 수 있다. In addition, the method of coating the LSR on the
본 발명에 따른 인공피혁(1)은 이와 같은 실리콘 코팅층(20) 상에 형성된 폴리우레탄 표면 코팅층(30)을 포함하여 이루어진 것이고, 상기 폴리우레탄 표면 코팅층(30)은 이 기술분야에서 널리 알려진 다양한 표면 코팅층을 포함하며, 특별히 폴리우레탄 수지로 이루어진 것을 사용하는 것이 바람직하다. 이러한 폴리우레탄 표면 코팅층(30)은 상기 형성된 실리콘 코팅층(20)을 보호함과 아울러 상기 실리콘 코팅층(20)이 가지는 내열성, 내광성, 난연 특성을 더욱 우수하게 한다. Artificial leather (1) according to the invention comprises a polyurethane
도 2는 본 발명에 따라 부직포 원단(10); 실리콘 코팅층(20); 접착제층(25); 제1폴리우레탄 표면 코팅층(31); 및 제2 폴리우레탄 표면 코팅층(32);을 포함하는 자동차 내장재용 인공피혁(1)에 대한 구조의 일례를 나타내는 단면도이고, 이를 참조로 하여 본 발명의 다른 실시형태에 따른 자동차 내장재용 인공피혁(1)과 이것의 제조방법을 설명한다. 2 is a
먼저, 본 발명에 따라 실리콘 코팅층을 포함하는 자동차 내장재용 인공피혁의 제조방법은, 부직포 원단(10)의 일면에 실리콘 고무액을 코팅해서 실리콘 코팅층(20)을 형성하고, 이어서 상기 형성된 실리콘 코팅층에 폴리우레탄 표면 코팅 층(30)을 형성하는 단계를 거친다. First, according to the present invention, a method for manufacturing artificial leather for automobile interior material comprising a silicone coating layer is formed by coating a silicone rubber solution on one surface of a
상기 부직포 원단(10)은 상술한 바와 같이 이 기술분야에서 알려진 다양한 형태의 원단을 사용할 수 있고, 예를 들면 섬도가 3.5 데니어인 폴리에스테르와 나일론으로 구성된 해도형 섬유 부직포를 폴리우레탄 수지 배합액을 이용하여 함침가공후 가성소다를 이용한 감량가공 방법으로 섬유내의 해성분인 폴리에스테르를 제거한 것을 이용할 수 있다. 그리고, 함침가공시 적용된 폴리우레탄 수지를 감량가공시 견딜수 있도록 에테르 타입의 폴리올을 사용한 폴리우레탄 수지를 사용할 수 있으며, 함침 가공시 색상이 필요할 경우에는 폴리우레탄 수지를 이용하여 제조된 토너를 첨가하여 함침 원단의 색상을 조절할 수도 있다. 나아가, 감량 가공된 원단을 나일론 염색시 통상적으로 사용되는 산성염료로 염색 가공한 후 이용하거나, 염색 가공 없이 감량 가공된 상태의 원단을 폴리우레탄 건식 코팅 가공을 위한 부직포 원단으로 사용할 수도 있다. The
이어서, 본 발명은 상기한 바와 같이 준비된 부직포 원단(10)의 일면에 실리콘 고무액을 코팅해서 실리콘 코팅층(20)을 형성한다. 즉, 감량 가공하거나 염색 가공한 부직포 원단(10)의 어느 한면에 LSR을 Direct 코팅 또는 그라비아 코팅 방법으로 코팅 가공하는 것이다. 상기 LSR 코팅 가공시 적용되는 실리콘 소재는 비닐기(Vinyl group)와 메틸하이드로젠기(Methyl hydrogen group)가 백금 촉매 존재 하에서 부가 경화반응으로 경화되는 LSR을 사용하는 것이 바람직하며, 내열특성, 난 연특성을 보다 향상시키기 위해서는 알루미늄하이드레이트(Alumina hydrate)와 티타늄다이옥사이드(Titanium dioxide), 실리카 등을 더 포함할 수 있다. 그래서, 예를 들면, 비닐기을 가지는 주쇄와 메틸하이드로젠기를 가지는 경화제를 혼합하여 교반한 실리콘 고무액을 준비하고, 상기 준비된 부직포 원단(10)의 일면에 상기 실리콘 고무액을 80～250 g/m2 의 양으로 도포하여 코팅 가공한 후, 건조 경화시키는 것이다. Subsequently, the present invention forms a
여기서, 제품의 표면 색상을 조절하기 위하여 상기 LSR의 주쇄 또는 실록산에 안료를 혼합한 코팅용 토너를 사용할 수도 있고, 상기 안료는 주쇄, 경화제 혼합시 5-20 part를 적용하여 다양한 색상을 발현시키는 것도 가능하다. 나아가, 자동차 내장재용 인공피혁에 요구되는 기계적 물성, 화학적 물성, 감성 물성 정도에 따라 LSR 종류 및 코팅량을 다양하게 적용시키는 것도 가능하다. Here, in order to control the surface color of the product, a coating toner may be used in which a pigment is mixed with the main chain or siloxane of the LSR, and the pigment may express various colors by applying 5-20 parts when the main chain and the curing agent are mixed. It is possible. Furthermore, it is also possible to apply various types of LSR and coating amount according to the mechanical, chemical and emotional properties required for artificial leather for automobile interior materials.
다음으로는, 상기와 같이 형성된 실리콘 코팅층(20)에 폴리우레탄 표면 코팅층(30)을 형성하는데, 상기 폴리우레탄 표면 코팅층(30)은 접착제층(25)을 이용한 건식 코팅 가공 방법으로 제1폴리우레탄 표면 코팅층(31)과 제2폴리우레탄 표면 코팅층(32)으로 구분하여 형성하는 것도 가능하다. Next, the polyurethane
예를 들면, 먼저 별도의 이형지에 MEK, DMF로 희석된 폴리우레탄 배합액을 코팅, 건조하여 제1폴리우레탄 표면 코팅층(31)과 제2폴리우레탄 표면 코팅층(32)을 위한 Top층을 형성하고, 여기에 접착제층(25)을 위한 Binder를 도포한다. 상기 Top층 형성용 폴리우레탄 수지로는 자동차 내장재 용도로 사용되는 실리콘 디올이 합성되어 내광성이 우수한 폴리우레탄 수지를 이용할 수 있고, Binder 수지는 2액형 타입의 폴리우레탄 Binder를 이용하는 것이 가능하다. 그리고, 이러한 이형지를 상기 준비된 부직포 원단(10)의 실리콘 코팅층(20)과 Binder가 마주하게 합포한 다음, 숙성시킨 후, 상기 이형지만을 박리하여 건식 코팅형 극세 폴리우레탄 인공피혁을 제조할 수 있다. For example, first coating a polyurethane mixture diluted with MEK and DMF on a separate release paper and drying to form a top layer for the first polyurethane
이상과 같은 방법으로, 본 발명에서 목적으로 하는 자동차 내장재용 폴리우레탄 인공피혁을 얻을 수 있었는데, 이렇게 제조된 폴리우레탄 인공피혁은 기존의 제조 방법으로 얻어진 폴리우레탄 인공피혁과 비교하여, 현저히 우수한 내열성, 안정적인 내광성 및 난연성을 가짐으로서, 자동차 내장재 분야 중에서 비교적 고 물성을 요하는 IP 판넬 등의 부위에 적용하는 것이 가능하다. According to the above method, the polyurethane artificial leather for automotive interior material, which is the object of the present invention, was obtained, and the polyurethane artificial leather thus prepared was significantly superior in heat resistance, compared with the polyurethane artificial leather obtained by the conventional manufacturing method. By having a stable light resistance and flame retardancy, it is possible to apply to parts such as IP panels that require relatively high physical properties in the field of automotive interior materials.
즉, 본 발명에 따른 자동차 내장재용 인공피혁은 폴리우레탄 인공피혁 제조시 실리콘 코팅을 접목 함으로서, 하기와 같이 우수한 내열성, 난연성, 내광성을 가짐을 확인하였다. That is, the artificial leather for automobile interior according to the present invention by combining the silicone coating in the production of polyurethane artificial leather, it was confirmed that it has excellent heat resistance, flame retardancy, light resistance as follows.
내열성 : 외관 - 이상없음, 변색 5급, 광택변화율 12 이하,Heat resistance: Appearance-No abnormality, discoloration 5 grade, gloss change rate 12 or less,
난연성 : SENBR～SE,Flame Retardant: SENBR ～ SE,
내광성 : 4～5급 이상Light resistance: 4 ~ 5 grade or more
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해 될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며, 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention may be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예 : 자동차 내장재용 인공피혁의 제조 Example: Preparation of artificial leather for automobile interior
실시예 1Example 1
실시예 1-1 : 부직포 원단의 준비Example 1-1 Preparation of Nonwoven Fabrics
< 기본 원단><Base fabric>
폴리에스테르와 나일론으로 구성된 3.5 데니어 해도형 원사을 사용하여 니들 펀칭 가공방법으로 제조된 부직포를 사용하였으며, 기계적 물성 보강을 위하여 스크림을 삽입하여 제조 하였다.A nonwoven fabric manufactured by needle punching was used using 3.5 denier islands-like yarns made of polyester and nylon, and a scrim was inserted to reinforce mechanical properties.
< PVA 처리 ><PVA treatment>
검화도가 98~99.5 mole% 인 PVA 3% 수용액을 제조하여, 위에서 제조된 원단을 침지후 열수 압착하여 PVA 함침된 원단을 제조하였다.A PVA 3% aqueous solution having a saponification degree of 98 to 99.5 mole% was prepared, and a PVA-impregnated fabric was prepared by immersing the fabric prepared above, followed by hydrothermal compression.
< 함침액 제조 ><Impregnation solution manufacturing>
에테르 타입의 폴리올과 방향족 이소시아네이트를 이용하여 제조된 폴리우레탄 수지를 이용하여 함침액을 제조하였는데, 폴리우레탄 수지 100을 기준하여 용제 인 디메틸포름알데하이드를 100～130부, 블랙 안료 1부 첨가하여 함침 배합액을 제조하였다. 최종 완제품의 요구 색상에 따라 적용 안료를 변경할 수도 있다.The impregnation solution was prepared using a polyurethane resin prepared using an ether type polyol and an aromatic isocyanate. The impregnation compound was added by adding 100 to 130 parts of solvent dimethylformaldehyde and 1 part of black pigment based on the polyurethane resin 100. Liquid was prepared. The applied pigments can also be changed according to the required color of the final finished product.
< 함침가공 ><Impregnation Processing>
위에서 제조된 함침 배합액을 PVA 함침된 원단에 함침후 망글 압력을 2～3 ㎏/㎠로 압착하여, 원단 중량 대비 함침 배합액이 80～120% 정도 포함 되도록 함침 원단을 제조하였다. 함침후 적용되는 응고조, 수세조는 통상적으로 폴리우레탄 인공피혁 제조시 사용되는 가공 조건을 적용하였다.After impregnating the impregnated formulation prepared above to the PVA impregnated fabric, the mangle pressure was compressed to 2 to 3 kg / cm 2 to prepare the impregnated fabric such that the impregnated formulation was contained in an amount of about 80 to 120% by weight. The coagulation bath and the washing bath applied after the impregnation are generally applied to the processing conditions used in the manufacture of polyurethane artificial leather.
< 감량가공 ><Weight Loss Processing>
위에서 함침 가공된 원단을 10% 가성소다 수용액에서 100℃, 30분간 유지하여 해성분인 폴리에스테르 부분을 용출함으로서, 폴리우레탄 수지가 포함된 나일론 극세 원단을 제조하였다.The fabric impregnated above was kept at 100 ° C. for 30 minutes in an aqueous 10% caustic soda solution to elute the polyester portion of the sea component, thereby preparing a nylon microfiber fabric containing a polyurethane resin.
< 버핑가공 ><Buffing process>
위에서 감량 가공된 원단을 인공피혁 제조시 통상적으로 사용되는 130～180 Mesh의 샌드 페이퍼를 이용하여 코팅면의 버핑 가공을 진행하였다. The weight-reduced fabric was subjected to buffing of the coated surface using sand paper of 130 to 180 mesh which is commonly used in manufacturing artificial leather.
실시예 1-2 : LSR 코팅 가공Example 1-2: LSR Coating
상기 실시예 1-1에 따라 버핑 가공된 원단을 LSR로 코팅하기 위하여, 하기 [표 1]의 주쇄와 [표 2]의 경화제가 [표 3]의 비율로 혼합된 LSR을 준비하였다.In order to coat the buffing fabric according to Example 1-1 with LSR, an LSR was prepared in which the main chain of [Table 1] and the curing agent of [Table 2] were mixed at the ratio of [Table 3].
[표 1 : LSR의 주쇄 구성][Table 1: Main chain configuration of LSR]
[표 2 : LSR의 경화제 구성][Table 2: Hardener composition of LSR]
[표 3 : LSR의 주쇄와 경화제 비율][Table 3: Main chain and hardener ratio of LSR]
그리고, 상기와 같이 준비된 LSR을 고점도용의 범용 교반기를 이용하여 저속 교반한 후, 상기 실시예 1-1에 따라 버핑 가공된 원단에 그라비아 코팅 또는 Direct Coating 가공 방법으로 코팅 가공하였다. Then, the LSR prepared as described above was stirred at a low speed using a general purpose stirrer for high viscosity, and then coated on the buffed fabric according to Example 1-1 by gravure coating or direct coating.
이 때, 교반시 발생되는 열에 의한 배합중 경화진행을 방지하기 위하여 저속 RPM(200～800)으로 교반을 진행 하였으며, 준비된 LSR 배합액을 Direct Coating 가공기를 이용하여 코팅 도포량을 80～250 G/M2 로 표면 코팅하였고, 이후 150～180℃ 온도에서 건조 경화하였다. At this time, in order to prevent the hardening process during the mixing due to the heat generated during the stirring, stirring was performed at a low speed RPM (200 to 800). The surface was coated with 2 , and then dried and cured at a temperature of 150 ~ 180 ℃.
또한, 그라비아 코팅 가공 방법으로 LSR 코팅 가공하는 경우에는 20 mesh 또는 40 mesh등의 저 Mesh Roll을 이용하며, 상기 Direct Coating시와 유사한 코팅량을 부직포 원단 표면에 코팅함으로서, 앞착에 의해 보다 우수한 실리콘 코팅층을 형성할 수 있었다.In addition, in the case of LSR coating processing by the gravure coating processing method, a low mesh roll such as 20 mesh or 40 mesh is used, and by coating the surface of the nonwoven fabric with a coating amount similar to that of the direct coating, a superior silicone coating layer is applied by front attachment. Could form.
실시예 1-3 : 표면 건식 코팅Examples 1-3: Surface Dry Coatings
상기 실시예 1-2에 따라 형성된 실리콘 코팅층 위에, 폴리우레탄 인공피혁 건식 코팅 가공방법을 이용하여 표면 코팅층을 형성함으로써 내열성, 내광성, 난연성이 우수한 인공피혁을 제조하였다.On the silicon coating layer formed in accordance with Example 1-2, by forming a surface coating layer using a polyurethane artificial leather dry coating processing method was prepared artificial leather excellent in heat resistance, light resistance, flame retardancy.
즉, 이형지에 폴리우레탄 건식 코팅형 인공피혁 제조시 통상적으로 사용되는 가공방법으로 1차, 2차 표면 코팅층을 형성한 후, 2액형 폴리우레탄 접착제를 이용하여 상기 실리콘 코팅층에 합포시켰다. 상기 1차, 2차 표면 코팅층 가공시 적용되는 폴리우레탄 수지는 내광성이 우수한 수지로 폴리카보네니트 타입의 폴리올과 실리콘 디올을 사용하여 제조된 폴리우레탄 수지를 사용하였으며, 접착제 수지도 폴리카보네이트 폴리올을 사용한 2액형 타입의 폴리우레탄 접착제를 이용하였다.That is, after forming a primary, secondary surface coating layer by a processing method commonly used in the manufacture of polyurethane dry coating type artificial leather on a release paper, it was laminated to the silicone coating layer using a two-component polyurethane adhesive. The polyurethane resin applied to the first and second surface coating layer processing is a resin having excellent light resistance, using a polyurethane resin prepared using a polycarbonate polyol and silicone diol, the adhesive resin is also a polycarbonate polyol The used two-component type polyurethane adhesive was used.
이어서, 합포된 원단을 70～80℃ 정도의 숙성실에서 접착제를 24시간 숙성후, 이형지만을 박리하여 폴리우레탄 인공피혁을 완성하였다. Subsequently, after the adhesive fabric was aged for 24 hours in a mating chamber of about 70 to 80 ° C., only the release mold was peeled off to complete the polyurethane artificial leather.
실시예 1-4 : 후처리Example 1-4 Post-treatment
< 열수 모미 ><Thermal water momi>
위에서 건식 코팅 가공후 박리된 제품을 100℃ 열수에서 30분 동안 열수 모미 가공하여 제품내 잔존하는 용제를 최대한 제거하고, 감성 물성을 개선하고자 하였다. After the dry coating process, the product peeled off was subjected to hydrothermal processing for 30 minutes at 100 ° C. hot water to remove the solvent remaining in the product as much as possible and to improve the emotional properties.
< 표면 처리 ><Surface treatment>
위에서 제조된 제품 표면에 그라비아 코팅 가공을 이용한 표면처리 가공 방법을 적용하여 표면 광택을 조절하거나 내광성을 향상 시킬 수 있었다.Using the gravure coating process on the surface of the product manufactured above, the surface treatment could be applied to improve surface gloss or improve light resistance.
< 후가공 ><Post-processing>
위에서 제조된 제품을 이용하여 펀칭 가공등의 후가공을 접목하여 제품 표면에 다양한 표면 패턴을 구현할 수 있었다.Using the product manufactured above, various surface patterns could be realized on the surface of the product by incorporating post-processing such as punching.
실시예 2Example 2
상기 실시예 1의 <감량가공> 과정 다음에, 아래와 같은 <염색가공> 공정을 추가하여 보다 고급스러운 외관을 가진 폴리우레탄 인공피혁을 제조하였다.After the <loss processing> process of Example 1, the following <dye processing> was added to prepare a polyurethane artificial leather having a more elegant appearance.
< 염색가공 ><Dyeing Process>
염색가공은 통상적으로 나일론 염색시 사용되는 블랙 염료 10%(극세원단 중량대비), 염료 분산첨가제 1～2 g/l, 감량가공된 원단을 염색기내에 같이 넣어 염색을 진행하였다. 이때 적용된 염색조건은 100℃, 40분간 균염시간을 주었으며 욕비는 20:1로 진행하였다.The dyeing process was performed by putting 10% black dye (based on the ultrafine fabric weight), dye dispersant 1 to 2 g / l and weight-reduced fabric into the dyeing machine. At this time, the applied dyeing condition was given a homogenization time at 100 ℃ for 40 minutes and the bath ratio was 20: 1.
실시예 3Example 3
상기 실시예 1-2의 LSR 코팅 가공시 사용되는 부가형 타입의 실리콘 수지 대 신에 축합 경화 타입의 실리콘 수지를 이용한 것으로 제외하고는, 상기 실시예 1과 동일하다. Except for the additional type of silicone resin used in the LSR coating process of Example 1-2, except that the condensation curing type silicone resin was used, the same as in Example 1.
상기 부가형 타입의 실리콘 수지는 예를 들어, 비닐기를 함유하는 폴리실록산과 Si-H 결합를 갖는 폴리실록산을 부가 반응시킴에 따라 상기 실론산이 서로 가교되는 타입의 실리콘 수지일 수 있고, 이와 비교하여 축합 경화 타입의 실리콘 수지는 주성분인 폴리머의 말단기 실란올(Si-OH)과 경화제(가교제) Si-X와의 가수분해 축합반응에 의해 경화되는 것으로서, 본 실시예에서는 상기 경화제로서 알콕시 실란을 사용하였다. The addition type silicone resin may be, for example, a silicone resin of a type in which the silonic acid is crosslinked with each other by addition reaction of a polysiloxane containing a vinyl group and a polysiloxane having a Si—H bond, and compared with the condensation curing type. The silicone resin is cured by the hydrolysis condensation reaction of the end group silanol (Si-OH) and the curing agent (crosslinking agent) Si-X of the main component polymer. In this embodiment, an alkoxy silane was used as the curing agent.
실시예 4Example 4
상기 실시예 1-2의 LSR 코팅 가공시 사용되는 LSR 배합액에 알루미늄하이드레이트을 주쇄 100부 기준으로 80～150부 첨가 배합하여 코팅 가공한 것을 제외하고는, 상기 실시예 1과 동일하다. The same procedure as in Example 1 was repeated except that 80-150 parts of aluminum hydrate was added to the LSR compounding solution used in the LSR coating process of Example 1-2 based on 100 parts of the main chain.
실시예 5Example 5
상기 실시예 1-2의 LSR 코팅 가공시 사용되는 LSR 배합액에 실리카와 탄산칼슘을 주쇄 100부 기준으로 80～150부 첨가 배합하여 코팅 가공한 것을 제외하고는, 상기 실시예 1과 동일하다. The same procedure as in Example 1 was repeated except that 80 to 150 parts of silica and calcium carbonate were added to the LSR compounding solution used in the LSR coating process of Example 1-2 based on 100 parts of the main chain.
실시예 6Example 6
상기 실시예 1-1의 <기본 원단>에서 나이론, 폴리에스테르 해도형 원사 대신에 PET/PET 해도형 원사를 사용한 것을 제외하고는, 상기 실시예 1과 동일하다. In Example 1-1, except that PET / PET islands-in-the-sea yarn was used instead of nylon and polyester islands-in-the-sea yarn in Example 1-1, it was the same as Example 1.
비교예Comparative example
비교예 1Comparative Example 1
상기 실시예 1-2의 LSR 코팅 가공 과정이 없는 것을 제외하고는, 상기 실시예 1과 동일하다. Except that there is no LSR coating process of Example 1-2, it is the same as Example 1.
비교예 2Comparative Example 2
상기 비교예 1에서 <함침 가공>시 할로겐계 난연제를 100～120부 적용한 함침 배합액을 이용하여 함침가공을 진행한 것을 제외하고는, 상기 비교예 1과 동일하다. In Comparative Example 1, the same procedure as in Comparative Example 1 was conducted except that impregnation processing was performed using an impregnation mixture solution in which 100 to 120 parts of a halogen-based flame retardant was applied.
비교예 3Comparative Example 3
상기 비교예 2에서 <함침 가공>시에 사용되는 기본 원단을 상기 실시예 6에서와 같이 PET/PET 해도형 원사를 사용한 것을 제외하고는, 상기 비교예 2와 동일하다. In Comparative Example 2, except that PET / PET islands-in-the-sea yarn was used as in Example 6, the basic fabric used in <impregnation process> was the same as in Comparative Example 2.
비교예 4Comparative Example 4
상기 비교예 3에서 제조된 완제품에 난연성을 보강하기 위하여 인계 난연제를 일반적인 스프레이 가공방법으로 코팅 가공한 것을 제외하고는, 상기 비교예 3과 동일하다. In order to reinforce the flame retardancy to the finished product prepared in Comparative Example 3, except that the phosphorus-based flame retardant coating process by a general spray processing method, it is the same as Comparative Example 3.
실험예 : 인공피혁의 물성 실험Experimental Example: Physical Properties of Artificial Leather
상기 실시예 및 비교예에 따라 제조된 자동차 내장재용 인공피혁에 대하여, 하기 3가지 평가방법으로 물성을 테스트 하였고, 그 결과를 하기 [표 4]에 정리하였다. 본 실험은 시험 분석 업무를 진행하는 사내 전문가 3명의 의견을 조합하여 평가 진행 하였다.About the artificial leather for automobile interior materials prepared according to the examples and comparative examples, the physical properties were tested by the following three evaluation methods, the results are summarized in the following [Table 4]. This experiment was conducted by combining the opinions of three in-house experts who are conducting test analysis.
실험예 1 : 내열성 측정Experimental Example 1 Measurement of Heat Resistance
제조된 폴리우레탄 인공피혁 제품을 5 x 13 cm(종 x 횡) 크기의 시편으로 준비하고, 110℃ 오븐에서 300시간 방치한 후 제품 표면의 외관을 관찰하여 아래의 평가 방법으로 평가 하였다.The prepared polyurethane artificial leather product was prepared as a specimen of 5 x 13 cm (length x side) size, and left for 300 hours in an oven at 110 ℃ after observing the appearance of the product surface was evaluated by the following evaluation method.
(1) 외관 평가 : 주로 육안으로 확인되는 변퇴색, 코팅층 벗겨짐 현상, 부풀음, 잔금, 균열, 박리, 현저한 경도 변화나 끈적거림 등을 위주로 관찰 하여 이상 있음, 이상 없음으로 판정(1) Appearance evaluation: Determination of abnormality, no abnormality mainly observed by visual observation of discoloration, coating layer peeling phenomenon, swelling, residue, crack, peeling, significant change in hardness or stickiness.
(2) 변색 : Gray Scale로 평가하였으며, 1급～5급 단계의 평가 기준이고, 각 급의 중간이라고 판정되는 것은 1?2급, 2?3급, 3?4급, 4?5급으로 하여 전부 9단계의 판정 기준으로 평가하였다. 평가는 적어도 3점의 임으로 샘플 채취하여 측정을 하고, 이들을 평균적으로 보아 등급을 판정하였다.(2) Discoloration: Evaluated by Gray Scale, it is the evaluation standard of 1st ~ 5th grade level, and it is judged to be the middle of each grade as 1 ~ 2 grade, 2 ~ 3 grade, 3 ~ 4 grade, 4 ~ 5 grade. All of them were evaluated according to the nine criteria. Evaluation was carried out by sampling at least 3 points and measured, and the grades were determined by viewing these on average.
(3) 광택변화 : 오븐 방치 전, 후의 표면 광택 변화율을 측정하였으며, 평가는 적어도 3점의 임으로 샘플 채취하여 측정을 하고, 이들을 평균 변화율을 측정하였다. (3) Gloss change: The rate of surface gloss change before and after the oven was left was measured, and evaluation was carried out by sampling at least three points, and the average change rate was measured.
실험예 2 : 난연성 측정Experimental Example 2: Flame Retardant Measurement
제조된 폴리우레탄 인공피혁을 100 x 356 mm(종 x 횡) 크기로 컷트한 샘플 표면(건식 표면 코팅층)을 위로하여 수평법 난연성 시험을 진행하였으며, 아래 3개의 기준(SE, SENBR, B)으로 난연성을 판정하였다.Horizontal flame retardancy test was conducted with the sample surface (dry surface coating layer) cut to 100 x 356 mm (length x width) of the manufactured polyurethane artificial leather, and the following three standards (SE, SENBR, B) Flame retardancy was determined.
(1) SE : 불은 붙었으나 '시작점' 표선(38mm) 이전에서 불이 꺼질 때(1) SE: When the light is on but the light goes out before the 'start point' mark (38mm)
(2) SENBR : 연소가 시작하여 '시작점'에서 시간을 측정하여 60초 이전에 꺼지고 탄화거리가 50mm 미만일때(2) SENBR: When combustion starts and the time is measured at the 'start point', it turns off before 60 seconds and the carbonization distance is less than 50mm.
(3) B : '시작점'에서 불이 붙기 시작하여 'end 지점(254mm)' 이후까지 지속적으로 연소가 되는 상태로 연소 속도를 계산한다.(3) B: Calculate the combustion speed with the fire starting at the 'starting point' and continuously burning until after the 'end point (254mm)'.
* 연소속도(B)공식 : B = D/T x 60 B: 연소속도(mm/min) * Burning rate (B) formula: B = D / T x 60 B: Burning rate (mm / min)
D: 연소거리(mm) D: combustion distance (mm)
T: 연소시간(초) T: burning time (sec)
실험예 3 : 내광성 측정Experimental Example 3 Measurement of Light Resistance
제조된 폴리우레탄 인공피혁을 5 x 13 cm(종 x 횡) 크기로 컷트한 샘플의 입모면(제품으로서의 소위 프론트 서페이스라고 하는 표면)을 광조사면으로 하고, 이하의 2가지 조건(A type, B type)으로 광조사 한다. 광조사후 JIS L0804 규정의 변퇴색용 그레이 그케일로 등급을 판정하였다. The napped surface (the so-called front surface as a product) of the sample which cut the manufactured polyurethane artificial leather to 5 x 13 cm (length x side) size as a light irradiation surface, and the following two conditions (A type, B type). After light irradiation, the grade was determined by the gray gray scale for fading color of JIS L0804.
(A) 광조사 장비로 SUGA Tester Instrument사의 SX-75(300～400nm)를 이용하여 126 MJ 연속조사 : 방사조도 60～100 W/m2, 블랙 패널 89±3℃, 상대습도 50±5% RH (A) 126 MJ continuous irradiation using SUGA Tester Instrument's SX-75 (300 ~ 400nm) as light irradiation equipment: irradiance 60 ～ 100 W / m2, black panel 89 ± 3 ℃, relative humidity 50 ± 5% RH
(B) 광조사 장비로 ATLAS CI14000 를 이용하여 451.2 KJ/m2 명암 조사(명: 3.8 hr, 암 : 1.0 hr) : 방사조도 0.55 W/m2, 블랙 패널 89±2℃, 상대습도 50±5% RH (B) 451.2 KJ / m2 light intensity (light: 3.8 hr, dark: 1.0 hr) using ATLAS CI14000 as light irradiation equipment: 0.55 W / m2 of irradiance, 89 ± 2 ℃ of black panel, 50 ± 5% relative humidity RH
또한, 판정은, 1급 ～ 5급 단계의 평가 기준이고, 각 급의 중간이라고 판정되는 것은 1?2급, 2?3급, 3?4급, 4?5급으로 하여 전부 9단계의 판정 기준으로 평가하였다. 평가는 적어도 3점의 임으로 샘플 채취하여 측정을 하고, 이들을 평균적으로 보아 판단하였다. In addition, the judgment is the evaluation criteria of the 1st grade-the 5th grade grade | grade, and the grade judged as intermediate | middle of each grade | grade is 1-2 grade, 2-3 grade, 3-4 grade, and 4-5 grade, all 9 grades of determination Evaluation was made based on the criteria. Evaluation was carried out by sampling at least three points and measured, and judged by seeing these on average.
실험예 4 : 실험예 1~3의 결과Experimental Example 4 Results of Experimental Examples 1 to 3
상기 실험예 1~3에 따른 내열성, 난연성, 내광성 실험 결과를 하기 [표 4]에 정리하였다.The heat resistance, flame retardancy, and light resistance test results according to Experimental Examples 1 to 3 are summarized in the following [Table 4].
[표 4 : 내열성, 난연성, 내광성 실험 결과][Table 4: Experimental results of heat resistance, flame retardancy, light resistance]
상기 [표 4]에 나타난 바와 같이, 본 발명에 의해 LSR코팅을 이용하여 제조된 건식 코팅형 폴리우레탄 인공피혁은 인공피혁 고유의 감성 물성을 유지하면서 우수한 내열성 및 안정적인 난연성, 내광성을 가질 수 있고, 동시에 경시변화에 의한 표면 백화 현상 등의 문제점 없는 것으로 확인되었다. As shown in Table 4, the dry-coated polyurethane artificial leather manufactured using the LSR coating according to the present invention may have excellent heat resistance and stable flame retardancy and light resistance, while maintaining intrinsic emotional properties of artificial leather. At the same time, it was confirmed that there was no problem such as surface whitening caused by the change over time.
특히, 자동차 내장재 중 고 내열성을 요하는 IP 판넬의 경우 비교예 1～4에 따른 제품은 내열성 평가시 광발생등의 문제로 적용에의 어려움이 있으나, 본 발명의 실시예에 따른 제품은 실리콘 고무의 내열성 보강 효과로 완제품 상태에서 보다 안정적인 내열성을 확보 함으로써 보다 높은 내열성 등의 물성을 요하는 자동차 내장재 부분에의 적용이 가능하다. 나아가, 자동차 내장재 뿐만 아니라 안정적인 난연성, 내광성을 요하는 가구용 등의 다양한 형태의 인공피혁의 제조시에도 활용될 수 있을 것으로 판단된다.Particularly, in the case of IP panel requiring high heat resistance among automotive interior materials, the products according to Comparative Examples 1 to 4 have difficulty in application due to problems such as light generation when evaluating heat resistance, but the product according to the embodiment of the present invention is silicone rubber. It can be applied to the interior parts of automobiles that require higher heat resistance and physical properties by securing more stable heat resistance in the finished product state due to the heat resistance reinforcing effect. Furthermore, it is believed that the present invention can be used not only for automobile interior materials but also for manufacturing various types of artificial leather, such as furniture for stable flame retardancy and light resistance.
한편, 상기에서는 본 발명을 특정의 바람직한 실시예에 관련하여 도시하고 설명하였지만, 이하의 특허청구범위에 의해 마련되는 본 발명의 기술적 특징이나 분야를 이탈하지 않는 한도 내에서 본 발명이 다양하게 개조 및 변화될 수 있다는 것은 당업계에서 통상의 지식을 가진 자에게 명백한 것이다. On the other hand, while the present invention has been shown and described with respect to certain preferred embodiments, the invention is variously modified and modified without departing from the technical features or fields of the invention provided by the claims below It will be apparent to those skilled in the art that such changes can be made.
본 발명은 부직포 원단과 폴리우레탄 표면 코팅층 사이에 실리콘 코팅층을 가짐으로서, 기존 인공피혁 제품의 감성과 물성을 유지하면서 기존의 방법으로는 구현이 어려운 내열성과 보다 안정적인 내광성 및 난연성을 가지는 자동차 내장재용 폴리우레탄 인공피혁을 제공할 수 있다. The present invention has a silicone coating layer between the non-woven fabric and the polyurethane surface coating layer, while maintaining the sensitivity and physical properties of the existing artificial leather products, the poly for automotive interior material having heat resistance and more stable light resistance and flame retardance difficult to implement by conventional methods Urethane artificial leather can be provided.
도 1은 본 발명에 따라 부직포 원단; 실리콘 코팅층; 및 폴리우레탄 표면 코팅층;을 포함하는 자동차 내장재용 인공피혁에 대한 구조의 일례를 나타내는 단면도이고,1 is a non-woven fabric according to the present invention; Silicon coating layer; And a polyurethane surface coating layer; a cross-sectional view showing an example of a structure for artificial leather for automobile interior including,
도 2는 본 발명에 따라 부직포 원단; 실리콘 코팅층; 접착제층; 제1폴리우레탄 표면 코팅층; 및 제2 폴리우레탄 표면 코팅층;을 포함하는 자동차 내장재용 인공피혁에 대한 구조의 일례를 나타내는 단면도이다.2 is a nonwoven fabric according to the present invention; Silicon coating layer; Adhesive layer; A first polyurethane surface coating layer; And a second polyurethane surface coating layer; a cross-sectional view showing an example of the structure for artificial leather for automobile interior including a.
**도면의 주요부분에 대한 기호의 간단한 설명**** Simple explanation of symbols for main parts of drawing **
10 : 부직포 원단 20: 실리콘 코팅층10: nonwoven fabric 20: silicone coating layer
25 : 접착제층 30 : 폴리우레탄 표면 코팅층25
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| CN105200807A (en) * | 2014-07-06 | 2015-12-30 | 耿云花 | Basketball leather |
| WO2017012240A1 (en) * | 2015-07-22 | 2017-01-26 | 江苏国信复合材料科技股份有限公司 | Nanometer artificial leather and manufacturing method therefor |
| CN108729244A (en) * | 2018-07-13 | 2018-11-02 | 广东天跃新材料股份有限公司 | The silicon rubber synthetic leather and its manufacturing technology of outdoor furniture |
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| CN112844994A (en) * | 2020-12-31 | 2021-05-28 | 东莞市朗晟材料科技有限公司 | Temperature-resistant silica gel leather and preparation method thereof |
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